Qiang He

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Organization: Harbin Institute of Technology
Department: Micro/Nano Technology Research Centre
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Co-reporter:Jingxin Shao;Caixia Wen;Mingjun Xuan;Hongyue Zhang;Johannes Frueh;Mingwei Wan;Lianghui Gao
Physical Chemistry Chemical Physics 2017 vol. 19(Issue 3) pp:2008-2016
Publication Date(Web):2017/01/18
DOI:10.1039/C6CP06787E
Lipid bilayer membranes supported on polyelectrolyte multilayers are widely used as a new biomembrane model that connects biological and artificial materials since these ultrathin polyelectrolyte supports may mimic the role of the extracellular matrix and cell skeleton in living systems. Polyelectrolyte multilayers were fabricated by a layer-by-layer self-assembly technique. A quartz crystal microbalance with dissipation was used in real time to monitor the interaction between phospholipids and polyelectrolytes in situ on a planar substrate. The surface properties of polyelectrolyte films were investigated by the measurement of contact angles and zeta potential. Phospholipid charge, buffer pH and substrate hydrophilicity were proved to be essential for vesicle adsorption, rupture, fusion and formation of continuous lipid bilayers on the polyelectrolyte multilayers. The results clearly demonstrated that only the mixture of phosphatidylcholine and phosphatidic acid (4 : 1) resulted in fluid bilayers on chitosan and alginate multilayers with chitosan as a top layer at pH 6.5. A coarse-grained molecular simulation study elucidated that the exact mechanism of the formation of fluid lipid bilayers resembles a “parachute” model. As the closest model to the real membrane, polyelectrolyte multilayer-cushioned fluid lipid bilayers can be appropriate candidates for application in biomedical fields.
Co-reporter:Zhihua Lin;Dr. Tieyan Si;Dr. Zhiguang Wu;Changyong Gao;Dr. Xiankun Lin; Qiang He
Angewandte Chemie 2017 Volume 129(Issue 43) pp:13702-13705
Publication Date(Web):2017/10/16
DOI:10.1002/ange.201708155
AbstractWe report a dynamic self-organization of self-propelled peanut-shaped hematite motors from non-equilibrium driving forces where the propulsion can be triggered by blue light. They result in one-dimensional, active colloid ribbons with a positive phototactic characteristic. The motion of colloid motors is ascribed to the diffusion-osmotic flow in a chemical gradient by the photocatalytic decomposition of hydrogen peroxide fuel. We show that self-propelled peanut-shaped colloids readily form one-dimensional, slithering ribbon structures under the out-of-equilibrium collisions. This self-organization intrinsically results from the competition among the osmotically driven motion, the phoretic attraction and the inherent magnetic moments. The giant size number fluctuation in colloid ribbons is observed above a critical point 4.1 % of the surface density of colloid motors. Such phototactic colloid ribbons may provide a model system to understand the emergence of function in biological systems and have potential to construct bioinspired active materials based on different active building blocks.
Co-reporter:Dr. Jingxin Shao;Dr. Mingjun Xuan;Hongyue Zhang;Dr. Xiankun Lin;Dr. Zhiguang Wu; Qiang He
Angewandte Chemie International Edition 2017 Volume 56(Issue 42) pp:12935-12939
Publication Date(Web):2017/10/09
DOI:10.1002/anie.201706570
AbstractEngineering self-propelled micromotors with good biocompatibility and biodegradability for actively seeking disease sites and targeted drug transport remains a huge challenge. In this study, neutrophils with intrinsic chemotaxis capability were transformed into self-guided hybrid micromotors by integrating mesoporous silica nanoparticles (MSNs) with high loading capability. To ensure the compatibility of neutrophil cells with drug-loaded MSNs, bacteria membranes derived from E. coli were coated on MSNs in advance by a camouflaging strategy. The resulting biohybrid micromotors inherited the characteristic chemotaxis capability of native neutrophils and could effectively move along the chemoattractant gradients produced by E. coli. Our studies suggest that this camouflaging approach, which favors the uptake of MSNs into neutrophils without loss of cellular activity and motility, could be used to construct synthetic nanoparticle-loaded biohybrid micromotors for advanced biomedical applications.
Co-reporter:Dr. Jingxin Shao;Dr. Mingjun Xuan;Hongyue Zhang;Dr. Xiankun Lin;Dr. Zhiguang Wu; Qiang He
Angewandte Chemie 2017 Volume 129(Issue 42) pp:13115-13119
Publication Date(Web):2017/10/09
DOI:10.1002/ange.201706570
AbstractEngineering self-propelled micromotors with good biocompatibility and biodegradability for actively seeking disease sites and targeted drug transport remains a huge challenge. In this study, neutrophils with intrinsic chemotaxis capability were transformed into self-guided hybrid micromotors by integrating mesoporous silica nanoparticles (MSNs) with high loading capability. To ensure the compatibility of neutrophil cells with drug-loaded MSNs, bacteria membranes derived from E. coli were coated on MSNs in advance by a camouflaging strategy. The resulting biohybrid micromotors inherited the characteristic chemotaxis capability of native neutrophils and could effectively move along the chemoattractant gradients produced by E. coli. Our studies suggest that this camouflaging approach, which favors the uptake of MSNs into neutrophils without loss of cellular activity and motility, could be used to construct synthetic nanoparticle-loaded biohybrid micromotors for advanced biomedical applications.
