Co-reporter:Wei Xiong, Yiming Tang, Changyu Shao, Yueqi Zhao, Biao Jin, Tingting Huang, Ya’nan Miao, Lei Shu, Weimin Ma, Xurong Xu, and Ruikang Tang
Environmental Science & Technology November 7, 2017 Volume 51(Issue 21) pp:12717-12717
Publication Date(Web):September 26, 2017
DOI:10.1021/acs.est.7b02985
Cyanobacterial blooms represent a significant threat to global water resources because blooming cyanobacteria deplete oxygen and release cyanotoxins, which cause the mass death of aquatic organisms. In nature, a large biomass volume of cyanobacteria is a precondition for a bloom, and the cyanobacteria buoyancy is a key parameter for inducing the dense accumulation of cells on the water surface. Therefore, blooms will likely be curtailed if buoyancy is inhibited. Inspired by diatoms with naturally generated silica shells, we found that silica nanoparticles can be spontaneously incorporated onto cyanobacteria in the presence of poly(diallyldimethylammonium chloride), a cationic polyelectrolyte that can simulate biosilicification proteins. The resulting cyanobacteria-SiO2 complexes can remain sedimentary in water. This strategy significantly inhibited the photoautotrophic growth of the cyanobacteria and decreased their biomass accumulation, which could effectively suppress harmful bloom events. Consequently, several of the adverse consequences of cyanobacteria blooms in water bodies, including oxygen consumption and microcystin release, were significantly alleviated. Based on the above results, we propose that the silica nanoparticle treatment has the potential for use as an efficient strategy for preventing cyanobacteria blooms.
Co-reporter:Pengqiang Duan, Tingting Huang, Wei Xiong, Lei Shu, Yuling Yang, Changyu Shao, Xurong XuWeimin Ma, Ruikang Tang
Langmuir March 7, 2017 Volume 33(Issue 9) pp:
Publication Date(Web):February 15, 2017
DOI:10.1021/acs.langmuir.6b04421
Photosynthetic microalgae play an important role in solar-to-chemical energy conversion on Earth, but the increasing solar ultraviolet (UV) radiation seriously reduces the biological photosynthesis. Here, we developed a one-step approach to construct cell-in-shell hybrid structure by using direct adsorption of CeO2 nanoparticles onto cells. The engineered CeO2 nanoshell can efficiently protect the enclosed Chlorella cell due to its excellent UV filter property, which can also eliminate UV-induced oxidative stress. The experiments demonstrate that the resulted algae–CeO2 composites can guarantee their biological photosynthetic process and efficiency even under UV. This study follows a feasible strategy to protect living organisms by using functional nanomaterials to improve their biological functions.
Co-reporter:Wenge Jiang, Haihua Pan, Zhisen Zhang, S. Roger Qiu, J. Dongun Kim, Xurong Xu, and Ruikang Tang
Journal of the American Chemical Society June 28, 2017 Volume 139(Issue 25) pp:8562-8562
Publication Date(Web):June 7, 2017
DOI:10.1021/jacs.7b03116
We herein show the chiral recognition and separation of aspartic acid (Asp) enantiomers by achiral brushite due to the asymmetries of their dynamical steps in its nonequilibrium states. Growing brushite has a higher adsorption affinity to d-Asp, while l-Asp is predominant on the dissolving brushite surface. Microstructural characterization reveals that chiral selection is mainly attributed to brushite [101] steps, which exhibit two different configurations during crystal growth and dissolution, respectively, with each preferring a distinct enantiomer due to this asymmetry. Because these transition step configurations have different stabilities, they subsequently result in asymmetric adsorption. By varying free energy barriers through solution thermodynamic driving force (i.e., supersaturation), the dominant nonequilibrium intermediate states can be switched and chiral selection regulated. This finding highlights that the dynamic steps can be vital for chiral selection, which may provide a potential pathway for chirality generation through the dynamic nature.
Co-reporter:Hangyu Zhou;Dr. Guangchuan Wang;Dr. Xiaoyu Wang;Dr. Zhiyong Song;Dr. Ruikang Tang
Angewandte Chemie International Edition 2017 Volume 56(Issue 42) pp:12792-12792
Publication Date(Web):2017/10/09
DOI:10.1002/anie.201708378
Avian influenza viruses cause cross-species infections in humans, but little is known about how they jump from Aves to humans. In their Communication on page 12908 ff., R. Tang et al. suggest that the avian influenza virus in Aves is in a mineralized state with eggshell structures. The mineralized virus is more robust, with enhanced infectivity and thermostability. Furthermore, the mineral exterior of the virus can alter its cellular internalization, expanding the possible tropisms.
Co-reporter:Hangyu Zhou;Dr. Guangchuan Wang;Dr. Xiaoyu Wang;Dr. Zhiyong Song;Dr. Ruikang Tang
Angewandte Chemie 2017 Volume 129(Issue 42) pp:12968-12968
Publication Date(Web):2017/10/09
DOI:10.1002/ange.201708378
Vogelgrippe-Viren können auch Menschen infizieren, über den Übertragungsweg ist aber nur wenig bekannt. In der Zuschrift auf S. 13088 schlagen R. Tang et al. vor, dass die Viren in Vögeln in einem mineralisierten Zustand in Eierschalen-artigen Strukturen vorliegen. Die mineralisierten Viren sind robuster, infektiöser und temperaturbeständiger. Die mineralische Hülle um die Viren ändert außerdem ihr Zellaufnahmeverhalten und eröffnet ihnen dadurch neue Möglichkeiten.
Co-reporter:Xiaoyu Wang;Yong-Qiang Deng;Dong Yang;Yun Xiao;Hui Zhao;Qing-Gong Nian;Xurong Xu;Xiao-Feng Li;Cheng-Feng Qin
Chemical Science (2010-Present) 2017 vol. 8(Issue 12) pp:8240-8246
Publication Date(Web):2017/11/20
DOI:10.1039/C7SC03868B
Pre-existing antibodies can aggravate disease during subsequent infection or vaccination via the mechanism of antibody-dependent enhancement (ADE) of infection. Herein, using dengue virus (DENV) as a model, we present a versatile surface-camouflage strategy to obtain a virus core-calcium phosphate shell hybrid by self-templated biomineralization. The shelled DENV stealthily avoids recognition by pre-existing antibodies under extracellular conditions, resulting in the efficient abrogation of the ADE of infection both in vitro and in vivo. Moreover, the nanoshell can spontaneously degrade under intracellular conditions to restore the virus activity and immunogenicity due to its pH-sensitive behaviour. This work demonstrates that the biomimetic material shell can significantly improve the administration safety and potency of the DENV vaccine, which provides the promising prospect of chemically designed virus-material hybrids for immune evasion.
Co-reporter:Hangyu Zhou;Dr. Guangchuan Wang;Dr. Xiaoyu Wang;Dr. Zhiyong Song;Dr. Ruikang Tang
Angewandte Chemie 2017 Volume 129(Issue 42) pp:13088-13092
Publication Date(Web):2017/10/09
DOI:10.1002/ange.201705769
AbstractAlthough the circulation of avian influenza viruses in humans is limited, they can be transmitted from Aves (birds) to humans, representing a great challenge. Herein, we suggest that influenza viruses from Aves might exist in a mineralized state owing to the high calcium concentrations in the avian intestine. Using two typical influenza viruses as examples, we demonstrate that these viruses can self-mineralize in simulated avian intestinal fluid, resulting in egg-like virus–mineral structured composites. The mineralized viruses are more robust, with enhanced infectivity and thermostability. More importantly, the mineral exterior of mineralized viruses can alter their cell internalization, expanding the possible tropisms. The discovery of a mineralized state of influenza viruses highlights the integration of nanomaterials and viruses in the environment, which provides a new understanding of avian influenza infection and its control.
Co-reporter:Hangyu Zhou;Dr. Guangchuan Wang;Dr. Xiaoyu Wang;Dr. Zhiyong Song;Dr. Ruikang Tang
Angewandte Chemie International Edition 2017 Volume 56(Issue 42) pp:12908-12912
Publication Date(Web):2017/10/09
DOI:10.1002/anie.201705769
AbstractAlthough the circulation of avian influenza viruses in humans is limited, they can be transmitted from Aves (birds) to humans, representing a great challenge. Herein, we suggest that influenza viruses from Aves might exist in a mineralized state owing to the high calcium concentrations in the avian intestine. Using two typical influenza viruses as examples, we demonstrate that these viruses can self-mineralize in simulated avian intestinal fluid, resulting in egg-like virus–mineral structured composites. The mineralized viruses are more robust, with enhanced infectivity and thermostability. More importantly, the mineral exterior of mineralized viruses can alter their cell internalization, expanding the possible tropisms. The discovery of a mineralized state of influenza viruses highlights the integration of nanomaterials and viruses in the environment, which provides a new understanding of avian influenza infection and its control.
Co-reporter:Xiaoyu Wang;Caijun Sun;Pingchao Li;Tongjin Wu;Hangyu Zhou;Dong Yang;Yichu Liu;Xiuchang Ma;Zhiyong Song;Qinggong Nian;Liqiang Feng;Chengfeng Qin;Ling Chen
Advanced Materials 2016 Volume 28( Issue 4) pp:694-700
Publication Date(Web):
DOI:10.1002/adma.201503740
Co-reporter:Zhaoming Liu;Xurong Xu
Advanced Functional Materials 2016 Volume 26( Issue 12) pp:1862-1880
Publication Date(Web):
DOI:10.1002/adfm.201504480
Biomineralization brings inorganic materials into biological organisms and it plays an important role in natural evolution. Inspired by biomineralized eggs and diatoms with protective shell structures, scientists have artificially endowed organisms with functional materials. The resulting organism–material hybrids become more robust and even evolve new functions. This feature article reviews recent achievements of organism improvements by various material shells and related applications in cell protection, storage, thermal stability, biological stealth, photosynthesis and biocatalysis, etc. Different from the previous understanding of biomineralization, the regulation effects of materials on organism functions are highlighted in these biomineralization-inspired biological improvements, which present an artificial evolution strategy by using material techniques. We suggest that rationally designed organism–materials with optimized functions can shed light on solving global problems such as energy crisis and environmental pollution, as well as on improving medical treatment and intricate material designing. More generally, the studies of material-based organism improvement can combine biological and material sciences together for a closer integration.
Co-reporter:Guangchuan Wang, Hangyu Zhou, Qing-Gong Nian, Yuling Yang, Cheng-Feng Qin and Ruikang Tang
Chemical Science 2016 vol. 7(Issue 3) pp:1753-1759
Publication Date(Web):10 Dec 2015
DOI:10.1039/C5SC03847B
Exploring formulations that can improve the thermostability and immunogenicity of vaccines holds great promise in advancing the efficacy of vaccination to combat infectious diseases. Inspired by biomineralized core–shell structures in nature, we suggest a polyethyleneimine (PEI)–silica–PEI hybrid coated vaccine formulation to improve both thermostability and immunogenicity. Through electrostatic adsorption, in situ silicification and capping treatment, a hybrid coating of silica and PEI was assembled around a vaccine to produce vaccine@PEI–silica structures. Both in vitro and in vivo experiments demonstrated that the thermostability and immunogenicity of the modified vaccine were significantly improved. The modified vaccine could be used efficiently after long-term exposure at room temperature, which would facilitate vaccine transport and storage without a cold chain. Furthermore, mechanistic studies revealed that the PEI–silica–PEI coating acted as a physiochemical anchor as well as a mobility-restricting hydration layer to stabilize the enclosed vaccine. This achievement demonstrates a biomimetic surface-modification-based strategy to confer desired properties on biological products.
