Co-reporter:Jia Tian, Lei Xu, Yudong Xue, Xiaoze Jiang, and Weian Zhang
Biomacromolecules December 11, 2017 Volume 18(Issue 12) pp:3992-3992
Publication Date(Web):October 16, 2017
DOI:10.1021/acs.biomac.7b01037
Drug resistance is a primary obstacle that seriously reduces the therapy efficiency of most chemotherapeutic agents. To address this issue, the photochemical internalization (PCI) was employed to help the anticancer drug escape from lysosome and improve their translocation to the nucleus. A pH-sensitive porphyrin-based amphiphilic block copolymer (PEG113-b-PCL54-a-porphyrin) was synthesized, which was acted not only as a carrier for the delivery of DOX but also as a photosensitizer for PCI. PEG113-b-PCL54-a-porphyrin as a drug carrier exhibited a higher drug loading capacity, entrapment efficiency, and DOX release content. The PCI effect of PEG113-b-PCL54-a-porphyrin was studied by confocal laser scanning microscopy, and the results showed that most of DOX could be translocated into the nucleus for DOX-loaded PEG113-b-PCL54-a-porphyrin micelles. Moreover, the IC50 of pH-sensitive DOX-loaded PEG113-b-PCL54-a-porphyrin micelles was much lower than that of its counterpart without pH-responsiveness, DOX-loaded PEG113-b-PCL54-porphyrin micelles. Therefore, this drug delivery system based on pH-sensitive porphyrin-containing block copolymer would act as a potential vehicle for overcoming drug resistance in chemotherapy.
Co-reporter:Pengcheng Zhang, Zhenghe Zhang, Xiaoze Jiang, Leilei Rui, Yun Gao, Weian Zhang
Polymer 2017 Volume 118(Volume 118) pp:
Publication Date(Web):2 June 2017
DOI:10.1016/j.polymer.2017.04.063
•We synthesized a biotin-functionalized POSS-(PCL-b-PDMAEMA)8-biotin copolymer by ROP and RAFT polymerization.•Owning to the unique amphiphilic star-shaped architecture, this copolymer could form uniform unimolecular micelles.•The biotin-functionalized micelles were responsive to pH and further utilized in encapsulation and release of PPa for PDT.•PPa-loaded tumor-targeted unimolecular micelles could boost the internalization rate in HeLa cells effectively.A biotin-functionalized amphiphilic star-shaped block copolymer, POSS-(PCL-b-PDMAEMA)8-biotin, with an inorganic POSS nucleus, a hydrophobic poly(ɛ-caprolactone) (PCL) middle layer, a hydrophilic poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) outer corona was synthesized for the targeting delivery and pH-responsive release of hydrophobic pheophorbide A (PPa) photosensitizers. In aqueous solution, this amphiphilic copolymer was able to form unimolecular micelles as determined by transmission electron microscopy (TEM) and dynamic light scattering (DLS). The biotin-functionalized unimolecular micelles were responsive to pH and further utilized in encapsulation and release of PPa for photodynamic therapy (PDT). The PPa release from PPa-loaded unimolecular micelles could be enhanced at acidic condition. Additionally, confocal laser scanning microscopy (CLSM) and flow cytometry results revealed that PPa-loaded tumor-targeted unimolecular micelles could boost the internalization rate in HeLa cells effectively. Moreover, PPa-loaded unimolecular micelles showed low dark toxicity and high PDT efficacy towards HeLa cells according to the 3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide (MTT) assay. Thus, PPa-loaded POSS-(PCL-b-PDMAEMA)8-biotin would have presented the potential application in PDT.Download high-res image (214KB)Download full-size image
Co-reporter:Leilei Rui;Yudong Xue;Yong Wang;Yun Gao
Chemical Communications 2017 vol. 53(Issue 21) pp:3126-3129
Publication Date(Web):2017/03/09
DOI:10.1039/C7CC00950J
A mitochondria-targeting supramolecular photosensitizer system TPP-QAS/WP5/DTAB was constructed based on a host–guest inclusion complex. The supramolecular system could efficiently release and activate TPP-QASs in an acidic environment, which have been demonstrated to preferentially accumulate in mitochondria. Singlet oxygen (1O2) could be in situ generated in mitochondria under light irradiation, further enhancing the PDT efficacy.