Co-reporter:Meiling Chen, Narisu Hu, Chang Zhou, Xiankun Lin, Hui Xie, Qiang He
Colloids and Surfaces A: Physicochemical and Engineering Aspects 2017 Volume 520(Volume 520) pp:
Publication Date(Web):5 May 2017
DOI:10.1016/j.colsurfa.2017.01.063
•The design strategies of a natural armor: turtle shells have been investigated.•Microplatelets stack orderly and compactly, constructing a layered structure.•The modulus, stiffness, deformation, and adhesion are studied by AFM.Turtle shells protect themselves from predatorial attack, which could provide ideas and pathways for bioinspired synthetic materials. Despite with relatively weak constituents and low biomineralization, turtle shells possess unusually robust mechanical properties due to their well organized and layered structures that are accurately designed from nanoscale to macroscale in nature. Minerals (calcium phosphate and calcium sulfate polycrystal mixture) randomly disperse in the keratin, and forming organic-inorganic nanocomposite platelets. Such platelets are basic building blocks that stack orderly and compactly in the radial direction, and constructing individual platelets into a layered micro-configuration. The outstanding tensile mechanical performance of turtle shells has much relationship with rehydration and the growth orientation of the keratin cells. Compressive mechanical properties, growth texture of keratin, topography and mineral components’ distribution of turtle shell are investigated by AFM experiment effectively. Such excellent mechanical properties of turtle shells, which integrated with nanocomposite ingredients and layered structure, may inspire the biomimetic strategies for advanced multi-functional materials, especially for artificial armor.Download high-res image (183KB)Download full-size image
Co-reporter:Xiankun Lin;Tieyan Si;Zhiguang Wu
Physical Chemistry Chemical Physics 2017 vol. 19(Issue 35) pp:23606-23613
Publication Date(Web):2017/09/13
DOI:10.1039/C7CP02561K
As artificial active colloids, micro-/nanomotors (MNMs) can convert energy from the environment into mechanical motion in different fluids, showing potential applications in diverse fields such as targeted drug delivery and photothermal therapy. However, chemical fuels for typical catalytic MNMs, e.g., hydrogen peroxide, are highly toxic to organisms, and thus fuel-free MNMs are required. Recently, we have developed near-infrared light (NIR) propelled MNMs through integrating plasmonic gold nanoshells into nanoparticles or layer-by-layer assemblies in an asymmetric manner. In this perspective, we give an account of self-thermophoresis motion of these NIR-powered MNMs. The design of the motor architectures, as well as the theoretical study on the propulsion mechanism, is highlighted. We believe that the insights into self-thermophoretic motion would pave the way to access powerful MNMs for future applications and to explore interesting collective behaviors of active matter.
Co-reporter:Xiankun Lin;Zhiguang Wu;Yingjie Wu;Mingjun Xuan
Advanced Materials 2016 Volume 28( Issue 6) pp:1060-1072
Publication Date(Web):
DOI:10.1002/adma.201502583

Synthetic micro-/nanomotors (MNMs) are capable of performing self-propelled motion in fluids through harvesting different types of energies into mechanical movement, with potential applications in biomedicine and other fields. To address the challenges in these applications, a promising strategy that combines controlled assembly (bottom-up approaches) with top-down approaches for engineering autonomous, multifunctionalized MNMs is under investigation, beginning in 2012. These MNMs, derived from layer-by-layer assembly or molecular self-assembly, display the advantages of: i) mass production, ii) response to the external stimuli, and iii) access to multifunctionality, biocompatibility, and biodegradability. The advance on how to integrate diverse functional components into different architectures based on controlled assemblies, to realize controlled fabrication, motion control (including the movement speed, direction, and state), and biomedical applications of MNMs, directed by the concept of nanoarchitectonics, are highlighted here. The remaining challenges and future research directions are also discussed.

Co-reporter:Changyong Gao, Zhiguang Wu, Zhihua Lin, Xiankun Lin and Qiang He  
Nanoscale 2016 vol. 8(Issue 6) pp:3548-3554
Publication Date(Web):11 Jan 2016
DOI:10.1039/C5NR08407E
We report a biomimetic delivery of microsized capsule-cushioned leukocyte membrane vesicles (CLMVs) through the conversion of freshly reassembled leukocyte membrane vesicles (LMVs), including membrane lipids and membrane-bound proteins onto the surface of layer-by-layer assembled polymeric multilayer microcapsules. The leukocyte membrane coating was verified by using electron microscopy, a quartz crystal microbalance, dynamic light scattering, and confocal laser scanning microscopy. The resulting CLMVs have the ability to effectively evade clearance by the immune system and thus prolong the circulation time in mice. Moreover, we also show that the right-side-out leukocyte membrane coating can distinctly improve the accumulation of capsules in tumor sites through the molecular recognition of membrane-bound proteins of CLMVs with those of tumor cells in vitro and in vivo. The natural cell membrane camouflaged polymeric multilayer capsules with the immunosuppressive and tumor-recognition functionalities of natural leukocytes provide a new biomimetic delivery platform for disease therapy.
Co-reporter:Wenping He, Johannes Frueh, Zhenwei Wu, and Qiang He
ACS Applied Materials & Interfaces 2016 Volume 8(Issue 7) pp:4407
Publication Date(Web):January 29, 2016
DOI:10.1021/acsami.5b10885
Modern drug delivery systems rely on either antibody-based single-surface recognition or on surface-hydrophobicity-based approaches. For a tumor showing various surface mutations, both approaches fail. This publication hereby presents Janus capsules based on polyelectrolyte multilayer microcapsules exhibiting human leucocyte (THP-1 cell line) cell membranes for discriminating HUVEC cells from three different cancer cell lines. Despite destroying the cellular integrity of leucocyte cells, the modified Janus capsules are able to adhere to cancer cells. Leucocyte cell-membrane-coated Janus capsules are phagocytosed with the cellular membrane part pointing to the cells.Keywords: biocompatible; Janus capsule; leukocyte cell; phagocytosis; target recognition
Co-reporter:Mingjun Xuan, Jingxin Shao, Luru Dai, Junbai Li, and Qiang He
ACS Applied Materials & Interfaces 2016 Volume 8(Issue 15) pp:9610
Publication Date(Web):April 4, 2016
DOI:10.1021/acsami.6b00853
Macrophage cell membrane (MPCM)-camouflaged gold nanoshells (AuNS) that can serve as a new generation of photothermal conversion agents for in vivo photothermal cancer therapy are presented. They are constructed by the fusion of biocompatible AuNSs and MPCM vesicles. The resulting MPCM-coated AuNSs exhibited good colloidal stability and kept the original near-infrared (NIR) adsorption of AuNSs. Because AuNS carried high-density coverage of MPCMs, the totally functional portions of macrophage cells membrane were grafted onto the surface of AuNSs. This surface functionalization provided active targeting ability by recognizing tumor endothelium and thus improved tumoritropic accumulation compared to the red blood cell membrane-coating approach. These biomimetic nanoparticles significantly enhance in vivo blood circulation time and local accumulation at the tumor when administered systematically. Upon NIR laser irradiation, local heat generated by the MPCM-coated AuNS achieves high efficiency to suppress tumor growth and selectively ablate cancerous cells within the illuminated zone. Therefore, MPCM-coated AuNSs remained the natural properties of their source cells, which may improve the efficacy of photothermal therapy modulated by AuNSs and other noble-metal nanoparticles.Keywords: Au nanoshell; biostealth coating; long circulation; macrophage cell membrane; photothermal therapy
Co-reporter:Meiyu Gai, Johannes Frueh, Narisu Hu, Tieyan Si, Gleb B. Sukhorukov and Qiang He  
Physical Chemistry Chemical Physics 2016 vol. 18(Issue 5) pp:3397-3401
Publication Date(Web):11 Jan 2016
DOI:10.1039/C5CP07697H
This communication sheds light on the production method and motion patterns of autonomous moving bubble propelled two dimensional micro-plate motors. The plate motors are produced by the well-known layer-by-layer self-assembly process in combination with micro-contact printing. The motion analysis covers instances of oscillating bubble development on one or more nucleation sites, which influence the motion speed and direction.