Co-reporter:Yuling Yang, Genxing Zhu, Guangchuan Wang, Yali Li and Ruikang Tang
Journal of Materials Chemistry A 2016 vol. 4(Issue 27) pp:4726-4731
Publication Date(Web):17 Jun 2016
DOI:10.1039/C6TB01355D
Biomolecules, especially enzymes, usually have poor thermal and operational stability as well as limited reuse cycles, which greatly limit their industrial practices. Inspired by the biomineralization strategy evolved by natural organisms, we suggest nanohybrid enzyme formulation by in situ encapsulating enzyme loaded functional Fe3O4@C nanoparticles with silica. By using glucose oxidase (GOD) as an example, we demonstrate that the obtained enzyme-material hybrids are featured by their significantly enhanced operational and thermal stabilities, which exhibit a relatively steady catalytic ability in a board range of 25 °C to 65 °C. Even after 4 h of incubation at 55 °C, the GOD-material composites still retain 77% of their initial activity while the native ones only retain 30%. Besides, the nanohybrids show excellent reusability because the magnetic character of the integrated Fe3O4 particles facilitates the enzyme separation and recycle. This attempt provides a valuable approach for biological improvement by using functional materials.
Co-reporter:Genxing Zhu, Ruibo Zhao, Yaling Li and Ruikang Tang
Journal of Materials Chemistry A 2016 vol. 4(Issue 22) pp:3903-3910
Publication Date(Web):28 Apr 2016
DOI:10.1039/C5TB02767E
Multifunctional Gd,Ce,Tb co-doped β-tricalcium phosphate (TCP) porous nanospheres are prepared by a facile solvothermal strategy with trimethyl phosphate as the phosphorus source. The as-prepared nanomaterial (average diameter of 100 nm) has a multiple level pore size distribution with the specific surface area of 124.33 m2 g−1, which benefits drug loading. Its photoluminescent and magnetic multifunctions are realized by the co-doping of Gd3+, Ce3+ and Tb3+ ions, which make the nanomaterial promising for both fluorescence and magnetic resonance imaging techniques. Furthermore, the nanomaterial exhibits excellent cytocompatibility and a relatively high doxorubicin loading capacity as well as sustained pH-sensitive drug release behaviour. It is suggested that the Gd,Ce,Tb co-doped β-TCP porous nanospheres are promising for applications in the biomedical fields such as multifunctional drug delivery systems and tissue engineering scaffolds with bioimaging guidance.
Co-reporter:Yong Yao, Yang Wang, Ruibo Zhao, Li Shao, Ruikang Tang and Feihe Huang
Journal of Materials Chemistry A 2016 vol. 4(Issue 15) pp:2691-2696
Publication Date(Web):17 Mar 2016
DOI:10.1039/C5TB02611C
In order to improve the effectiveness of cancer therapy and reduce the adverse effects of conventional chemotherapy, the development of less toxic, biocompatible, decomposable and pH-responsive nano-containers is of great importance. In this work a novel nano-container is designed and synthesized by doping a water-soluble pillar[5]arene WP5 onto hollow mesoporous silica nanoparticles (HMNPs) via host–guest complexation. This nano-container decomposes into small water-soluble fragments to achieve a highly efficient release of the loaded anticancer drug doxorubicin. Importantly, the complexation of WP5 molecules with HMNPs significantly improves the inhibition of tumor growth in vivo with minimal side effects, which can be attributed to the pH-responsiveness of the host–guest interactions. Under the extracelluar conditions, the host–guest complexation between WP5 and HMNPs enhances the loading of doxorubicin molecules. However, this host–guest complexation is prohibited under the low pH conditions in intracellular lysosomes, so that doxorubicin is released readily from the vector. The present novel drug delivery system demonstrates the great potential of host–guest complexation for cancer therapy improvement.
Co-reporter:Hangyu Zhou, Guangchuan Wang, Xiao-Feng Li, Yaling Li, Shun-Ya Zhu, Cheng-Feng Qin and Ruikang Tang
Chemical Communications 2016 vol. 52(Issue 38) pp:6447-6450
Publication Date(Web):11 Apr 2016
DOI:10.1039/C6CC02595A
Developing vaccine formulations with excellent thermostability and immunogenicity remains a great challenge. By in situ encapsulating a live-attenuated strain of human enterovirus 71 (EV71) in alumina, we obtained a robust vaccine formulation named EV71@NanoAlum, which features significantly enhanced thermostability and immunogenicity. This attempt follows a material-based tactic for vaccine improvement.
Co-reporter:Zhiyong Song, Long Liu, Xiaoyu Wang, Yongqiang Deng, Qinggong Nian, Guangchuan Wang, Shunya Zhu, Xiaofeng Li, Hangyu Zhou, Tao Jiang, Xurong Xu, Ruikang Tang and Chengfeng Qin
Chemical Communications 2016 vol. 52(Issue 9) pp:1879-1882
Publication Date(Web):09 Dec 2015
DOI:10.1039/C5CC09252C
Conventional therapeutic monoclonal antibodies (mAbs) are invalid for intracellular viruses but by using in situ biomineralization treatment, they can be successfully delivered into cells to inhibit intracellular viral replication. This achievement significantly expands the applications of mAbs and provides a new intracellular strategy to control viral infections.
Co-reporter:Cuilian Liu, Halei Zhai, Zhisen Zhang, Yaling Li, Xurong Xu, and Ruikang Tang
ACS Applied Materials & Interfaces 2016 Volume 8(Issue 44) pp:29997
Publication Date(Web):October 18, 2016
DOI:10.1021/acsami.6b10374
Hydroxyapatite (HAP) nanocrystallites in all types of bones are distinguished by their ultrathin characteristics, which are uniaxially oriented with fibrillar collagen to uniquely expose the (100) faces. We speculate that living organisms prefer the specific crystal morphology and orientation of HAP because of the interactions between cells and crystals at the mineral–cell interface. Here, bone-like platy HAP (p-HAP) and two different rod-like HAPs were synthesized to investigate the ultrathin mineral modulating effect on cell bioactivity and bone generation. Cell viability and osteogenic differentiation of mesenchymal stem cells (MSCs) were significantly promoted by the platy HAP with (100) faces compared to rod-like HAPs with (001) faces as the dominant crystal orientation, which indicated that MSCs can recognize the crystal face and prefer the (100) HAP faces. This face-specific preference is dependent on the selective adsorption of fibronectin (FN), a plasma protein that plays a central role in cell adhesion, on the HAP surface. This selective adsorption is further confirmed by molecule dynamics (MD) simulation. Our results demonstrate that it is an intelligent choice for cells to use ultrathin HAP with a large (100) face as a basic building block in the hierarchical structure of bone, which is crucial to the promotion of MSCs osteoinductions during bone formation.Keywords: biomineralization; crystallography; fibronectin; hydroxyapatite; mesenchymal stem cells
Co-reporter:Ruibo Zhao;Ben Wang;Xinyan Yang;Yun Xiao;Xiaoyu Wang;Changyu Shao;Dr. Ruikang Tang
Angewandte Chemie International Edition 2016 Volume 55( Issue 17) pp:5225-5229
Publication Date(Web):
DOI:10.1002/anie.201601364
Abstract
Herein, we propose a drug-free approach to cancer therapy that involves cancer cell targeting calcification (CCTC). Several types of cancer cells, such as HeLa cells, characterized by folate receptor (FR) overexpression, can selectively adsorb folate (FA) molecules and then concentrate Ca2+ locally to induce specific cell calcification. The resultant calcium mineral encapsulates the cancer cells, inducing their death, and in vivo assessments confirm that CCTC treatment can efficiently inhibit tumor growth and metastasis without damaging normal cells compared with conventional chemotherapy. Accordingly, CCTC remarkably improve the survival rate of tumor mice. Notably, both FA and calcium ions are essential ingredients in human metabolism, which means that CCTC is a successful drug-free method for tumor therapy. This achievement may further represent an alternative cancer therapy characterized by selective calcification-based substitution of sclerosis for tumor disease.
Co-reporter:Genxing Zhu, Shasha Yao, Halei Zhai, Zhaoming Liu, Yaling Li, Haihua Pan, and Ruikang Tang
Langmuir 2016 Volume 32(Issue 35) pp:8999-9004
Publication Date(Web):August 12, 2016
DOI:10.1021/acs.langmuir.6b01594
Aggregation-based crystal growth is distinct from the classical understanding of solution crystallization. In this study, we reveal that N-stearoyl-l-glutamic acid (C18-Glu, an amphiphile that mimics a biomineralization-relevant biomolecule) can switch calcite crystallization from a classical ion-by-ion growth to a non-classical particle-by-particle pathway, which combines the classical and non-classical crystallization in one system. This growth mechanism change is controlled by the concentration ratio of [C18-Glu]/[Ca2+] in solution. The high [C18-Glu]/[Ca2+] can stabilize precursor nanoparticles to provide building blocks for aggregation-based crystallization, in which the interaction between C18-Glu and the nanoprecursor phase rather than that of C18-Glu on calcite steps is highlighted. Our finding emphasizes the enrollment of organic additives on metastable nano building blocks, which provides an alternative understanding about organic control in inorganic crystallization.
Co-reporter:Yang Wang, Ruibo Zhao, Shibing Wang, Zhaoming Liu, Ruikang Tang
Biomaterials 2016 75() pp: 71-81
Publication Date(Web):January 2016
DOI:10.1016/j.biomaterials.2015.09.030
Co-reporter:Ruibo Zhao;Ben Wang;Xinyan Yang;Yun Xiao;Xiaoyu Wang;Changyu Shao;Dr. Ruikang Tang
Angewandte Chemie 2016 Volume 128( Issue 17) pp:5311-5315
Publication Date(Web):
DOI:10.1002/ange.201601364
Abstract
Herein, we propose a drug-free approach to cancer therapy that involves cancer cell targeting calcification (CCTC). Several types of cancer cells, such as HeLa cells, characterized by folate receptor (FR) overexpression, can selectively adsorb folate (FA) molecules and then concentrate Ca2+ locally to induce specific cell calcification. The resultant calcium mineral encapsulates the cancer cells, inducing their death, and in vivo assessments confirm that CCTC treatment can efficiently inhibit tumor growth and metastasis without damaging normal cells compared with conventional chemotherapy. Accordingly, CCTC remarkably improve the survival rate of tumor mice. Notably, both FA and calcium ions are essential ingredients in human metabolism, which means that CCTC is a successful drug-free method for tumor therapy. This achievement may further represent an alternative cancer therapy characterized by selective calcification-based substitution of sclerosis for tumor disease.
Co-reporter:Yuling Yang, Guangchuan Wang, Genxing Zhu, Xurong Xu, Haihua Pan and Ruikang Tang
Chemical Communications 2015 vol. 51(Issue 41) pp:8705-8707
Publication Date(Web):20 Apr 2015
DOI:10.1039/C5CC01420D
The hybrid nanoparticles of amorphous calcium phosphate (ACP)–catalase (CAT) developed by in situ biomineralization can create a stable semi-aqueous nanoscale environment for entrapped proteins against thermal denaturation. This finding indicates the importance of an amorphous mineral phase in the preservation of organic macromolecules.
Co-reporter:Zhaoming Liu, Yadong Hu, Hongqing Zhao, Yang Wang, Xurong Xu, Haihua Pan and Ruikang Tang
Physical Chemistry Chemical Physics 2015 vol. 17(Issue 15) pp:10080-10085
Publication Date(Web):2015/03/04
DOI:10.1039/C4CP04115A
Living organisms such as corals can carry out CO2 looping efficiently via biomineralization under ambient conditions. Inspired by this natural process, we establish a solution system of calcium acetate–ethanol–water (Ca(Ac)2–C2H5OH–H2O) for CO2 chemical looping at constant room temperature. The CO2 capture is achieved by its reaction with Ca(Ac)2 to form calcium carbonate (CaCO3) mineral and HAc in the binary solvent with a high C2H5OH content. However, an increase in the H2O content in the system triggers acetic acid (HAc)-induced CaCO3 dissolution to release CO2. The system can be recovered for CO2 capture readily by the replenishment of C2H5OH. This biomimetic mineralization-based CO2 capture/release is controlled by the ionization states of the electrolytes, and is precisely regulated in the C2H5OH–H2O binary solvent. Our attempt highlights the fundamental principle of solution chemistry in reaction control and provides a bioinspired strategy for CO2 capture/release with very low cost and easy availability.