Co-reporter:Yong Zhang;Tao Yue;Hongliang Cao; Yun Gao; Weian Zhang
Asian Journal of Organic Chemistry 2017 Volume 6(Issue 8) pp:1034-1042
Publication Date(Web):2017/08/01
DOI:10.1002/ajoc.201700223
AbstractIn this study, we have synthesized a new photosensitive organic–inorganic POSS-containing hybrid porphyrin derivative (H2TPP−Azo−POSS), in which azobenzene was used as a bridge to conjugate the porphyrin and POSS, by using click chemistry. The self-assembly behavior of H2TPP−Azo−POSS was studied at different concentrations in CHCl3 and in CHCl3/n-hexane mixed solvent systems. Our results showed that the self-assembled morphology of H2TPP−Azo−POSS could be tuned by varying the concentration and polarity of the solvent. Spherical micelles and linear nanowires could be obtained in CHCl3, whilst vesicles could be formed in CHCl3/n-hexane mixtures with low polarities. The supramolecular self-assembled morphologies of H2TPP−Azo−POSS demonstrated a light-triggered transition behavior, whilst the size of the assembled aggregates decreased significantly under UV irradiation.
Co-reporter:Wenzhen Guo, Xiuwei Pan, Yuanhao Zhang, Haibo Cai, Weian Zhang
Materials Letters 2017 Volume 205(Volume 205) pp:
Publication Date(Web):15 October 2017
DOI:10.1016/j.matlet.2017.06.023
•A novel HA/GO hybrid hydrogels was first prepared by in-situ free-radical polymerization.•The hydrogels have adjustable mechanical property.•The hydrogels could support the expansion of CD34+ cells ex vivo.HA/GO hydrogels were prepared by methacrylated GO (MeGO) and methacrylated HA (MeHA) via an in-situ free radical polymerization, and then a series of HA/GO hydrogels with highly porous structure were obtained. All hydrogels exhibited excellent water absorption ability. Additionally, the elastic moduli of hydrogels were clearly enhanced by GO. CD34+ cells cultured on HA/GO-0.05 hydrogel showed higher expansion of CD34+ cells and CD34+CD38− cells compared to the other three hydrogels. Therefore, HA/GO-0.05 hydrogels have a potential for clinical-applied ex vivo expansion of hematopoietic stem cells.HA/GO hybrid hydrogels with adjustable mechanical property were prepared via an in-situ free-radical polymerization, and then utilized for ex vivo expansion of CD34+ cells. Subsequently, the influence of physical property of the hydrogels on ex vivo expansion of CD34+ cells was evaluated.Download high-res image (63KB)Download full-size image
Co-reporter:Chaochao Wang;Lichao Liu;Hongliang Cao
Biomaterials Science (2013-Present) 2017 vol. 5(Issue 2) pp:274-284
Publication Date(Web):2017/01/31
DOI:10.1039/C6BM00482B
Ligand-targeted cancer therapeutics has been developed to minimize non-specific cytotoxicity via ligand–drug conjugates during the past few decades. We present here the design and synthesis of a GSH-activated amphiphilic photosensitizer conjugated with galactose (TPP-S-S-Gal) for targeted photodynamic therapy. Furthermore, the galactoside photosensitizer as supramolecular amphiphiles can self-assemble into micelles, which can be applied in integrative cancer treatment with chemotherapy drugs such as camptothecin (CPT) encapsulated in the hydrophobic core of micelles. Upon reaction with free thiol GSH that is relatively abundant in tumor cells, disulfide bond cleavage occurs as well as the active photosensitizer TPP and chemotherapy drug CPT release, which can cause cell apoptosis. The in vitro biological assessment of TPP-S-S-Gal micelles against the A549 cell line was evaluated by MTT assay, flow cytometry and confocal scanning laser microscopy, respectively. According to the MTT assay, TPP-S-S-Gal micelles exhibited low dark toxicity and efficient integrative efficacy of PDT and chemotherapy towards A549 cells after light irradiation.
Co-reporter:Leilei Rui, Lichao Liu, Yong Wang, Yun Gao, and Weian Zhang
ACS Macro Letters 2016 Volume 5(Issue 1) pp:112
Publication Date(Web):December 30, 2015
DOI:10.1021/acsmacrolett.5b00900
A reduction-responsive supramolecular diblock copolymer was successfully constructed by the orthogonal assembly of two homopolymers in aqueous solution via pillar[5]arene-based host–guest interactions for the first time. The homopolymers, namely, polystyrene modified with ethyl viologen as the terminal group (PS-EV) and polyethylene glycol bearing pillar[5]arene (PEG-P[5]A), were synthesized via reversible addition–fragmentation chain transfer (RAFT) polymerization and coupling reaction, respectively. The supramolecular diblock copolymer can self-assemble into stable binary cell-like vesicles in aqueous solution, where a spherical micelle as the cell nucleus was embedded in a clear outer vesicle as the cell membrane. The cell-like vesicles can be disassembled into spherical aggregates through addition of reducing agent and further used for encapsulation and controlled release of model molecules.