Co-reporter:Meiling Chen, Yuncheng Mo, Zesheng Li, Xiankun Lin, Qiang He
European Polymer Journal 2016 Volume 84() pp:622-630
Publication Date(Web):November 2016
DOI:10.1016/j.eurpolymj.2016.10.005
•PBO nanofibers are used as a polymeric building block to assemble layered films.•(PBO-PBO)50 films possess outstanding thermal stability and fire retardancy.•(PBO-PVA)50 nanocomposites exhibit enhanced mechanical strength and flexibility.Assembling nanoscale building blocks derived from ultrastrong polymer fibers into ordered architectures should offer an effectively alternative way to access high-performance nanocomposites with extremely high strength and heat resistance for advanced applications. Poly(p-phenylenebenzobisoxazole) (PBO) fibers possess outstanding mechanical and thermal properties among the synthetic organic fibers. Here, commercial PBO fibers have been disintegrated into uniform nanofibers with the diameter of ca. 20 nm by a mixed acid treatment, and then served as a polymeric building block to be assembled into layered architectures through layer-by-layer deposition. The resulting (PBO-PBO)50 films exhibit superior mechanical and thermomechanical properties with the modulus of 3.29 GPa, the toughness of 2.1 MJ m−3, and the strength of 181.08 MPa. Through employing the poly(vinyl alcohol) (PVA) as a connecting layer in the deposition, the (PBO-PVA)50 nanocomposite films possess remarkable mechanical properties demonstrated by the modulus of 6.48 GPa, the toughness of 4.6 MJ m−3, and the strength of 304.34 MPa, due to the synergistic interfacial interaction between the PBO nanofibers and the matrix. In addition, the (PBO-PBO)50 films possess the thermal stability up to 625 °C and excellent fire retardancy.
Co-reporter:Yingjie Wu;Tieyan Si;Jingxin Shao;Zhiguang Wu
Nano Research 2016 Volume 9( Issue 12) pp:3747-3756
Publication Date(Web):2016 December
DOI:10.1007/s12274-016-1245-0
We report a fuel-free, near-infrared (NIR)-driven Janus microcapsule motor. The Janus microcapsule motors were fabricated by template-assisted polyelectrolyte layer-by-layer assembly, followed by spraying of a gold layer on one side. The NIR-powered Janus motors achieved high propulsion with a maximum speed of 42 µm·s-1 in water. The propulsion mechanism of the Janus motor was attributed to the self-thermophoresis effect: The asymmetric distribution of the gold layer generated a local thermal gradient, which in turn generated thermophoretic force to propel the Janus motor. Such NIR-propelled Janus capsule motors can move efficiently in cell culture medium and have no obvious effects on the cell at the power of the NIR laser, indicating considerable promise for future biomedical applications.
Co-reporter:Changyong Gao, Zhihua Lin, Zhiguang WuXiankun Lin, Qiang He
ACS Applied Materials & Interfaces 2016 Volume 8(Issue 50) pp:
Publication Date(Web):December 2, 2016
DOI:10.1021/acsami.6b12865
The upconversion nanoparticle (UCNP)-based photodynamic therapy (PDT) agents are promising for deep-tissue cancer treatment because they may overcome current limitations due to the shallow penetration depth of visible light. However, limited blood circulation time and poor tumor-targeting capability challenge the therapeutic efficacy of UCNP-based PDT in vivo. Here, we demonstrate intravenous injectable stem-cell-membrane-camouflaged upconversion nanoarchitectures as a biomimetic tumor PDT platform. The biomimetic PDT system is constructed by fusing mesoporous-silica-encapsulated β-NaYF4:Yb3+,Er3+ UCNPs with stem-cell membranes. Translocation of the stem-cell membranes to the UCNPs led to the translation of multiple membrane components, bringing the membranes’ long circulation and tumor-targeting capability to the resulting platform. Multiphotosensitizers were encapsulated and simultaneously activated by a 980 nm single laser because of the multicolor emission capability of the UCNP cores. In vitro and in vivo experiments demonstrate that this novel platform inherits the tumor-targeting properties of stem cells and exhibits remarkable accumulation at the tumor site. In vivo tumor PDT results show higher tumor inhibition efficacy by tail intravenous administration of this new photosensitizer-loaded system. This stem-cell-membrane-camouflaged upconversion nanoarchitecture provides artificial UCNPs with natural cell membranes and holds considerable promise for deep-tissue PDT cancer treatment by systemic administration.Keywords: intravenous administration; photodynamic therapy; stem-cell membrane; tumor targeting; upconversion;
Co-reporter:Wenping He, Johannes Frueh, Zhenwei Wu, and Qiang He
Langmuir 2016 Volume 32(Issue 15) pp:3637-3644
Publication Date(Web):March 29, 2016
DOI:10.1021/acs.langmuir.5b04762
Polyelectrolyte multilayer (PEM) capsules are promising candidates for many kinds of cancer detection and treatment but are usually intended to deliver cargo to specific sites or to destroy cancer cells based on photothermal effects from the outside. In this publication we prove that it is possible to kill cancer cells from the inside based on phagocytosed PEM capsules. In addition we show how to open the cells and bring the PEM capsules to the surface of cancer cells based on photothermal effects and rapid evaporation of water. Diffusion-based temperature determinations of the photothermal effect up to the evaporation temperature of water are presented.