Co-reporter:Genxing Zhu, Yadong Hu, Yuling Yang, Ruibo Zhao and Ruikang Tang
RSC Advances 2015 vol. 5(Issue 30) pp:23958-23964
Publication Date(Web):25 Feb 2015
DOI:10.1039/C5RA01606A
β-tricalcium phosphate (TCP) is an important biomedical material but the synthesis of β-TCP with uniform nanostructure still remains a challenge. We report that β-TCP porous nanospheres could be prepared feasibly by a solvothermal method, in which trimethyl phosphate was used as the organic phosphorus source. The as-prepared 120 nm nanospheres were assembled by 15–25 nm nano building blocks with a multilevel structure, resulting in multiple pore size distributions. As a result, they have excellent cytocompatibility, high drug loading and protein adsorption capacities, and sustained release behaviours. It follows that the uniform porous β-TCP nanospheres are more promising for applications in biomedical fields.
Co-reporter:Guangchuan Wang, Hong-Jiang Wang, Hangyu Zhou, Qing-Gong Nian, Zhiyong Song, Yong-Qiang Deng, Xiaoyu Wang, Shun-Ya Zhu, Xiao-Feng Li, Cheng-Feng Qin, and Ruikang Tang
ACS Nano 2015 Volume 9(Issue 1) pp:799
Publication Date(Web):January 9, 2015
DOI:10.1021/nn5063276
Heat-lability is a key roadblock that strangles the widespread applications of many biological products. In nature, archaeal and extremophilic organisms utilize amorphous silica as a protective biomineral and exhibit considerable thermal tolerance. Here we present a bioinspired approach to generate thermostable virus by introducing an artificial hydrated silica exterior on individual virion. Similar to thermophiles, silicified viruses can survive longer at high temperature than their wild-type relatives. Virus inactivation assays showed that silica hydration exterior of the modified virus effectively prolonged infectivity of viruses by ∼10-fold at room temperature, achieving a similar result as that obtained by storing native ones at 4 °C. Mechanistic studies indicate that amorphous silica nanoclusters stabilize the inner virion structure by forming a layer that restricts molecular mobility, acting as physiochemical nanoanchors. Notably, we further evaluate the potential application of this biomimetic strategy in stabilizing clinically approved vaccine, and the silicified polio vaccine that can retain 90% potency after the storage at room temperature for 35 days was generated by this biosilicification approach and validated with in vivo experiments. This approach not only biomimetically connects inorganic material and living virus but also provides an innovative resolution to improve the thermal stability of biological agents using nanomaterials.Keywords: biomimetic; hydrated silica; silicification; thermal stability; vaccine; virus;
Co-reporter:Ben Wang, Guangchuan Wang, Binjie Zhao, Jiajun Chen, Xueyun Zhang and Ruikang Tang
Chemical Science 2014 vol. 5(Issue 9) pp:3463-3468
Publication Date(Web):15 May 2014
DOI:10.1039/C4SC01120A
Blood type mismatching is a critical problem in blood transfusions and it occasionally leads to severe transfusion reactions and even patient death. Inspired by the adhesive proteins secreted by mussels, we suggest a catecholic chemistry-based strategy to shelter antigenic epitopes on red blood cells (RBCs) by using polydopamine (PDA), which can guard against coagulation reaction without other negative effects on the RBC structure, function and viability. Both in vitro and in vivo studies confirm that the PDA-engineered RBCs (PDA-RBCs) can be applied in blood transfusion practices. The systemic assessment using a murine model demonstrates that the modified RBCs have a perfect survival profile even with repeated transfusion and high transfusion rates up to around 60%. It follows that an appropriate biogenic-chemical modification can produce antigenically shielded universal RBCs and provide insight for cell transplantation by using cell surface engineering.
Co-reporter:Zhaoming Liu, Yun Xiao, Wei Chen, Yang Wang, Ben Wang, Guangchuan Wang, Xurong Xu and Ruikang Tang
Journal of Materials Chemistry A 2014 vol. 2(Issue 22) pp:3480-3489
Publication Date(Web):02 Apr 2014
DOI:10.1039/C4TB00056K
The application of nanotechnology for in medicine is developing rapidly, thereby increasing human exposure to nanomaterials and significantly so. A rising question is the biosecurity of nanoparticles (NPs). Although calcium phosphate (CaP) phase is biocompatible and biodegradable, many in vitro experiments have demonstrated that its NPs have significant cytotoxicity. This toxicity is due to that the released Ca2+ ions from the internalized CaP NPs within cells initiate apoptosis. Different from such an understanding, we reveal that the internalized CaP NPs actually result in lysosomal ruptures caused by the fast dissolution of CaP under acidic conditions. The suddenly released ions disturb the osmotic pressure balance across the lysosomal membranes destroying the lysosomes, and excessive lysosomal ruptures lead to cell necrosis. We find that the necrosis process can be regulated by intracellular environments. For examples, the lysosomal ruptures can be inhibited by increasing either cytoplasmic osmotic pressure or lysosomal pH (reduce the dissolution rates of CaP). These changes can significantly decrease the cytotoxicity of CaP NPs. It follows that lysosomal rupture prevention is important in the biomedical applications of CaP NPs. More generally, the study suggests that control of material degradation in lysosomes and cytoplasm osmotic pressure may improve the biosecurity of nanomaterials, which is of special importance to biomimetic nanomaterials.
Co-reporter:Yang Wang, Guangchuan Wang, Yun Xiao, Yuling Yang, and Ruikang Tang
ACS Applied Materials & Interfaces 2014 Volume 6(Issue 21) pp:19092
Publication Date(Web):October 10, 2014
DOI:10.1021/am505041a
Recent developments of nanotechnology encourage novel materials for facile separations and purifications of recombinant proteins, which are of great importance in disease diagnoses and treatments. We find that Fe3O4@NiSiO3 with yolk–shell nanostructure can be used to specifically purify histidine-tagged (His-tagged) proteins from mixtures of lysed cells with a recyclable process. Each individual nanoparticle composes by a mesoporous nickel silicate shell and a magnetic Fe3O4 core in the hollow inner, which is featured by its great loading efficiency and rapid response toward magnetic fields. The abundant Ni2+ cations on the shell provide docking sites for selective coordination of histidine and the reversible release is induced by excess imidazole solution. Because of the Fe3O4 cores, the separation, concentration, and recycling of the nanocomposites become feasible under the controls of magnets. These characteristics would be highly beneficial in nanoparticle-based biomedical applications for targeted-drug delivery and biosensors.Keywords: magnetic nanocomposites; protein separation; recyclability; yolk−shell
Co-reporter:Yan Chen, Wenjia Gu, Haihua Pan, Shuqin Jiang and Ruikang Tang
CrystEngComm 2014 vol. 16(Issue 10) pp:1864-1867
Publication Date(Web):24 Dec 2013
DOI:10.1039/C3CE42274G
The regulation of citrate on amorphous calcium phosphate (ACP)-mediated crystallization of hydroxyapatite (HAP) is revealed in this work. The surface associated citrate on ACP plays the key role in controlling the nucleation of HAP by inhibiting the reaction of surface nucleation, and the effect of embedded citrate inside ACP or citrate in solution is weak.
Co-reporter:Yaling Li, Cuilian Liu, Halei Zhai, Genxing Zhu, Haihua Pan, Xurong Xu and Ruikang Tang
RSC Advances 2014 vol. 4(Issue 48) pp:25398-25403
Publication Date(Web):30 May 2014
DOI:10.1039/C4RA02821J
A graphene oxide–hydroxyapatite hybrid is synthesized via in situ mineralization. The integrated HAP nanoplates share similar size, morphology and orientations with those of natural bones. With their excellent mechanical properties and biocompatibility, the composites offer potential applications in load-bearing bone repair, scaffold materials and as an alternative model for biomimetic research.
Co-reporter:Yang Wang;Yun Xiao; Ruikang Tang
Chemistry - A European Journal 2014 Volume 20( Issue 37) pp:11826-11834
Publication Date(Web):
DOI:10.1002/chem.201403480
Abstract
The monodispersed spindle-like polypyrrole hollow nanocapsules (PPy HNCs) as the multifunctional platforms for combining chemotherapy with photothermal therapy for cancer cells are reported. Whereas the hollow cavity of nanocapsules can be used to load the anticancer drug (i.e., doxorubicin) for chemotherapy, the PPy shells can convert NIR light into heat for photothermal therapy. The release of the drug from the spindle-like PPy HNCs is pH-sensitive and near-infrared (NIR) light-enhanced. More importantly, the spindle-like PPy HNCs can penetrate cells more rapidly and efficiently in comparison with the spherical PPy HNCs. Both in vitro and in vivo experiments demonstrated that the combination of DOX-loaded spindle-like PPy HNCs and NIR light provide a highly effective and feasible chemo-photothermal therapy cancer method with a synergistic effect. Owing to their high photothermal conversion efficiency, large hollow cavity, and good biocompatibility, the spindle-like PPy HNCs could be used as a promising new cancer drug-nanocarrier and photothermal agent for localized tumorous chemo-photothermal therapy.
Co-reporter:Wei Chen;Guangchuan Wang
Nano Research 2014 Volume 7( Issue 10) pp:1404-1428
Publication Date(Web):2014 October
DOI:10.1007/s12274-014-0509-9
In nature, a few living organisms such as diatoms, magnetotactic bacteria, and eggs have developed specific mineral structures, which can provide extensive protection or unique functions. However, most organisms do not have such structured materials due to their lack of biomineralization ability. The artificial introduction of biomimetic-constructed nanominerals is challenging but holds great promise. In this overview, we highlight two typical types of mineral-living complex systems. One involves biological surface-induced nanomaterials, which produces artificial living-mineral core-shell structures such as the mineralencapsulated yeast, cyanobacteria, bacteria and viruses. The other involves internal nanominerals that could endow organisms with unique structures and properties. The applications of these biomimetic generated nanominerals are further discussed, mainly in four potential areas: storage, protection, “stealth” and delivery. Since biomineralization combines chemical, nano and biological technologies, we suggest that nanobiomimetic mineralization may open up another window for interdisciplinary research. Specifically, this is a novel material-based biological regulation strategy and the integration of living organisms with functional nanomaterials can create “super” or intelligent nanoscale living complexes for biotechnological practices.
Co-reporter:Halei Zhai, Yan Quan, Li Li, Xiang-Yang Liu, Xurong Xu and Ruikang Tang
Nanoscale 2013 vol. 5(Issue 7) pp:3006-3012
Publication Date(Web):06 Feb 2013
DOI:10.1039/C3NR33782K
Most spiral coiled biomaterials in nature, such as gastropod shells, are homochiral, and the favoured chiral feature can be precisely inherited. This inspired us that selected material structures, including chirality, could be specifically replicated into the self-similar populations; however, a physicochemical understanding of the material-based heritage is unknown. We study the homochirality by using calcium phosphate mineralization in the presence of racemic amphiphilic molecules and biological protein. The organic–inorganic hybrid materials with spiral coiling characteristics are produced at the nanoscale. The resulted helixes are chiral with the left- and right-handed characteristics, which are agglomerated hierarchically to from clusters and networks. It is interesting that each cluster or network is homochiral so that the enantiomorphs can be separated readily. Actually, each homochiral architecture is evolved from an original chiral helix, demonstrating the heritage of the matrix chirality during the material proliferation under a racemic condition. By using the Ginzburg–Landaue expression we find that the chiral recognition in the organic–inorganic hybrid formation may be determined by a spontaneous chiral separation and immobilization of asymmetric amphiphilic molecules on the mineral surface, which transferred the structural information from the mother matrix to the descendants by an energetic control. This study shows how biomolecules guide the selective amplification of chiral materials via spontaneous self-replication. Such a strategy can be applied generally in the design and production of artificial materials with self-similar structure characteristics.
Co-reporter:Wei Chen, Yun Xiao, Xueyao Liu, Yanhong Chen, Jiaojiao Zhang, Xurong Xu and Ruikang Tang
Chemical Communications 2013 vol. 49(Issue 43) pp:4932-4934
Publication Date(Web):10 Apr 2013
DOI:10.1039/C3CC41872C
Nano-solidified intermedias (NSI) of cisplatin were prepared via biomineralization and applied to reverse the drug resistance of cancers in vitro and in vivo by an alternative internalization pathway.
Co-reporter:Wei Xiong, Zhou Yang, Hailei Zhai, Guangchuan Wang, Xurong Xu, Weimin Ma and Ruikang Tang
Chemical Communications 2013 vol. 49(Issue 68) pp:7525-7527
Publication Date(Web):26 Jun 2013
DOI:10.1039/C3CC42766H
Bioinspired by diatoms, biomimetic silicification confers an artificial shell on cyanobacteria to alleviate photoinhibition; thus, the photosynthesis of the resulting cyanobacteria@SiO2 becomes more efficient under high light conditions.
Co-reporter:Shuqin Jiang, Yan Chen, Haihua Pan, Yin-Jia Zhang and Ruikang Tang
Physical Chemistry Chemical Physics 2013 vol. 15(Issue 30) pp:12530-12533
Publication Date(Web):04 Jun 2013
DOI:10.1039/C3CP51466H
Faster nucleation of hydroxyapatite (HAP) at lower pH (with lower supersaturation) contradicts classical understanding. We find that the residue calcium ion in the mother liquor is the key to trigger ACP phase transformation, which gives an understanding of nonclassical nucleation kinetics of ACP-mediated crystallization and sheds light on biomineralization.
Co-reporter:Jianming Wang, Yi Chen, Li Li, Jian Sun, Xinhua Gu, Xurong Xu, Haihua Pan and Ruikang Tang
CrystEngComm 2013 vol. 15(Issue 31) pp:6151-6158
Publication Date(Web):22 Apr 2013
DOI:10.1039/C3CE40449H
Biomineralization of collagenous mineralized tissues (CMT), in vivo, stands as a precisely cell-controlled process. An organic insoluble collagenous matrix forms, then inorganic mineral is deposited on the matrix. The exact mechanism of action remains elusive and most researchers agree the amorphous mineral phase is crucial in CMT's development. Artificial demineralized dentin can be remineralized via amorphous calcium phosphate (ACP) precursor stage stabilized by 500 μg ml−1 polyacrylic acid (PAA). This remineralization is a step-by-step progression. ACP initially forms in the collagen matrix at its base, transforms into hydroxyapatite, and migrates towards the surface. The state of ACP, which is labile in liquid environments, can be controlled by PAA in a dose-dependent manner. Thus, the concentration of PAA is a key parameter influencing dentin remineralization. Low concentration of PAA (100 μg ml−1) fails to maintain liquidity of ACP, resulting in superficial remineralization. Conversely, high concentration of PAA (1000 μg ml−1) retards phase transformation of ACP and, thereby, inhibits remineralization. The purpose of this study is to demonstrate the balance between meta-stability and crystallization of ACP precursor phase. Our findings also provide evidence for the role of ACP during biomineralization and reveal a possible approach to repair CMT.
Co-reporter:Yang Wang, Yun Xiao, Hangyu Zhou, Wei Chen and Ruikang Tang
RSC Advances 2013 vol. 3(Issue 45) pp:23133-23138
Publication Date(Web):26 Sep 2013
DOI:10.1039/C3RA43441A
A novel versatile system combining chemotherapy and photothermal therapy for cancer cells using CuS NCs is reported. CuS NCs were synthesized by a solid–liquid reaction between Cu2O nanocubes and thiourea. While the hollow nanocage can be used to load anticancer drugs for chemotherapy, the CuS can convert NIR light into heat for photothermal therapy. More importantly, CuS NCs display exceptionally high drug loading capacity of DOX with 500 wt% and release of DOX is pH-controllable, which is a spontaneous process under intracellular conditions. Compared with chemotherapy or photothermal therapy alone, the combination of chemotherapy and phototherapy can significantly improve the therapeutic efficacy. This improvement strategy using multifunctional nanomaterials may be particularly useful in biomedical applications.
Co-reporter:Guangchuan Wang;Rong Chen;Rui-Yuan Cao;Yong-Qiang Deng;Xurong Xu;Tao Jiang;Xiaoyu Wang;Shun-Ya Zhu;Ke Lyu;Lijuan Mo;Cheng-Feng Qin;E-De Qin;Jian-Feng Han
PNAS 2013 Volume 110 (Issue 19 ) pp:7619-7624
Publication Date(Web):2013-05-07
DOI:10.1073/pnas.1300233110
The development of vaccines against infectious diseases represents one of the most important contributions to medical science.
However, vaccine-preventable diseases still cause millions of deaths each year due to the thermal instability and poor efficacy
of vaccines. Using the human enterovirus type 71 vaccine strain as a model, we suggest a combined, rational design approach
to improve the thermostability and immunogenicity of live vaccines by self-biomineralization. The biomimetic nucleating peptides
are rationally integrated onto the capsid of enterovirus type 71 by reverse genetics so that calcium phosphate mineralization
can be biologically induced onto vaccine surfaces under physiological conditions, generating a mineral exterior. This engineered
self-biomineralized virus was characterized in detail for its unique structural, virological, and chemical properties. Analogous
to many exteriors, the mineral coating confers some new properties on enclosed vaccines. The self-biomineralized vaccine can
be stored at 26 °C for more than 9 d and at 37 °C for approximately 1 wk. Both in vitro and in vivo experiments demonstrate
that this engineered vaccine can be used efficiently after heat treatment or ambient temperature storage, which reduces the
dependence on a cold chain. Such a combination of genetic technology and biomineralization provides an economic solution for
current vaccination programs, especially in developing countries that lack expensive refrigeration infrastructures.
Co-reporter:Xiaoyu Wang;Yongqiang Deng;Shihua Li;Guangchuan Wang;Ede Qin;Xurong Xu;Chengfeng Qin
Advanced Healthcare Materials 2012 Volume 1( Issue 4) pp:443-449
Publication Date(Web):
DOI:10.1002/adhm.201200034
Co-reporter:Xiaoyu Wang;Yongqiang Deng;Shihua Li;Guangchuan Wang;Ede Qin;Xurong Xu;Chengfeng Qin
Advanced Healthcare Materials 2012 Volume 1( Issue 4) pp:
Publication Date(Web):
DOI:10.1002/adhm.201290019
Co-reporter:Yan Quan, Halei Zhai, Zhisen Zhang, Xurong Xu and Ruikang Tang
CrystEngComm 2012 vol. 14(Issue 21) pp:7184-7188
Publication Date(Web):06 Jul 2012
DOI:10.1039/C2CE25805F
The fabrication of organic–inorganic composites with well-defined lamellar internal structure is of great interest in current materials society. Inspired by the biomineralization of nacre, we found that an organic–inorganic lamellar hybrid can be achieved spontaneously and readily using classical screw growth, which is well-described by Burton–Cabrera–Frank (BCF) theory for solution crystal growth. Herein, we demonstrate that a combination of calcium phosphate and sodium bis(2-ethylhexyl) sulfosuccinate in the presence of bovine serum albumin leads to hybrid crystals with nacre-like structure via the conventional crystallization strategy. Accordingly, solution techniques for crystallization regulation can be used readily to control product habits. This study demonstrates how the BCF mechanism is of relevance in biomimetic composition generation. Such a biomimetic approach may aid in creating novel organic–inorganic composites through classical pathways.
Co-reporter:Guangchuan Wang;Xiaofeng Li;Lijuan Mo;Zhiyong Song;Wei Chen;Yongqiang Deng;Hui Zhao;Ede Qin;Dr. Chengfeng Qin;Dr. Ruikang Tang
Angewandte Chemie International Edition 2012 Volume 51( Issue 42) pp:10576-10579
Publication Date(Web):
DOI:10.1002/anie.201206154
Co-reporter:Li Li;Caiyun Mao;Jianming Wang;Xurong Xu;Haihua Pan;Yan Deng;Xinhua Gu
Advanced Materials 2011 Volume 23( Issue 40) pp:4695-4701
Publication Date(Web):
DOI:10.1002/adma.201102773
Co-reporter:Jia Wu;ZhiShen Zhang;XinWei Yu;HaiHua Pan;WenGe Jiang
Science Bulletin 2011 Volume 56( Issue 7) pp:633-639
Publication Date(Web):2011 March
DOI:10.1007/s11434-010-4314-x
The formation of dipeptides from amino acids can be driven by hydroxyapatite at a relatively low temperature in air. For example, the formation of (Ala)2 from Ala is induced on hydroxyapatite at 110°C with considerable yield. Typically, condensing agents, high temperatures (>250°C) or high pressures (>25 MPa) are required to drive the condensation of amino acids. Similar effects are observed in the condensation of Gly, Glu and Asp. Experiments demonstrate that hydroxyapatite is an effective inorganic catalytic agent, reducing the activation barrier for the formation of dipeptides by more than 50%. HAP promotes condensation by adsorbing amino acid monomers in an organized manner, which decreases the distance between amino and carboxyl groups on neighboring molecules and extends the contact time of the reaction groups. This work provides a chemical understanding of the primitive condensation of amino acids and reveals a mechanism for enhancement of mineral catalysts. It is important that the conditions used for hydroxyapatite-assisted dipeptide formation are not harsh and can be readily achieved, revealing a possible mechanism for the chemical evolution of biomolecules over geologic ages.
Co-reporter:Xiaobin Chu, Wenge Jiang, Zhisen Zhang, Yang Yan, Haihua Pan, Xurong Xu, and Ruikang Tang
The Journal of Physical Chemistry B 2011 Volume 115(Issue 5) pp:1151-1157
Publication Date(Web):December 29, 2010
DOI:10.1021/jp106863q
Although phase transformation is suggested as a key step in biomineralization, the chemical scenario about how organic molecules mediate inorganic phase transformations is still unclear. The inhibitory effect of amino acids on hydroxyapatite (HAP, the main inorganic component of biological hard tissues such as bone and enamel) formation was concluded by the previous biomimetic modeling based upon direct solution crystallization. Here we demonstrate that acidic amino acids, Asp and Glu, could promote HAP crystallization from its precursor crystal, brushite (DCPD). However, such a promotion effect could not be observed when the nonacidic amino acids were applied in the transformation-based HAP formation. We found that the specific modification of acidic amino acid on crystal−solution interfaces played a key role in the phase transition. The distinct properties between DCPD and HAP in the solution resulted in an interfacial energy barrier to suppress the spontaneous formation of HAP phase on DCPD phase. Different from the other amino acids, the carboxylate-rich amino acids, Asp and Glu, could modify the interfacial characteristics of these two calcium phosphate crystals to make them similar to each other. The experiments confirmed that the involvement of Asp or Glu reduced the interfacial energy barrier between DCPD and HAP, leading to a trigger effect on the phase transformation. An in-depth understanding about the unique roles of acidic amino acids may contribute to understanding phase transformation controls druing biomineralization.
Co-reporter:Halei Zhai;Wenge Jiang;Jinhui Tao;Siyi Lin;Xiaobin Chu;Xurong Xu
Advanced Materials 2010 Volume 22( Issue 33) pp:3729-3734
Publication Date(Web):
DOI:10.1002/adma.201000941
Co-reporter:Halei Zhai, Xiaobin Chu, Li Li, Xurong Xu and Ruikang Tang
Nanoscale 2010 vol. 2(Issue 11) pp:2456-2462
Publication Date(Web):13 Oct 2010
DOI:10.1039/C0NR00542H
An understanding of controlled formation of biomimetic mesocrystals is of great importance in materials chemistry and engineering. Here we report that organic–inorganic hybrid plates and even mesocrystals can be conveniently synthesized using a one-pot reaction in a mixed system of protein (bovine serum albumin (BSA)), surfactant (sodium bis(2-ethylhexyl) sulfosuccinate (AOT)) and supersaturated calcium phosphate solution. The morphologies of calcium-phosphate-based products are analogous to the general inorganic crystals but they have abnormal and interesting substructures. The hybrids are constructed by the alternate stacking of organic layer (thickness of 1.31 nm) and well-crystallized inorganic mineral layer (thickness of 2.13 nm) at the nanoscale. Their morphologies (spindle, rhomboid and round) and sizes (200 nm–2 μm) can be tuned gradually by changing BSA, AOT and calcium phosphate concentrations. This modulation effect can be explained by a competition between the anisotropic and isotropic assembly of the ultrathin plate-like units. The anisotropic assembly confers mesocrystal characteristics on the hybrids while the round ones are the results of isotropic assembly. However, the basic lamellar organic–inorganic substructure remains unchanged during the hybrid formation, which is a key factor to ensure the self-assembly from molecule to micrometre scale. A morphological ternary diagram of BSA–AOT–calcium phosphate is used to describe this controlled formation process, providing a feasible strategy to prepare the required materials. This study highlights the cooperative effect of macromolecule (frame structure), small biomolecule (binding sites) and mineral phase (main component) on the generation and regulation of biomimetic hybrid mesocrystals.