Co-reporter:Wenping He, Johannes Frueh, Jingxin Shao, Meiyu Gai, Narisu Hu, Qiang He
Colloids and Surfaces A: Physicochemical and Engineering Aspects 2016 Volume 511() pp:73-81
Publication Date(Web):20 December 2016
DOI:10.1016/j.colsurfa.2016.09.052
•Diffusion based temperatures detect temperatures closer to observations than competing techniques.•Guidable dyes show preferable welding properties due to higher number density.•Guidable dyes allow future applications in internal haemostatic applications.•Mechanical test prove restoration of mechanical properties of tissue.•The guiding mechanism also works in blood not only water.Photothermal therapies utilizing gold nanostructures are widely investigated and used within state-of-the-art noninvasive approaches. Single, isolated gold nanoparticles are unable to produce high enough temperatures to perform a sufficient wound closure, requiring therefore large amounts and concentrations to facilitate a therapeutic effect. In this proof of principle study we prepare composite micro-particles which contain near-infrared laser sensitive gold nanorods (GNRs) and Fe3O4 superparamagnetic particles which are agglommerated in a layered polyelectrolyte multilayer (PEM) matrix. The GNRs-Fe3O4-PEM particles can be enriched in tissue incisions by applying a magnetic field. With this magnetic filed a targeted agglomeration is observed which is beneficial for near-infrared laser based wound sealing. Mechanical tests show that laser treated skin recovered closest to pristine samples and is comparable with nanoparicle gluing. The healing effect of this system is comparable with clinical sutures and nanoparticle gluing in in-vivo experiments. The observation that internal organs like liver can be welded with such composite particles opens new applications for laser tissue welding.
Co-reporter:Jingxin Shao, Mingjun Xuan, Tieyan Si, Luru Dai and Qiang He  
Nanoscale 2015 vol. 7(Issue 45) pp:19092-19098
Publication Date(Web):22 Oct 2015
DOI:10.1039/C5NR06350G
Seeking safe and effective water-soluble drug carriers is of great significance in nanomedicine. To achieve this goal, we present a novel drug delivery system based on biointerfacing hollow polymeric microcapsules for effectively encapsulating water-soluble antitumor drug and gold nanorod (GNR) functionalization for triggered release of therapeutic drugs on-demand using low power near-infrared (NIR) radiation. The surface of polymeric microcapsules is covered with fluidic lipid bilayers to decrease the permeability of the wall of polymeric capsules. The temperature increase upon NIR illumination deconstructs the structure of the lipid membrane and polyelectrolyte multilayers, which in turn results in the rapid release of encapsulated water-soluble drug. In vivo antitumor tests demonstrate that this microcapsule has the effective ability of inhibiting tumor growth and preventing metastases. Real time in vivo fluorescence imaging results confirm that capsules can be excreted gradually from the animal body which in turn demonstrates the biocompatibility and biodegradation of these biointerfacing GNR-microcapsules. This intelligent system provides a novel anticancer platform with the advantages of controlled release, biological friendliness and credible biosafety.
Co-reporter:Yingjie Wu, Tieyan Si, Xiankun Lin and Qiang He  
Chemical Communications 2015 vol. 51(Issue 3) pp:511-514
Publication Date(Web):13 Nov 2014
DOI:10.1039/C4CC07182D
The use of a near-infrared (NIR) laser for reversible modulation of a bubble-driven Janus polymer capsule motor is demonstrated. This process was mediated through illumination of the metal face of the Janus capsule motor at the critical concentration of peroxide fuel. Such an effective control of the propulsion of chemically powered microengines holds a considerable promise for diverse applications.
Co-reporter:Zhiguang Wu, Xiankun Lin, Xian Zou, Jianmin Sun, and Qiang He
ACS Applied Materials & Interfaces 2015 Volume 7(Issue 1) pp:250
Publication Date(Web):December 12, 2014
DOI:10.1021/am507680u
We describe a biodegradable, self-propelled bovine serum albumin/poly-l-lysine (PLL/BSA) multilayer rocket as a smart vehicle for efficient anticancer drug encapsulation/delivery to cancer cells and near-infrared light controlled release. The rockets were constructed by a template-assisted layer-by-layer assembly of the PLL/BSA layers, followed by incorporation of a heat-sensitive gelatin hydrogel containing gold nanoparticles, doxorubicin, and catalase. These rockets can rapidly deliver the doxorubicin to the targeted cancer cell with a speed of up to 68 μm/s, through a combination of biocatalytic bubble propulsion and magnetic guidance. The photothermal effect of the gold nanoparticles under NIR irradiation enable the phase transition of the gelatin hydrogel for rapid release of the loaded doxorubicin and efficient killing of the surrounding cancer cells. Such biodegradable and multifunctional protein-based microrockets provide a convenient and efficient platform for the rapid delivery and controlled release of therapeutic drugs.Keywords: autonomous propulsion; biodegradation; drug release; layer-by-layer; rocket
Co-reporter:Minjun Xuan;Jingxin Shao;Luru Dai;Junbai Li
Advanced Healthcare Materials 2015 Volume 4( Issue 11) pp:1645-1652
Publication Date(Web):
DOI:10.1002/adhm.201500129
Co-reporter:Zhiguang Wu;Changyong Gao;Johannes Frueh;Jianming Sun
Macromolecular Rapid Communications 2015 Volume 36( Issue 15) pp:1444-1449
Publication Date(Web):
DOI:10.1002/marc.201500207
Co-reporter:Yingjie Wu, Johannes Frueh, Tieyan Si, Helmuth Möhwald and Qiang He  
Physical Chemistry Chemical Physics 2015 vol. 17(Issue 5) pp:3281-3286
Publication Date(Web):09 Dec 2014
DOI:10.1039/C4CP05231E
In this study we investigated the effect of laser-induced membrane fusion of polyelectrolyte multilayer (PEM) based microcapsules bearing surface-attached gold nanoparticles (AuNPs) in aqueous media. We demonstrate that a dense coating of the capsules with AuNPs leads to enhanced light absorption, causing an increase of local temperature. This enhances the migration of polyelectrolytes within the PEMs and thus enables a complete fusion of two or more capsules. The encapsulated substances can achieve complete merging upon short-term laser irradiation (30 s, 30 mW @ 650 nm). The whole fusion process is followed by optical microscopy and scanning electron microscopy. In control experiments, microcapsules without AuNPs do not show a significant capsule fusion upon irradiation. It was also found that the duration of capsule fusion is affected by the density of AuNPs on the shell – the higher the density of AuNPs the shorter the fusion time. All these findings confirm that laser-induced microcapsule fusion is a new type of membrane fusion. This effect helps to study the interior exchange reactions of functional microcapsules, micro-reactors and drug transport across multilayers.
Co-reporter:Meiyu Gai, Johannes Frueh, Agnes Girard-Egrot, Samuel Rebaud, Bastien Doumeche and Qiang He  
RSC Advances 2015 vol. 5(Issue 64) pp:51891-51899
Publication Date(Web):05 Jun 2015
DOI:10.1039/C5RA08456C
Polyelectrolyte multilayer (PEM) thin films are popular candidates for surface coating due to their versatility, tunability and simple production method. Often these films are used in a 2D structured manner for creating defined cell scaffolds or electronic applications. Although these films were successfully printed in the past, the conditions and energies necessary for a successful printing were only investigated as isolated parameters or as a function of the substrate but not the PEM surface energy and therefore the dominating forces remained controversial. We hereby present a theory and method for microcontact printing of condensed polyelectrolyte multilayer thin films, based on surface energies and the line tension. The theory relies on the surface energy of the substrate, stamp and PEM as well as the PEM line tension ratios to create the desired pattern. The presented theory is able to predict the printability, quality and resolution limit of a chosen system and was evaluated with experiments. A reduction of the production time from the beginning of PEM assembly to the final pattern from several hours down to 30 minutes was achieved while increasing reproducibility and resolution of the printed patterns at the same time. We would like to point out that this approach can generally be used for any kind of adsorbed thin film on substrates.
Co-reporter:Meiyu Gai, Johannes Frueh, Gleb B. Sukhorukov, Agnes Girard-Egrot, Samuel Rebaud, Bastien Doumeche, Qiang He
Colloids and Surfaces A: Physicochemical and Engineering Aspects 2015 Volume 483() pp:271-278
Publication Date(Web):20 October 2015
DOI:10.1016/j.colsurfa.2015.05.009
•Glass–viscous flow transition effects influences the quality of PEM patterns during printing.•PEM that dissolves within stamp structure increases osmotic pressure.•Osmotic pressure can be used to expel printed PEM structures from stamps.•Cold water vapour from a humidifier can be used for humidifying PEM.•Active printing area necessary for printing PEM not total stamp area.Micro and nano-patterned surfaces are important for many applications ranging from antibiofouling over tissue engineering to electronics. Often the incorporation of functional entities is of interest. Polymer coatings especially polyelectrolyte multilayer (PEM) films and patterns are materials offering a large variety of tuning and engineering. The PEM pattern printing quality bases not only on the surface force balance but also in the way the PEM is softened, which can be done by printing the PEM in water, using an ultrasound humidifier or by exposing the film to (hot) water vapor. In this publication it is shown, that cold water vapor from an ultrasound humidifier or direct printing in water is superior to steam evaporation onto PEM thin films as humidification method. In addition the capillary pressure of the patterns within the stamp and the glass–viscous flow transition point of the PEM thin film are the significant parameters for PEM printing. This is because the PEM can surpass the glass–viscous flow transition point due to the shear forces and be sucked into the stamp microwells (or holes) preventing a structure replication. Under high temperatures and in aqueous conditions, the PEM can be expelled from the microwells due to the osmotic pressure produced by the counter ions of PEM in glass–viscous flow state and dissolving polyelectrolyte if a PEM with counter ion based charge balance is used.Micro and nanostructured surfaces and samples are of fundamental importance for electronics, tissue engineering and drug delivery. The effect of glass–viscous flow transition on thin polymer films for microcontact printing was investigated by the example of polyelectrolyte multilayers depending on the softening method (cold versus hot solvent) and for different temperatures in relation to the glass–viscous flow transition point. Interestingly PEM structures can not only be printed but also be expelled from stamps in aqueous solution when the stamp is removed. This is due to emerging osmotic pressures created by dissolving PEM at temperatures exceeding the PEM glass transition point.
Co-reporter:Mingjun Xuan;Xiankun Lin;Jingxin Shao;Dr. Luru Dai; Qiang He
ChemPhysChem 2015 Volume 16( Issue 1) pp:147-151
Publication Date(Web):
DOI:10.1002/cphc.201402795

Abstract

We report a self-propelled Janus silica micromotor as a motion-based analytical method for achieving fast target separation of polyelectrolyte microcapsules, enriching different charged organics with low molecular weights in water. The self-propelled Janus silica micromotor catalytically decomposes a hydrogen peroxide fuel and moves along the direction of the catalyst face at a speed of 126.3 μm s−1. Biotin-functionalized Janus micromotors can specifically capture and rapidly transport streptavidin-modified polyelectrolyte multilayer capsules, which could effectively enrich and separate different charged organics in water. The interior of the polyelectrolyte multilayer microcapsules were filled with a strong charged polyelectrolyte, and thus a Donnan equilibrium is favorable between the inner solution within the capsules and the bulk solution to entrap oppositely charged organics in water. The integration of these self-propelled Janus silica micromotors and polyelectrolyte multilayer capsules into a lab-on-chip device that enables the separation and analysis of charged organics could be attractive for a diverse range of applications.

Co-reporter:Mingjun Xuan;Xiankun Lin;Jingxin Shao;Dr. Luru Dai; Qiang He
ChemPhysChem 2015 Volume 16( Issue 1) pp:
Publication Date(Web):
DOI:10.1002/cphc.201590004
Co-reporter:Mingjun Xuan, Jingxin Shao, Xiankun Lin, Luru Dai, Qiang He
Colloids and Surfaces A: Physicochemical and Engineering Aspects 2015 Volume 482() pp:92-97
Publication Date(Web):5 October 2015
DOI:10.1016/j.colsurfa.2015.04.032
•Fuel-free, light-activated Janus polymer multilayer capsule motors were described.•Biocompatible Janus capsule motors were fabricated by layer-by-layer assembly.•The speed of Janus capsule motors can be regulated by changing laser power.•Forming thermal gradient by photothermal effect explains the propulsion mechanism.We report a self-propelled Janus micromotor composed by chitosan (CHI) and alginate (ALG) multilayer capsule driven by near-infrared (NIR) illumination. The CHI/ALG multilayer capsules were prepared using conventional template-assisted layer-by-layer (LbL) self-assembly. Subsequently, gold nanorods (GNRs) were deposited on one side of the assembled capsules using microcontact printing method. The GNRs-modified Janus capsules can be driven by NIR irradiation owing to the generated thermal gradient and no additional chemical fuel are requested. It is also shown the moving speed of these Janus micromotors can be regulated by irradiation intensity and reach to 23.27 μm/s at a laser power of 9.6 J/cm2. Since no additional chemical component as fuel, this GNRs-modified ALG/CHI multilayer Janus capsule micromotor shows great potential as a biomimetic delivery platform in biomedical field.Near infra-red (NIR) laser-driven layer-by-layer assembled Janus chitosan/alginate multilayer capsule micromotors have been demostrated and has potential in biomedical and environmental fields.