Co-reporter:Jinhui Tao, Haihua Pan, Halei Zhai, Jieru Wang, Li Li, Jia Wu, Wenge Jiang, Xurong Xu and Ruikang Tang
Crystal Growth & Design 2009 Volume 9(Issue 7) pp:3154
Publication Date(Web):May 12, 2009
DOI:10.1021/cg801130w
Different from the conventional solution precipitation, amorphous precursor involves widely in biomineralizations. It is believed that the development of crystalline structures with a well-defined shape in biological systems is essentially facilitated by the occurrence of these transient amorphous phases. However, the previous studies have not elucidated the physicochemical factors influencing the transformation from the transient phase into the stable phase. In this study, the evolutions from the amorphous calcium phosphate to the different-shaped (hexagon and octahedron; octahedron is an unexpected morphology of the crystal with space group of R3̅c) single crystals of β-tricalcium phosphate (β-TCP) were examined. The hexagonal β-TCP crystals were formed via the phase transformation of amorphous precursor in CaCl2−Na2HPO4-ethylene glycol solution; however, the octahedral β-TCP crystals were formed in Ca(OH)2-(NH4)2HPO4-ethylene glycol solution. Because the interfacial energies between amorphous phase and crystals were much smaller than those between solutions and crystals, the crystallization of the β-TCP phase occurred directly in the amorphous substrate rather than from the solution. It was interesting that the final morphology of product was also determined by the interfacial energy between the transformed crystal and solution. The current work demonstrated that the amorphous precursor epitaxial nucleation process and morphology selection of crystals in the amorphous phase could also be understood by an interfacial energy control. This result might provide an in-depth understanding of the biomimetic synthesis of crystals via a pathway of amorphous precursors.
Co-reporter:Rui Liu, Xurong Xu, Yurong Cai, Anhua Cai, Haihua Pan, Ruikang Tang and Kilwon Cho
Crystal Growth & Design 2009 Volume 9(Issue 7) pp:3095
Publication Date(Web):May 15, 2009
DOI:10.1021/cg800872j
Abalone shell is natural inorganic/organic hybrid material, which is biologically constructed by using two calcium carbonates, aragonite and calcite. Aragonite can provide an enhanced mechanical support for the shell, and the stable phase, calcite, acts as the outer layer. In the current study, large-area aragonite film is deposited onto a calcite film in the presence of magnesium ion to biomimetically construct an aragonite−calcite complex structure. A calcite film is fabricated on a silicon wafer by a controlled phase transformation of amorphous calcium carbonate film at 120 °C, which is used as a substrate to induce the deposition of the aragonite layer with the addition of magnesium ion. We demonstrated the importance of the transition process from calcite to aragonite during the formation of the aragonite−calcite complex layer. This study could be used to mimic a sharp transition process of calcite to aragonite in vitro without any organic macromolecules.
Co-reporter:Wenge Jiang, Xiaobin Chu, Ben Wang, Haihua Pan, Xurong Xu and Ruikang Tang
The Journal of Physical Chemistry B 2009 Volume 113(Issue 31) pp:10838-10844
Publication Date(Web):July 10, 2009
DOI:10.1021/jp904633f
Phase transformation is an important strategy in biomineralization. However, the role of biomolecules in the mineral transition is poorly understood despite the fact that the biomineralization society greatly highlights the organic controls in the formation of the inorganic phase. Here, we report an induced biomimetic phase transformation from brushite (a widely used calcium phosphate precursor in biological cement) to hydroxyapatite (main inorganic composition of skeletal mineral) by citrate (a rich organic component in bone tissue). The transformation in the absence of the organic additive cannot be spontaneously initiated in an aqueous solution with a pH of 8.45 (no phase transition is detected in 4 days), which is explained by a high interfacial energy barrier between brushite−solution and hydroxyapatite−solution interfaces. Citrate can oppositely regulate these two interfaces, which decreases and increases the stabilities of brushite and hydroxyapatite surfaces in the solution, respectively. Thus, the interfacial energy barrier can be greatly reduced in the presence of citrate and the reaction is triggered; e.g., at 1 mM citrate, the total transformation from brushite to hydroxyapatite can be completed within 3 days. The relationship between the transition kinetics and citrate concentration is also studied. The work reveals how the organic components direct solid−solid phase transformation, which can be understood by an energetic control of the interfacial barrier. It is emphasized that the terms of interfacial energy must be taken into account in the studies of phase transformation. We suggest that this biomimetic approach may provide an in-depth understanding of biomineralization.
Co-reporter:Jinhui Tao;Dongming Zhou;Zhisen Zhang;Xurong Xu
PNAS 2009 Volume 106 (Issue 52 ) pp:22096-22101
Publication Date(Web):2009-12-29
DOI:10.1073/pnas.0909040106
Many animals such as crustacean periodically undergo cyclic molt of the exoskeleton. During this process, amorphous calcium
mineral phases are biologically stabilized by magnesium and are reserved for the subsequent rapid formation of new shell tissue.
However, it is a mystery how living organisms can regulate the transition of the precursor phases precisely. We reveal that
the shell mineralization from the magnesium stabilized precursors is associated with the presence of Asp-rich proteins. It
is suggested that a cooperative effect of magnesium and Asp-rich compound can result into a crystallization switch in biomineralization.
Our in vitro experiments confirm that magnesium increases the lifetime of amorphous calcium carbonate and calcium phosphate
in solution so that the crystallization can be temporarily switched off. Although Asp monomer alone inhibits the crystallization
of pure amorphous calcium minerals, it actually reduces the stability of the magnesium-stabilized precursors to switch on
the transformation from the amorphous to crystallized phases. These modification effects on crystallization kinetics can be
understood by an Asp-enhanced magnesium desolvation model. The interesting magnesium-Asp-based switch is a biologically inspired
lesson from nature, which can be developed into an advanced strategy to control material fabrications.
Co-reporter:Ling Li, Jinhui Tao, Haihua Pan, Hanmin Chen, Xiaowei Wu, Feijian Zhu, Xurong Xu and Ruikang Tang
Journal of Materials Chemistry A 2008 vol. 18(Issue 44) pp:5363-5367
Publication Date(Web):14 Oct 2008
DOI:10.1039/B811552D
Generally, two or more phosphors are mixed to achieve multiplex colour in the fluorescence industry. However, such a simple mixture of fluorescent materials usually leads to colour discrepancy and may even affect the colour uniformity due to the distinct physicochemical properties of the different components. Fabrication of a core–shell structure is a novel strategy to prepare colour-tuned fluorescent materials. Here we report a core–shell structure made up from two phosphors, Y2O3:Eu and LnPO4, which can emit red and green light respectively. It is important to control the homogeneous and relatively low supersaturation of LnPO4 (Ln = La, Ce, and Tb) in the solution so that the precipitates of LnPO4 can deposit onto the Y2O3:Eu particles uniformly. This could result in an LnPO4 shell around the Y2O3:Eu core to form micron-sized complex particles. In the preparation of the core–shell structure, the slow hydrolysis of tripolyphosphate to release free phosphate ions is a key factor. It is well known that dissociation of tripolyphosphate is temperature sensitive so that this reaction can be controlled by heating the solution. Under UV excitation, both the core (Y2O3:Eu) and the newly formed shell (LnPO4) can emit their characteristic light; it is interesting that each individual core–shell complex can provide the multiplex colour homogeneously at the micron scale. By adjusting the proportion of core and shell in the complex, the fluorescence colours of the micron-sized phosphor can be tuned conveniently.
Co-reporter:Li Li, Haihua Pan, Jinhui Tao, Xurong Xu, Caiyun Mao, Xinhua Gu and Ruikang Tang
Journal of Materials Chemistry A 2008 vol. 18(Issue 34) pp:4079-4084
Publication Date(Web):18 Jul 2008
DOI:10.1039/B806090H
The application of calcium phosphates and their nanoparticles have been received great attention. However, hydroxyapatite (HAP) is not suggested in dental therapy to repair the damaged enamel directly although this compound has a similar chemical composition to enamel. We note that the size-effects of HAP are not taken into account in the previous studies as these artificial particles frequently have sizes of hundreds of nanometres. It has recently been revealed that the basic building blocks of enamel are 20–40 nm HAP nanoparticles. We suggest that the repair effect of HAP can be greatly improved if its dimensions can be reduced to the scale of the natural building blocks. Compared with conventional HAP and nano amorphous calcium phosphate (ACP), our in vitro experimental results demonstrate the advantages of 20 nm HAP in enamel repairs. The results of scanning electron microscopy, confocal laser scanning microscopy, quantitative measurement of the adsorption, dissolution kinetics, and nanoindentation, show the strong affinity, excellent biocompatibility, mechanical improvement, and the enhancement of erosion-free by using 20 nm particles as the repairing agent. However, these excellent in vitro repair effects cannot be observed when conventional HAP and ACP are applied. Clearly, nano HAP with a size of 20 nm shares similar characteristics to the natural building blocks of enamel so that it may be used as an effective repair material and anticaries agent. Our current study highlights the analogues of nano building blocks of biominerals during biomedical applications, which provide a novel pathway for biomimetic repair.
Co-reporter:Yurong Cai and Ruikang Tang
Journal of Materials Chemistry A 2008 vol. 18(Issue 32) pp:3775-3787
Publication Date(Web):27 Jun 2008
DOI:10.1039/B805407J
Recent developments in biomineralization and biomaterials have demonstrated that nano-calcium phosphate particles play an important role in the formation of hard tissues in nature. It is suggested that the basic inorganic building blocks of bone and enamel are nanosized apatite although their hierarchical structures differ. Nanoparticles can confer on biominerals remarkable physical and chemical characteristics such as enhanced mechanical strength and self-preservation in biological fluids. In living organisms, tens to hundreds of nano-blocks, under the control of an organic matrix, combine into self-assembled biominerals. It is also confirmed experimentally that enamel- or bone-like apatite can be achieved by oriented aggregation by using nano-calcium phosphates as the raw materials, determined by the biomolecules. Interestingly, features of smaller hydroxyapatite (HAP) nanoparticles may more closely approximate features of HAP during biomineralization than features of the larger HAP particles that are conventionally used. The application and prospective use of nano-calcium phosphate in the biological repair of bone and enamel are also introduced. It is emphasized that the cell experiments reveal improved cytophilicity of nanophase calcium phosphate minerals. Greater cell viability and proliferation of bone marrow mesenchymal stem cells are measured on smaller calcium phosphates. Furthermore, studies of amorphous calcium phosphate and crystallized HAP particles are used to investigate the effect of crystallinity of nanoparticles on living cells, and show that the differentiation of stem cells is promoted significantly by nano-HAP. It is suggested that nano-HAP may be the ideal biomaterial due to its good biocompatibility and bone/enamel integration. Lots of studies of calcium phosphates are expected in the nano-zone such as for drug delivery systems and resorbable scaffolds. In this feature article, a new view on calcium phosphates highlights the importance of size and phase controls in the application of biomedical materials.
Co-reporter:Jinhui Tao, Wenge Jiang, Halei Zhai, Haihua Pan, Xurong Xu and Ruikang Tang
Crystal Growth & Design 2008 Volume 8(Issue 7) pp:2227
Publication Date(Web):June 5, 2008
DOI:10.1021/cg700808h
Large-scale β-tricalcium phosphate (β-TCP) hexagonal single crystals were synthesized at a relatively low temperature (150 °C) by using a solution-phase method. The solvent, ethylene glycol, played an important role during the formation of the homogeneous submicron-sized crystals. Unlike the conventional understanding of a single crystal, the wall of the formed β-TCP hexagonal was well crystallized, showing different physicochemical properties from the bulk part. The dissolution spots were anisotropically distributed throughout the single crystal. The bulk part dissolved readily from the top and bottom planes in the undersaturated solutions, but the thin hexagonal wall could be stable against any dissolution even in pure water. These differences between the wall and the bulk part were attributed to the different crystallinities and defect densities in their structures. It was suggested that the low defect number might stem from the solvent−interface exchange that was allowed the edge surfaces in contact with the solution. And the rapid growth of the particles resulted in the randomly distributed defects in the bulk part, which induced a selective dissolution along the c-axis of β-TCP. Furthermore, the stability of wall could be explained by a size effect during the nanodemineralization. It was interesting that both the wall and the bulk part shared the exact same lattice fringes under the transmission electron microscope. This phenomenon implied that both components were crystallographically identical so that they were constructed into an integral single crystal of β-TCP. The distinct dissolution behaviors of these two parts in one single crystal resulted in the formation of porous, gearlike, and ringlike single crystals at different demineralization stages, which demonstrated an easy control of crystal morphology patterns by using the anisotropic dissolution behavior.
Co-reporter:Wenge Jiang, Haihua Pan, Yurong Cai, Jinhui Tao, Peng Liu, Xurong Xu and Ruikang Tang
Langmuir 2008 Volume 24(Issue 21) pp:12446-12451
Publication Date(Web):September 30, 2008
DOI:10.1021/la801720w
An approach to organic−inorganic interfacial structure at the atomic level is a great challenge in the studies of biomineralization. We demonstrate that atomic force microscopy (AFM) is powerful tool to discover the biomineral interface in detail. By using a model system of (100) hydroxyapatite (HAP) face and citrate, it reveals experimentally that only a side carboxylate and a surface calcium ion are involved in the binding effect during the citrate adsorption, which is against the previous understandings by using Langmuir adsorption and computer simulation. Furthermore, the adsorbed citrate molecules can use their free carboxylate and hydroxyl groups to be self-assembled on the HAP surface. AFM examination also finds that the presence of citrate molecules on the HAP crystal faces can enhance the adhesion force of the HAP surface. We suggest that the established AFM method can be used for a precise and direct understanding of biointerfaces at the atomic level.
Co-reporter:Haihua Pan, Jinhui Tao, Xinwei Yu, Lei Fu, Jiali Zhang, Xiangxuan Zeng, Guohua Xu and Ruikang Tang
The Journal of Physical Chemistry B 2008 Volume 112(Issue 24) pp:7162-7165
Publication Date(Web):May 27, 2008
DOI:10.1021/jp802739f
It is interesting to note that the demineralization of natural enamel does not happen as readily as that of the synthesized hydroxyapatite (HAP), although they share a similar chemical composition. We suggest that the hierarchical structure of enamel is an important factor in the preservation of the natural material against dissolution. The anisotropic demineralization of HAP is revealed experimentally, and this phenomenon is understood by the different interfacial structures of HAP−water at the atomic level. It is found that HAP {001} facets can be more resistant against dissolution than {100} under acidic conditions. Although {100} is the largest surface of the typical HAP crystal, it is {001}, the smallest habit face, that is chosen by the living organisms to build the outer surface of enamel by an oriented assembly of the rodlike crystals. We reveal that such a biological construction can confer on enamel protections against erosion, since {001} is relatively dissolution-insensitive. Thus, the spontaneous dissolution of enamel surface can be retarded in biological milieu by such a smart construction. The current study demonstrates the importance of hierarchical structures in the functional biomaterials.
Co-reporter:Ling Li ; Yukan Liu ; Jinhui Tao ; Ming Zhang ; Haihua Pan ; Xurong Xu
The Journal of Physical Chemistry C 2008 Volume 112(Issue 32) pp:12219-12224
Publication Date(Web):July 22, 2008
DOI:10.1021/jp8026463
As the main inorganic component of biological bone and tooth enamel, hydroxyapatite (HAP) is highly biocompatible and bioactive. Our recent work has shown that 20 nm HAP can be readily internalized by living cells. However, HAP nanoparticles are not luminescent so that they are difficult to measure in living cells during in vitro experiments. A novel inorganic biological probe was suggested by doping 20 nm HAP with terbium. The calcium ions on the HAP particle surface could be partially replaced by Tb, which resulted in the 20 nm Tb-HAP particles. The Tb-doped HAP became luminescent and could be observed under a visible excitation of 488 nm. Compared with the usual probes, the modified HAP nanoparticles were more photostable and were almost nontoxic. It was important that the HAP characteristics remained after the surface modification with a small amount of Tb. After incubating with rabbit bone marrow mesenchymal stem cells (MSCs) in culture, the luminescence of the internalized HAP in the living cells was clearly observed under a fluorescent microscope. Transmission electron microscopy analysis also confirmed the uptake of the particles by MSCs. It was demonstrated that the modified HAP was a stable biological probe for cellular research. We suggested that the Tb-doped HAP should have a great potential to trace the evolvement of nanoparticles, which is a key topic in nanobiotechnology.
Co-reporter:Ben Wang;Peng Liu;Wenge Jiang;Haihua Pan Dr.;Xurong Xu Dr.
Angewandte Chemie 2008 Volume 120( Issue 19) pp:3616-3620
Publication Date(Web):
DOI:10.1002/ange.200704718
Co-reporter:Anhua Cai, Xurong Xu, Haihua Pan, Jinhui Tao, Rui Liu, Ruikang Tang and Kilwon Cho
The Journal of Physical Chemistry C 2008 Volume 112(Issue 30) pp:11324-11330
Publication Date(Web):July 3, 2008
DOI:10.1021/jp801408k
A new and simple method for preparation of hollow calcium carbonate nanospheres under mild conditions is developed. Hollow vaterite nanospheres are achieved by water-induced phase transformation of poly(4-sodium styrene sulfonate)-stabilized amorphous calcium carbonate (PSS−ACC) in water−ethanol solution at room temperature. It is found that the sizes of the resulting hollow-structured nanospheres can be easily regulated by the content of PSS and the phase transformation can be greatly affected by the ratio of water to ethanol in the mixed solvent. A combination effect of PSS and water is emphasized in this formation process. It is important to control the amounts of PSS and water in the experiments so that a large scale of hollow vaterite nanospheres with different sizes can be achieved. We suggest that the PSS−ACC particles use themselves as the templates to form the new crystallized shells, and its mechanism is also discussed.
Co-reporter:Ben Wang;Peng Liu;Wenge Jiang;Haihua Pan Dr.;Xurong Xu Dr.
Angewandte Chemie International Edition 2008 Volume 47( Issue 19) pp:3560-3564
Publication Date(Web):
DOI:10.1002/anie.200704718
Co-reporter:Jinhui Tao ; Haihua Pan ; Jieru Wang ; Jia Wu ; Ben Wang ; Xurong Xu
The Journal of Physical Chemistry C 2008 Volume 112(Issue 38) pp:14929-14933
Publication Date(Web):August 27, 2008
DOI:10.1021/jp804371u
Amorphous calcium phosphate (ACP) is an important intermediate phase during the biomineralization of apatite. But the detailed mechanism of transformation from ACP to crystallized hydroxyapatite (HAP) is still unclear. Gold nanoparticles are used as ex-situ probes to monitor the detailed evolution process of ACP in vitro. The rearrangement of gold nanoparticles during the evolution of ACP indicates the aggregation and surface-mediated crystallization subprocesses. The former process can be observed by the bottleneck-like connection and the distribution of gold nanoparticles inside the microspheres. After aggregation, surface-mediated crystallization dominated. The HAP nanoneedles first formed at the ACP-solution interface and extended outward radially. In this process, the ACP microsphere provides a template and nutrient for the growth and assembly of HAP nanoneedles, which is consistent with the well-known modified Kirkendall process. Neither the dissolution−recrystallization process nor the internal rearrangement mechanism is applicable for the explanation of such phenomena. Accordingly, the aggregation and Kirkendall process coupled with surface crystallization are proposed for an alternative mechanism for the evolution of ACP into HAP probed by gold nanoparticles. Although biomineralization is a complicated process in the presence of numerous biomolecules, our conceptual mechanism, revealed by the gold probe, may be also applied to understand the phase transformation in living organisms. This study shows that the involvement of gold nanoparticles can provide a new strategy to investigate the detailed evolution process of amorphous materials.
Co-reporter:Qinghong Hu, Zhou Tan, Yukan Liu, Jinhui Tao, Yurong Cai, Ming Zhang, Haihua Pan, Xurong Xu and Ruikang Tang
Journal of Materials Chemistry A 2007 vol. 17(Issue 44) pp:4690-4698
Publication Date(Web):24 Sep 2007
DOI:10.1039/B710936A
The biomedical materials research community frequently accepts that amorphous calcium phosphate (ACP) can be adsorbed and assimilated more readily by living organisms to produce new bone tissue than crystallized calcium phosphates such as hydroxyapatite (HAP). Previous studies also confirm that ACP has improved bioactivity compared to HAP since more adhesion and proliferation of osteogenic cells are observed on the ACP substrates. However, we note that the different size -effects of calcium phosphates are not taken into account in these studies and the used ACP are always smaller than the HAP. Our recent study reveals that the dimensions of nanoparticles are directly related to the bioactivities of calcium phosphates, e.g. the smaller nanocrystallites have a greater promotion effect on the proliferation of bone marrow mesenchymal stem cells (BMSCs). In order to understand the influence of crystallinity of calcium phosphate on the osteogenic cells correctly, it is critical to use ACP and HAP nanoparticles which have the same size distribution in such comparisons. In the present work, ∼20 nm ACP and HAP particles are synthesized and the effects of crystallinity of calcium phosphates are studied. The adhesion, proliferation, and differentiation of BMSCs are measured on ACP and HAP films, which are compared at the same size scale. It is surprising that more cells adsorb and proliferate on the film of well crystallized HAP than those on the ACP film. Alkaline phosphatase (ALP) activity assay and reverse transcription-polymerase chain reaction (RT-PCR) assay are also used to evaluate the differentiation of BMSCs. The results show that the differentiation of BMSCs to osteoblasts is promoted significantly by NanoHAP. The current experimental phenomena clearly demonstrate that the crystallized phase of calcium phosphate, HAP, provides a better substrate for BMSCs than the amorphous one, ACP, when the factor of size effect is removed. A new view on the relationship between the crystallinity of calcium phosphate and the responses of BMSCs indicates the importance of size and phase controls in the application of biomedical materials.
Co-reporter:Yurong Cai, Yukan Liu, Weiqi Yan, Qinghong Hu, Jinhui Tao, Ming Zhang, Zhongli Shi and Ruikang Tang
Journal of Materials Chemistry A 2007 vol. 17(Issue 36) pp:3780-3787
Publication Date(Web):06 Jun 2007
DOI:10.1039/B705129H
Hydroxyapatite (HAP) nanoparticles, typically 20 ± 5, 40 ± 10 and 80 ± 12 nm in diameter, were prepared and their effects on the proliferation of two bone-related cells, bone marrow mesenchymal stem cells (MSCs) and osteosarcoma cells (U2OS) were studied. The cell culture experiments showed improved cytophilicity of the nanophase mineral as compared with conventional HAP. Greater cell viability and proliferation of MSCs were measured on the nano HAP, remarkably for 20 nm sized particles. Interestingly, the growth of osteosarcoma cells was inhibited by the nano HAP and 20 nm sized particles were the best retardant. It is suggested that the HAP nanoparticles can exhibit favorable cell proliferation to optimize biological functionality, in which the particle size is believed to play a key role. These in vitro findings are of great significance for the understanding of cytophilicity and biological activity of nanoparticles during biomineralization.