Co-reporter:Zhiguang Wu, Xiankun Lin, Yingjie Wu, Tieyan Si, Jianmin Sun, and Qiang He
ACS Nano 2014 Volume 8(Issue 6) pp:6097
Publication Date(Web):May 7, 2014
DOI:10.1021/nn501407r
We describe an approach to modulating the on-demand motion of catalytic polymer-based microengines via near-infrared (NIR) laser irradiation. The polymer multilayer motor was fabricated by the template-assisted layer-by-layer assembly and subsequently deposition of platinum nanoparticles inside and a thin gold shell outside. Then a mixed monolayer of a tumor-targeted peptide and an antifouling poly(ethylene glycol) was functionalized on the gold shell. The microengines remain motionless at the critical peroxide concentration (0.1%, v/v); however, NIR illumination on the engines leads to a photothermal effect and thus rapidly triggers the motion of the catalytic engines. Computational modeling explains the photothermal effect and gives the temperature profile accordingly. Also, the photothermal effect can alone activate the motion of the engines in the absence of the peroxide fuel, implying that it may eliminate the use of toxic fuel in the future. The targeted recognition ability and subsequently killing of cancer cells by the photothermal effect under the higher power of a NIR laser were illustrated. Our results pave the way to apply self-propelled synthetic engines in biomedical fields.Keywords: autonomous motion; layer-by-layer; photothermal effect; recognition; synthetic motor
Co-reporter:Mingjun Xuan;Jingxin Shao;Dr. Xiankun Lin;Dr. Luru Dai; Qiang He
ChemPhysChem 2014 Volume 15( Issue 11) pp:2255-2260
Publication Date(Web):
DOI:10.1002/cphc.201402111

Abstract

The synthesis of an innovative self-propelled Janus nanomotor with a diameter of about 75 nm that can be used as a drug carrier is described. The Janus nanomotor is based on mesoporous silica nanoparticles (MSNs) with chromium/platinum metallic caps and propelled by decomposing hydrogen peroxide to generate oxygen as a driving force with speeds up to 20.2 μm s−1 (about 267 body lengths per second). The diffusion coefficient (D) of nanomotors with different H2O2 concentrations is calculated by tracking the movement of individual particles recorded by means of a self-assembled fluorescence microscope and is significantly larger than free Brownian motion. The traction of a single Janus MSN nanomotor is estimated to be about 13.47×10−15 N. Finally, intracellular localization and drug release in vitro shows that the amount of Janus MSN nanomotors entering the cells is more than MSNs with same culture time and particle concentrations, meanwhile anticancer drug doxorubicin hydrochloride loaded in Janus MSNs can be slowly released by biodegradation of lipid bilayers in cells.

Co-reporter:Mingjun Xuan;Jingxin Shao;Dr. Xiankun Lin;Dr. Luru Dai; Qiang He
ChemPhysChem 2014 Volume 15( Issue 11) pp:
Publication Date(Web):
DOI:10.1002/cphc.201490051
Co-reporter:Johannes Frueh, Gerald Reiter, Helmuth Möhwald, Qiang He and Rumen Krastev  
Physical Chemistry Chemical Physics 2013 vol. 15(Issue 2) pp:483-488
Publication Date(Web):31 Oct 2012
DOI:10.1039/C2CP43302H
Polyelectrolyte multilayers (PEMs) deposited on flexible supports are promising candidates for many applications ranging from controlled wettability over stimuli responsive nanovalves to lithography free surface structuring. Since many potential applications involve elongation of these films, we investigated the effect of elongation on the PEM thickness and density with ellipsometry. To our surprise PEM films with known amorphous internal structure show auxetic behavior that depends on the PEM preparation condition. The measured refractive index was compared with simulated values using the Garnet equation to evaluate if the incorporation of water or air causes the observed phenomena.
Co-reporter:Johannes Frueh, Gerald Reiter, Janos Keller, Helmuth Möhwald, Qiang He, and Rumen Krastev
The Journal of Physical Chemistry B 2013 Volume 117(Issue 10) pp:2918-2925
Publication Date(Web):February 18, 2013
DOI:10.1021/jp310727f
Polyelectrolyte multilayers (PEMs) deposited on flexible supports, such as silicone rubber, show interesting properties upon elongation and release, like controlled wrinkling, elongation-based wetting, or dewetting and stimuli responsive nanovalves. To understand the underlying physical effects of PEM experiencing linear elongation, the orientation change of molecular groups within PEM experiencing linear elongation was investigated. The model PEM consists of polystyrenesulphonate and polydimethyldiallyl chloride. The investigation method was infrared attenuated total reflectance. In the study, the orientation change of the benzene and the sulfate groups of polystyrenesulphonate upon elongation of the PEM, prepared at high and low ionic strengths, was tracked. The gained results show that the benzene group shows no sign of orientation change upon elongation, whereas the sulfate group does, whereby the reorientation depends on the ionic strength of the preparation solution. Upon release of elongation, the PEM prepared at low ionic strength shows no orientation change, whereas PEM prepared at high ionic strength does show further orientation change, indicating that the formed wrinkles elongate the PEM on the top of the wrinkles.