Co-reporter:Haihua Pan;Jinhui Tao;Tao Wu
Frontiers of Chemistry in China 2007 Volume 2( Issue 2) pp:156-163
Publication Date(Web):2007 April
DOI:10.1007/s11458-007-0032-6
The water behavior on (001) and (100) crystal faces of hydroxyapatite (HAP) were studied using molecular dynamics (MD) simulations. The study showed that the water molecules between the HAP faces were under conditions of strong electrical field and high pressure, and hence formed 2–3 well-organized water layers on the crystal surfaces. These structured water layers had ice-like features. Compared with the crystallographic [100] direction of HAP, the polarity along the [001] direction was stronger, which resulted in more structured water layers on the surface. The interaction of water molecules with the calcium and phosphate sites at the HAP-water interface was also studied. The results indicated the multiple pathways of water adsorption onto the HAP surfaces. This study revealed the formation and the detailed structure of water layers on HAP surfaces and suggested that the interfacial water played an important role in stabilizing the HAP particles in aqueous solutions.
Co-reporter:Xiaoyu Wang, Dong Yang, Shihua Li, Xurong Xu, Cheng-Feng Qin, Ruikang Tang
Biomaterials (November 2016) Volume 106() pp:286-294
Publication Date(Web):November 2016
DOI:10.1016/j.biomaterials.2016.08.035
Frequent outbreaks and the rapid global spread of infectious diseases have increased the urgent need for massive vaccination especially in countries with limited resources. Intranasal vaccination facilitates the mass vaccination via needle-free delivery of vaccine through nasal mucosal surfaces. Inspired by the strong capability of calcium phosphate (CaP) materials to adhere to cells and tissues, we propose to improve nasal vaccination by using a biomineralization-based strategy. The vaccine nanohybrid was obtained by covering the viral surface with CaP nanoshell, which changed the physiochemical properties of original vaccine, resulting in the increase of mucosal adhesion to the nasal tissues. The core-shell structure was beneficial for the receptor-independent uptake and the induction of elevated local IgA response within the nasal cavity. Moreover, the vaccine complex elicited enhanced systemic antibody response that neutralized wild type of dengue virus and promoted the systemic cellular immune responses. This achievement presents the potential of CaP based vaccine biomineralization for the fabrication of needle-free vaccine formulation.
Co-reporter:Xiaoyu Wang, Dong Yang, Shihua Li, Xurong Xu, Cheng-Feng Qin, Ruikang Tang
Biomaterials (November 2016) Volume 106() pp:286-294
Publication Date(Web):November 2016
DOI:10.1016/j.biomaterials.2016.08.035
Co-reporter:Zhaoming Liu, Yun Xiao, Wei Chen, Yang Wang, Ben Wang, Guangchuan Wang, Xurong Xu and Ruikang Tang
Journal of Materials Chemistry A 2014 - vol. 2(Issue 22) pp:NaN3489-3489
Publication Date(Web):2014/04/02
DOI:10.1039/C4TB00056K
The application of nanotechnology for in medicine is developing rapidly, thereby increasing human exposure to nanomaterials and significantly so. A rising question is the biosecurity of nanoparticles (NPs). Although calcium phosphate (CaP) phase is biocompatible and biodegradable, many in vitro experiments have demonstrated that its NPs have significant cytotoxicity. This toxicity is due to that the released Ca2+ ions from the internalized CaP NPs within cells initiate apoptosis. Different from such an understanding, we reveal that the internalized CaP NPs actually result in lysosomal ruptures caused by the fast dissolution of CaP under acidic conditions. The suddenly released ions disturb the osmotic pressure balance across the lysosomal membranes destroying the lysosomes, and excessive lysosomal ruptures lead to cell necrosis. We find that the necrosis process can be regulated by intracellular environments. For examples, the lysosomal ruptures can be inhibited by increasing either cytoplasmic osmotic pressure or lysosomal pH (reduce the dissolution rates of CaP). These changes can significantly decrease the cytotoxicity of CaP NPs. It follows that lysosomal rupture prevention is important in the biomedical applications of CaP NPs. More generally, the study suggests that control of material degradation in lysosomes and cytoplasm osmotic pressure may improve the biosecurity of nanomaterials, which is of special importance to biomimetic nanomaterials.
Co-reporter:Qinghong Hu, Zhou Tan, Yukan Liu, Jinhui Tao, Yurong Cai, Ming Zhang, Haihua Pan, Xurong Xu and Ruikang Tang
Journal of Materials Chemistry A 2007 - vol. 17(Issue 44) pp:NaN4698-4698
Publication Date(Web):2007/09/24
DOI:10.1039/B710936A
The biomedical materials research community frequently accepts that amorphous calcium phosphate (ACP) can be adsorbed and assimilated more readily by living organisms to produce new bone tissue than crystallized calcium phosphates such as hydroxyapatite (HAP). Previous studies also confirm that ACP has improved bioactivity compared to HAP since more adhesion and proliferation of osteogenic cells are observed on the ACP substrates. However, we note that the different size -effects of calcium phosphates are not taken into account in these studies and the used ACP are always smaller than the HAP. Our recent study reveals that the dimensions of nanoparticles are directly related to the bioactivities of calcium phosphates, e.g. the smaller nanocrystallites have a greater promotion effect on the proliferation of bone marrow mesenchymal stem cells (BMSCs). In order to understand the influence of crystallinity of calcium phosphate on the osteogenic cells correctly, it is critical to use ACP and HAP nanoparticles which have the same size distribution in such comparisons. In the present work, ∼20 nm ACP and HAP particles are synthesized and the effects of crystallinity of calcium phosphates are studied. The adhesion, proliferation, and differentiation of BMSCs are measured on ACP and HAP films, which are compared at the same size scale. It is surprising that more cells adsorb and proliferate on the film of well crystallized HAP than those on the ACP film. Alkaline phosphatase (ALP) activity assay and reverse transcription-polymerase chain reaction (RT-PCR) assay are also used to evaluate the differentiation of BMSCs. The results show that the differentiation of BMSCs to osteoblasts is promoted significantly by NanoHAP. The current experimental phenomena clearly demonstrate that the crystallized phase of calcium phosphate, HAP, provides a better substrate for BMSCs than the amorphous one, ACP, when the factor of size effect is removed. A new view on the relationship between the crystallinity of calcium phosphate and the responses of BMSCs indicates the importance of size and phase controls in the application of biomedical materials.
Co-reporter:Yurong Cai, Yukan Liu, Weiqi Yan, Qinghong Hu, Jinhui Tao, Ming Zhang, Zhongli Shi and Ruikang Tang
Journal of Materials Chemistry A 2007 - vol. 17(Issue 36) pp:NaN3787-3787
Publication Date(Web):2007/06/06
DOI:10.1039/B705129H
Hydroxyapatite (HAP) nanoparticles, typically 20 ± 5, 40 ± 10 and 80 ± 12 nm in diameter, were prepared and their effects on the proliferation of two bone-related cells, bone marrow mesenchymal stem cells (MSCs) and osteosarcoma cells (U2OS) were studied. The cell culture experiments showed improved cytophilicity of the nanophase mineral as compared with conventional HAP. Greater cell viability and proliferation of MSCs were measured on the nano HAP, remarkably for 20 nm sized particles. Interestingly, the growth of osteosarcoma cells was inhibited by the nano HAP and 20 nm sized particles were the best retardant. It is suggested that the HAP nanoparticles can exhibit favorable cell proliferation to optimize biological functionality, in which the particle size is believed to play a key role. These in vitro findings are of great significance for the understanding of cytophilicity and biological activity of nanoparticles during biomineralization.
Co-reporter:Yurong Cai and Ruikang Tang
Journal of Materials Chemistry A 2008 - vol. 18(Issue 32) pp:NaN3787-3787
Publication Date(Web):2008/06/27
DOI:10.1039/B805407J
Recent developments in biomineralization and biomaterials have demonstrated that nano-calcium phosphate particles play an important role in the formation of hard tissues in nature. It is suggested that the basic inorganic building blocks of bone and enamel are nanosized apatite although their hierarchical structures differ. Nanoparticles can confer on biominerals remarkable physical and chemical characteristics such as enhanced mechanical strength and self-preservation in biological fluids. In living organisms, tens to hundreds of nano-blocks, under the control of an organic matrix, combine into self-assembled biominerals. It is also confirmed experimentally that enamel- or bone-like apatite can be achieved by oriented aggregation by using nano-calcium phosphates as the raw materials, determined by the biomolecules. Interestingly, features of smaller hydroxyapatite (HAP) nanoparticles may more closely approximate features of HAP during biomineralization than features of the larger HAP particles that are conventionally used. The application and prospective use of nano-calcium phosphate in the biological repair of bone and enamel are also introduced. It is emphasized that the cell experiments reveal improved cytophilicity of nanophase calcium phosphate minerals. Greater cell viability and proliferation of bone marrow mesenchymal stem cells are measured on smaller calcium phosphates. Furthermore, studies of amorphous calcium phosphate and crystallized HAP particles are used to investigate the effect of crystallinity of nanoparticles on living cells, and show that the differentiation of stem cells is promoted significantly by nano-HAP. It is suggested that nano-HAP may be the ideal biomaterial due to its good biocompatibility and bone/enamel integration. Lots of studies of calcium phosphates are expected in the nano-zone such as for drug delivery systems and resorbable scaffolds. In this feature article, a new view on calcium phosphates highlights the importance of size and phase controls in the application of biomedical materials.
Co-reporter:Ling Li, Jinhui Tao, Haihua Pan, Hanmin Chen, Xiaowei Wu, Feijian Zhu, Xurong Xu and Ruikang Tang
Journal of Materials Chemistry A 2008 - vol. 18(Issue 44) pp:NaN5367-5367
Publication Date(Web):2008/10/14
DOI:10.1039/B811552D
Generally, two or more phosphors are mixed to achieve multiplex colour in the fluorescence industry. However, such a simple mixture of fluorescent materials usually leads to colour discrepancy and may even affect the colour uniformity due to the distinct physicochemical properties of the different components. Fabrication of a core–shell structure is a novel strategy to prepare colour-tuned fluorescent materials. Here we report a core–shell structure made up from two phosphors, Y2O3:Eu and LnPO4, which can emit red and green light respectively. It is important to control the homogeneous and relatively low supersaturation of LnPO4 (Ln = La, Ce, and Tb) in the solution so that the precipitates of LnPO4 can deposit onto the Y2O3:Eu particles uniformly. This could result in an LnPO4 shell around the Y2O3:Eu core to form micron-sized complex particles. In the preparation of the core–shell structure, the slow hydrolysis of tripolyphosphate to release free phosphate ions is a key factor. It is well known that dissociation of tripolyphosphate is temperature sensitive so that this reaction can be controlled by heating the solution. Under UV excitation, both the core (Y2O3:Eu) and the newly formed shell (LnPO4) can emit their characteristic light; it is interesting that each individual core–shell complex can provide the multiplex colour homogeneously at the micron scale. By adjusting the proportion of core and shell in the complex, the fluorescence colours of the micron-sized phosphor can be tuned conveniently.
Co-reporter:Yuling Yang, Genxing Zhu, Guangchuan Wang, Yali Li and Ruikang Tang
Journal of Materials Chemistry A 2016 - vol. 4(Issue 27) pp:NaN4731-4731
Publication Date(Web):2016/06/17
DOI:10.1039/C6TB01355D
Biomolecules, especially enzymes, usually have poor thermal and operational stability as well as limited reuse cycles, which greatly limit their industrial practices. Inspired by the biomineralization strategy evolved by natural organisms, we suggest nanohybrid enzyme formulation by in situ encapsulating enzyme loaded functional Fe3O4@C nanoparticles with silica. By using glucose oxidase (GOD) as an example, we demonstrate that the obtained enzyme-material hybrids are featured by their significantly enhanced operational and thermal stabilities, which exhibit a relatively steady catalytic ability in a board range of 25 °C to 65 °C. Even after 4 h of incubation at 55 °C, the GOD-material composites still retain 77% of their initial activity while the native ones only retain 30%. Besides, the nanohybrids show excellent reusability because the magnetic character of the integrated Fe3O4 particles facilitates the enzyme separation and recycle. This attempt provides a valuable approach for biological improvement by using functional materials.
Co-reporter:Genxing Zhu, Ruibo Zhao, Yaling Li and Ruikang Tang
Journal of Materials Chemistry A 2016 - vol. 4(Issue 22) pp:NaN3910-3910
Publication Date(Web):2016/04/28
DOI:10.1039/C5TB02767E
Multifunctional Gd,Ce,Tb co-doped β-tricalcium phosphate (TCP) porous nanospheres are prepared by a facile solvothermal strategy with trimethyl phosphate as the phosphorus source. The as-prepared nanomaterial (average diameter of 100 nm) has a multiple level pore size distribution with the specific surface area of 124.33 m2 g−1, which benefits drug loading. Its photoluminescent and magnetic multifunctions are realized by the co-doping of Gd3+, Ce3+ and Tb3+ ions, which make the nanomaterial promising for both fluorescence and magnetic resonance imaging techniques. Furthermore, the nanomaterial exhibits excellent cytocompatibility and a relatively high doxorubicin loading capacity as well as sustained pH-sensitive drug release behaviour. It is suggested that the Gd,Ce,Tb co-doped β-TCP porous nanospheres are promising for applications in the biomedical fields such as multifunctional drug delivery systems and tissue engineering scaffolds with bioimaging guidance.
Co-reporter:Yong Yao, Yang Wang, Ruibo Zhao, Li Shao, Ruikang Tang and Feihe Huang
Journal of Materials Chemistry A 2016 - vol. 4(Issue 15) pp:NaN2696-2696
Publication Date(Web):2016/03/17
DOI:10.1039/C5TB02611C
In order to improve the effectiveness of cancer therapy and reduce the adverse effects of conventional chemotherapy, the development of less toxic, biocompatible, decomposable and pH-responsive nano-containers is of great importance. In this work a novel nano-container is designed and synthesized by doping a water-soluble pillar[5]arene WP5 onto hollow mesoporous silica nanoparticles (HMNPs) via host–guest complexation. This nano-container decomposes into small water-soluble fragments to achieve a highly efficient release of the loaded anticancer drug doxorubicin. Importantly, the complexation of WP5 molecules with HMNPs significantly improves the inhibition of tumor growth in vivo with minimal side effects, which can be attributed to the pH-responsiveness of the host–guest interactions. Under the extracelluar conditions, the host–guest complexation between WP5 and HMNPs enhances the loading of doxorubicin molecules. However, this host–guest complexation is prohibited under the low pH conditions in intracellular lysosomes, so that doxorubicin is released readily from the vector. The present novel drug delivery system demonstrates the great potential of host–guest complexation for cancer therapy improvement.
Co-reporter:Ben Wang, Guangchuan Wang, Binjie Zhao, Jiajun Chen, Xueyun Zhang and Ruikang Tang
Chemical Science (2010-Present) 2014 - vol. 5(Issue 9) pp:NaN3468-3468
Publication Date(Web):2014/05/15
DOI:10.1039/C4SC01120A
Blood type mismatching is a critical problem in blood transfusions and it occasionally leads to severe transfusion reactions and even patient death. Inspired by the adhesive proteins secreted by mussels, we suggest a catecholic chemistry-based strategy to shelter antigenic epitopes on red blood cells (RBCs) by using polydopamine (PDA), which can guard against coagulation reaction without other negative effects on the RBC structure, function and viability. Both in vitro and in vivo studies confirm that the PDA-engineered RBCs (PDA-RBCs) can be applied in blood transfusion practices. The systemic assessment using a murine model demonstrates that the modified RBCs have a perfect survival profile even with repeated transfusion and high transfusion rates up to around 60%. It follows that an appropriate biogenic-chemical modification can produce antigenically shielded universal RBCs and provide insight for cell transplantation by using cell surface engineering.
Co-reporter:Wei Xiong, Zhou Yang, Hailei Zhai, Guangchuan Wang, Xurong Xu, Weimin Ma and Ruikang Tang
Chemical Communications 2013 - vol. 49(Issue 68) pp:NaN7527-7527
Publication Date(Web):2013/06/26
DOI:10.1039/C3CC42766H
Bioinspired by diatoms, biomimetic silicification confers an artificial shell on cyanobacteria to alleviate photoinhibition; thus, the photosynthesis of the resulting cyanobacteria@SiO2 becomes more efficient under high light conditions.
Co-reporter:Hangyu Zhou, Guangchuan Wang, Xiao-Feng Li, Yaling Li, Shun-Ya Zhu, Cheng-Feng Qin and Ruikang Tang
Chemical Communications 2016 - vol. 52(Issue 38) pp:NaN6450-6450
Publication Date(Web):2016/04/11
DOI:10.1039/C6CC02595A
Developing vaccine formulations with excellent thermostability and immunogenicity remains a great challenge. By in situ encapsulating a live-attenuated strain of human enterovirus 71 (EV71) in alumina, we obtained a robust vaccine formulation named EV71@NanoAlum, which features significantly enhanced thermostability and immunogenicity. This attempt follows a material-based tactic for vaccine improvement.
Co-reporter:Zhiyong Song, Long Liu, Xiaoyu Wang, Yongqiang Deng, Qinggong Nian, Guangchuan Wang, Shunya Zhu, Xiaofeng Li, Hangyu Zhou, Tao Jiang, Xurong Xu, Ruikang Tang and Chengfeng Qin
Chemical Communications 2016 - vol. 52(Issue 9) pp:NaN1882-1882
Publication Date(Web):2015/12/09
DOI:10.1039/C5CC09252C
Conventional therapeutic monoclonal antibodies (mAbs) are invalid for intracellular viruses but by using in situ biomineralization treatment, they can be successfully delivered into cells to inhibit intracellular viral replication. This achievement significantly expands the applications of mAbs and provides a new intracellular strategy to control viral infections.
Co-reporter:Yuling Yang, Guangchuan Wang, Genxing Zhu, Xurong Xu, Haihua Pan and Ruikang Tang
Chemical Communications 2015 - vol. 51(Issue 41) pp:NaN8707-8707
Publication Date(Web):2015/04/20
DOI:10.1039/C5CC01420D
The hybrid nanoparticles of amorphous calcium phosphate (ACP)–catalase (CAT) developed by in situ biomineralization can create a stable semi-aqueous nanoscale environment for entrapped proteins against thermal denaturation. This finding indicates the importance of an amorphous mineral phase in the preservation of organic macromolecules.
Co-reporter:Wei Chen, Yun Xiao, Xueyao Liu, Yanhong Chen, Jiaojiao Zhang, Xurong Xu and Ruikang Tang
Chemical Communications 2013 - vol. 49(Issue 43) pp:NaN4934-4934
Publication Date(Web):2013/04/10
DOI:10.1039/C3CC41872C
Nano-solidified intermedias (NSI) of cisplatin were prepared via biomineralization and applied to reverse the drug resistance of cancers in vitro and in vivo by an alternative internalization pathway.
Co-reporter:Guangchuan Wang, Hangyu Zhou, Qing-Gong Nian, Yuling Yang, Cheng-Feng Qin and Ruikang Tang
Chemical Science (2010-Present) 2016 - vol. 7(Issue 3) pp:NaN1759-1759
Publication Date(Web):2015/12/10
DOI:10.1039/C5SC03847B
Exploring formulations that can improve the thermostability and immunogenicity of vaccines holds great promise in advancing the efficacy of vaccination to combat infectious diseases. Inspired by biomineralized core–shell structures in nature, we suggest a polyethyleneimine (PEI)–silica–PEI hybrid coated vaccine formulation to improve both thermostability and immunogenicity. Through electrostatic adsorption, in situ silicification and capping treatment, a hybrid coating of silica and PEI was assembled around a vaccine to produce vaccine@PEI–silica structures. Both in vitro and in vivo experiments demonstrated that the thermostability and immunogenicity of the modified vaccine were significantly improved. The modified vaccine could be used efficiently after long-term exposure at room temperature, which would facilitate vaccine transport and storage without a cold chain. Furthermore, mechanistic studies revealed that the PEI–silica–PEI coating acted as a physiochemical anchor as well as a mobility-restricting hydration layer to stabilize the enclosed vaccine. This achievement demonstrates a biomimetic surface-modification-based strategy to confer desired properties on biological products.
Co-reporter:Li Li, Haihua Pan, Jinhui Tao, Xurong Xu, Caiyun Mao, Xinhua Gu and Ruikang Tang
Journal of Materials Chemistry A 2008 - vol. 18(Issue 34) pp:NaN4084-4084
Publication Date(Web):2008/07/18
DOI:10.1039/B806090H
The application of calcium phosphates and their nanoparticles have been received great attention. However, hydroxyapatite (HAP) is not suggested in dental therapy to repair the damaged enamel directly although this compound has a similar chemical composition to enamel. We note that the size-effects of HAP are not taken into account in the previous studies as these artificial particles frequently have sizes of hundreds of nanometres. It has recently been revealed that the basic building blocks of enamel are 20–40 nm HAP nanoparticles. We suggest that the repair effect of HAP can be greatly improved if its dimensions can be reduced to the scale of the natural building blocks. Compared with conventional HAP and nano amorphous calcium phosphate (ACP), our in vitro experimental results demonstrate the advantages of 20 nm HAP in enamel repairs. The results of scanning electron microscopy, confocal laser scanning microscopy, quantitative measurement of the adsorption, dissolution kinetics, and nanoindentation, show the strong affinity, excellent biocompatibility, mechanical improvement, and the enhancement of erosion-free by using 20 nm particles as the repairing agent. However, these excellent in vitro repair effects cannot be observed when conventional HAP and ACP are applied. Clearly, nano HAP with a size of 20 nm shares similar characteristics to the natural building blocks of enamel so that it may be used as an effective repair material and anticaries agent. Our current study highlights the analogues of nano building blocks of biominerals during biomedical applications, which provide a novel pathway for biomimetic repair.
Co-reporter:Zhaoming Liu, Yadong Hu, Hongqing Zhao, Yang Wang, Xurong Xu, Haihua Pan and Ruikang Tang
Physical Chemistry Chemical Physics 2015 - vol. 17(Issue 15) pp:NaN10085-10085
Publication Date(Web):2015/03/04
DOI:10.1039/C4CP04115A
Living organisms such as corals can carry out CO2 looping efficiently via biomineralization under ambient conditions. Inspired by this natural process, we establish a solution system of calcium acetate–ethanol–water (Ca(Ac)2–C2H5OH–H2O) for CO2 chemical looping at constant room temperature. The CO2 capture is achieved by its reaction with Ca(Ac)2 to form calcium carbonate (CaCO3) mineral and HAc in the binary solvent with a high C2H5OH content. However, an increase in the H2O content in the system triggers acetic acid (HAc)-induced CaCO3 dissolution to release CO2. The system can be recovered for CO2 capture readily by the replenishment of C2H5OH. This biomimetic mineralization-based CO2 capture/release is controlled by the ionization states of the electrolytes, and is precisely regulated in the C2H5OH–H2O binary solvent. Our attempt highlights the fundamental principle of solution chemistry in reaction control and provides a bioinspired strategy for CO2 capture/release with very low cost and easy availability.
Co-reporter:Shuqin Jiang, Yan Chen, Haihua Pan, Yin-Jia Zhang and Ruikang Tang
Physical Chemistry Chemical Physics 2013 - vol. 15(Issue 30) pp:NaN12533-12533
Publication Date(Web):2013/06/04
DOI:10.1039/C3CP51466H
Faster nucleation of hydroxyapatite (HAP) at lower pH (with lower supersaturation) contradicts classical understanding. We find that the residue calcium ion in the mother liquor is the key to trigger ACP phase transformation, which gives an understanding of nonclassical nucleation kinetics of ACP-mediated crystallization and sheds light on biomineralization.
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