Co-reporter:Zhiguang Wu;Yingjie Wu;Wenping He;Dr. Xiankun Lin; Jianmin Sun ; Qiang He
Angewandte Chemie International Edition 2013 Volume 52( Issue 27) pp:7000-7003
Publication Date(Web):
DOI:10.1002/anie.201301643
Co-reporter:Zhiguang Wu;Yingjie Wu;Wenping He;Dr. Xiankun Lin; Jianmin Sun ; Qiang He
Angewandte Chemie 2013 Volume 125( Issue 27) pp:7138-7141
Publication Date(Web):
DOI:10.1002/ange.201301643
Co-reporter:Xiankun Lin, Qiang He and Junbai Li  
Chemical Society Reviews 2012 vol. 41(Issue 9) pp:3584-3593
Publication Date(Web):16 Mar 2012
DOI:10.1039/C2CS15316E
Confined surface gradients consisting of polymer brushes have great potential in various applications such as microfluidic devices, sensors, and biophysical research. Among the available fabrication approaches, nanolithographies combined with self-assembled monolayers and surface-initiated polymerization have became powerful tools to engineer confined gradients or predefined complex gradients on the nanometre size. In this tutorial review, we mainly highlight the research progress of the fabrication of confined polymer brush gradients by using electron beam, laser, and probe-based nanolithographies and the physical base for these approaches. The application of these polymer brush gradients in biomedical research is also addressed.
Co-reporter:Yingjie Wu, Zhiguang Wu, Xiankun Lin, Qiang He, and Junbai Li
ACS Nano 2012 Volume 6(Issue 12) pp:10910
Publication Date(Web):November 15, 2012
DOI:10.1021/nn304335x
We demonstrate the first example of a self-propelled Janus polyelectrolyte multilayer hollow capsule that can serve as both autonomous motor and smart cargo. This new autonomous Janus capsule motor composed of partially coated dendritic platinum nanoparticles (Pt NPs) was fabricated by using a template-assisted layer-by-layer (LbL) self-assembly combined with a microcontact printing method. The resulting Janus capsule motors still retain outstanding delivery capacities and can respond to external stimuli for controllable encapsulation and triggered release of model drugs. The Pt NPs on the one side of the Janus capsule motors catalytically decompose hydrogen peroxide fuel, generating oxygen bubbles which then recoil the movement of the capsule motors in solution or at an interface. They could autonomously move at a maximum speed of above 1 mm/s (over 125 body lengths/s), while exerting large forces exceeding 75 pN. Also, these asymmetric hollow capsules can be controlled by an external magnetic field to achieve directed movement. This LbL-assembled Janus capsule motor system has potential in making smart self-propelling delivery systems.Keywords: autonomous motor; bubble propulsion; Janus capsule; layer-by-layer assembly; smart cargo
Co-reporter:Johannes Frueh, Gerald Reiter, Helmuth Möhwald, Qiang He, Rumen Krastev
Colloids and Surfaces A: Physicochemical and Engineering Aspects 2012 Volume 415() pp:366-373
Publication Date(Web):5 December 2012
DOI:10.1016/j.colsurfa.2012.08.070
Supported polyelectrolyte multilayer (PEM) thin films produced by layer-by-layer self assembly, show interesting phenomena upon elongation and release like lithography-free surface structuring, controlled wettability, and stimuli-responsive nanovalves. To understand these effects, the structure and orientation change of PEM, when exposed to linear elongation were investigated by means of pyrene labeled polystyrenesulphonate and polarized UV spectroscopy. The samples were prepared either in solution containing 0.5 M NaCl or in salt free solutions, deposited on sheets of PDMS rubber and elongated laterally up to 10%. Our results show, that if the PEM is produced in the presence of salt the PEM contains a local polarity, depending on the orientation of molecules within the PEM. Upon elongation, the differences in oriented local polarity disappear. In the case of PEM prepared in salt free condition, the polarity within the PEM is independent of the molecular orientation. Upon elongation the orientation of the transition dipole moment changes from isotropic to anisotropic. This effect is strongly enhanced by the presence of NaCl in the solutions from which the PEM were formed.Graphical abstractHighlights► The polyelectrolytes change their orientation upon elongation. ► The degree of orientation change depends on the ionic strength during preparation. ► The degree of directed local polarity depends on the preparation condition. ► The directed local polarity changes upon elongation.
Co-reporter:Mingjun Xuan; Zhiguang Wu; Jingxin Shao; Luru Dai; Tieyan Si
Journal of the American Chemical Society () pp:
Publication Date(Web):May 6, 2016
DOI:10.1021/jacs.6b00902
We describe fuel-free, near-infrared (NIR)-driven Janus mesoporous silica nanoparticle motors (JMSNMs) with diameters of 50, 80, and 120 nm. The Janus structure of the JMSNMs is generated by vacuum sputtering of a 10 nm Au layer on one side of the MSNMs. Upon exposure to an NIR laser, a localized photothermal effect on the Au half-shells results in the formation of thermal gradients across the JMSNMs; thus, the generated self-thermophoresis can actively drive the nanomotors to move at an ultrafast speed, for instance, up to 950 body lengths/s for 50 nm JMSNMs under an NIR laser power of 70.3 W/cm2. The reversible “on/off” motion of the JMSNMs and their directed movement along the light gradient can be conveniently modulated by a remote NIR laser. Moreover, dynamic light scattering measurements are performed to investigate the coexisting translational and rotational motion of the JMSNMs in the presence of both self-thermophoretic forces and strong Brownian forces. These NIR-powered nanomotors demonstrate a novel strategy for overcoming the necessity of chemical fuels and exhibit a significant improvement in the maneuverability of nanomotors while providing potential cargo transportation in a biofriendly manner.
Co-reporter:Yingjie Wu ; Xiankun Lin ; Zhiguang Wu ; Helmuth Möhwald
ACS Applied Materials & Interfaces () pp:
Publication Date(Web):
DOI:10.1021/am502458h
We present herein a novel hybrid, polymer-based motor that was fabricated by the template-assisted polyelectrolyte layer-by-layer (LbL) deposition of a thin gold layer on one side, followed by chemical immobilization of a catalytic enzyme. Such Janus capsule motors can self-propel at 0.1% peroxide fuel concentration at physiological temperature and have a higher speed as compared to Pt-based synthetic motors. They were exploited for encapsulation of the chemotherapeutic anticancer drug, doxorubicin, for navigation to target a cell layer by an external magnetic field, and for triggered drug release activated by NIR light. This work provides high potential in the development of multifunctional polymer-based engines for biomedical applications such as targeted drug delivery.
Co-reporter:Jingxin Shao, Caixia Wen, Mingjun Xuan, Hongyue Zhang, Johannes Frueh, Mingwei Wan, Lianghui Gao and Qiang He
Physical Chemistry Chemical Physics 2017 - vol. 19(Issue 3) pp:NaN2016-2016
Publication Date(Web):2016/12/02
DOI:10.1039/C6CP06787E
Lipid bilayer membranes supported on polyelectrolyte multilayers are widely used as a new biomembrane model that connects biological and artificial materials since these ultrathin polyelectrolyte supports may mimic the role of the extracellular matrix and cell skeleton in living systems. Polyelectrolyte multilayers were fabricated by a layer-by-layer self-assembly technique. A quartz crystal microbalance with dissipation was used in real time to monitor the interaction between phospholipids and polyelectrolytes in situ on a planar substrate. The surface properties of polyelectrolyte films were investigated by the measurement of contact angles and zeta potential. Phospholipid charge, buffer pH and substrate hydrophilicity were proved to be essential for vesicle adsorption, rupture, fusion and formation of continuous lipid bilayers on the polyelectrolyte multilayers. The results clearly demonstrated that only the mixture of phosphatidylcholine and phosphatidic acid (4:1) resulted in fluid bilayers on chitosan and alginate multilayers with chitosan as a top layer at pH 6.5. A coarse-grained molecular simulation study elucidated that the exact mechanism of the formation of fluid lipid bilayers resembles a “parachute” model. As the closest model to the real membrane, polyelectrolyte multilayer-cushioned fluid lipid bilayers can be appropriate candidates for application in biomedical fields.
Co-reporter:Yingjie Wu, Tieyan Si, Xiankun Lin and Qiang He
Chemical Communications 2015 - vol. 51(Issue 3) pp:NaN514-514
Publication Date(Web):2014/11/13
DOI:10.1039/C4CC07182D
The use of a near-infrared (NIR) laser for reversible modulation of a bubble-driven Janus polymer capsule motor is demonstrated. This process was mediated through illumination of the metal face of the Janus capsule motor at the critical concentration of peroxide fuel. Such an effective control of the propulsion of chemically powered microengines holds a considerable promise for diverse applications.
Co-reporter:Johannes Frueh, Gerald Reiter, Helmuth Möhwald, Qiang He and Rumen Krastev
Physical Chemistry Chemical Physics 2013 - vol. 15(Issue 2) pp:NaN488-488
Publication Date(Web):2012/10/31
DOI:10.1039/C2CP43302H
Polyelectrolyte multilayers (PEMs) deposited on flexible supports are promising candidates for many applications ranging from controlled wettability over stimuli responsive nanovalves to lithography free surface structuring. Since many potential applications involve elongation of these films, we investigated the effect of elongation on the PEM thickness and density with ellipsometry. To our surprise PEM films with known amorphous internal structure show auxetic behavior that depends on the PEM preparation condition. The measured refractive index was compared with simulated values using the Garnet equation to evaluate if the incorporation of water or air causes the observed phenomena.
Co-reporter:Yingjie Wu, Johannes Frueh, Tieyan Si, Helmuth Möhwald and Qiang He
Physical Chemistry Chemical Physics 2015 - vol. 17(Issue 5) pp:NaN3286-3286
Publication Date(Web):2014/12/09
DOI:10.1039/C4CP05231E
In this study we investigated the effect of laser-induced membrane fusion of polyelectrolyte multilayer (PEM) based microcapsules bearing surface-attached gold nanoparticles (AuNPs) in aqueous media. We demonstrate that a dense coating of the capsules with AuNPs leads to enhanced light absorption, causing an increase of local temperature. This enhances the migration of polyelectrolytes within the PEMs and thus enables a complete fusion of two or more capsules. The encapsulated substances can achieve complete merging upon short-term laser irradiation (30 s, 30 mW @ 650 nm). The whole fusion process is followed by optical microscopy and scanning electron microscopy. In control experiments, microcapsules without AuNPs do not show a significant capsule fusion upon irradiation. It was also found that the duration of capsule fusion is affected by the density of AuNPs on the shell – the higher the density of AuNPs the shorter the fusion time. All these findings confirm that laser-induced microcapsule fusion is a new type of membrane fusion. This effect helps to study the interior exchange reactions of functional microcapsules, micro-reactors and drug transport across multilayers.
Co-reporter:Meiyu Gai, Johannes Frueh, Narisu Hu, Tieyan Si, Gleb B. Sukhorukov and Qiang He
Physical Chemistry Chemical Physics 2016 - vol. 18(Issue 5) pp:NaN3401-3401
Publication Date(Web):2016/01/11
DOI:10.1039/C5CP07697H
This communication sheds light on the production method and motion patterns of autonomous moving bubble propelled two dimensional micro-plate motors. The plate motors are produced by the well-known layer-by-layer self-assembly process in combination with micro-contact printing. The motion analysis covers instances of oscillating bubble development on one or more nucleation sites, which influence the motion speed and direction.
Co-reporter:Xiankun Lin, Qiang He and Junbai Li
Chemical Society Reviews 2012 - vol. 41(Issue 9) pp:NaN3593-3593
Publication Date(Web):2012/03/16
DOI:10.1039/C2CS15316E
Confined surface gradients consisting of polymer brushes have great potential in various applications such as microfluidic devices, sensors, and biophysical research. Among the available fabrication approaches, nanolithographies combined with self-assembled monolayers and surface-initiated polymerization have became powerful tools to engineer confined gradients or predefined complex gradients on the nanometre size. In this tutorial review, we mainly highlight the research progress of the fabrication of confined polymer brush gradients by using electron beam, laser, and probe-based nanolithographies and the physical base for these approaches. The application of these polymer brush gradients in biomedical research is also addressed.
Poly(ethylene glycol) methyl ether thiol (Mn 1000)
sodium 2-(4-(1,3-dibutyltetrahydro-4,6-dioxo-2-thioxo-5(2H)-pyrimidinylidene)-2-butenylidene)-3(2H)-benzoxazolepropane sulfonate
Poly(benzo[1,2-d:5,4-d']bisoxazole-2,6-diyl-1,4-phenylene)
POLY-L-LYSINE HYDROCHLORIDE
sodium yttrium(3+) tetrafluoride
Streptavidin
Adriamycin