Co-reporter:Ye Chen, Leilei Rui, Lichao Liu and Weian Zhang
Polymer Chemistry 2016 vol. 7(Issue 19) pp:3268-3276
Publication Date(Web):11 Apr 2016
DOI:10.1039/C6PY00505E
Supramolecular amphiphiles based on a pillar[5]arene with enhanced photodynamic therapy have been fabricated. Supramolecular amphiphiles based on host–guest complexation between a poly(ethylene glycol)-functionalized pillar[5]arene (PEG-P[5]A) and a pyridinium-terminated porphyrin derivative bearing a disulfide bond (TPPC6-SS-Py) could self-assemble into spherical micelles in aqueous solution with good colloidal stability as confirmed by transmission electron microscopy (TEM) and dynamic light scattering (DLS). Also, PEG-P[5]A/TPPC6-SS-Py micelles exhibited rapid release of porphyrin photosensitizers in a reducing environment. In addition, these micelles demonstrated nearly no toxicity in the dark but a higher photocytotoxicity upon light irradiation evaluated by the MTT assay. Flow cytometry and confocal laser scanning microscopy (CLSM) revealed a more effective cellular uptake property compared with free porphyrin. Therefore, novel reduction-responsive supramolecular amphiphiles with rapid drug release and superior cell internalization ability are constructed, which may provide a platform for drug delivery systems.
Co-reporter:Zhenghe Zhang, Pengcheng Zhang, Yong Wang and Weian Zhang
Polymer Chemistry 2016 vol. 7(Issue 24) pp:3950-3976
Publication Date(Web):02 May 2016
DOI:10.1039/C6PY00675B
Hybrid organic–inorganic materials comprised of well-defined polymers have been widely recognized for a variety of applications due to their extraordinary properties based on the combination of the different building compositions. During the past decades, many kinds of well-defined hybrid polymers with a variety of architectures have been constructed by polymerization in the presence of inorganic compositions, or by the coupling reaction of functional polymers with inorganic nanoparticles. Thus, techniques could be utilized for the preparation of well-defined organic–inorganic hybrid polymers, including controlled living radical polymerizations (CLRP), such as atom transfer radical polymerization (ATRP) and reversible addition–fragmentation chain transfer (RAFT) polymerization. Organic–inorganic hybrid polymers based on polyhedral oligomeric silsesquioxane (POSS), poly(dimethylsiloxane) (PDMS), silica nanoparticles, graphene, carbon nanotubes (CNTs) and fullerene will be discussed in this paper.
Co-reporter:Xiuwei Pan, Hao Gao, Guodong Fu, Yun Gao and Weian Zhang
RSC Advances 2016 vol. 6(Issue 28) pp:23471-23478
Publication Date(Web):26 Feb 2016
DOI:10.1039/C5RA27989E
Polyhedral oligomeric silsesquioxanes (POSS)-based hybrid hydrogels were successfully prepared via a fast azide-alkyne click reaction between octa-azido-functionalized POSS (OAPOSS) and alkyne-functionalized poly(ethylene glycol) (PEG). A series of hybrid POSS-PEG hydrogels with the highly ordered porous structures were achieved and the pore size could be well controlled by varying the PEG chain length to 3k, 6k and 10k. After immersing in phosphate buffered saline (PBS), POSS-PEG hydrogels exhibited a good water absorption capacity, and their swelling ratio increased with the increase of the PEG chain length. Rheological measurements indicated that all hydrogels exhibited the characteristics of an elastomer. The elastic modulus and ultimate stress (at break) were significantly enhanced with the increase of the PEG chain length which has been revealed by stress–strain mechanical analysis. In vitro cell culture showed that all POSS-PEG hydrogels could well support chondrocytes attachment, spreading and proliferation, especially for the POSS-PEG (10k) hydrogel. Thus, POSS-PEG hydrogels exhibited the potential for cartilage tissue engineering.
Co-reporter:Lei-Lei Rui, Hong-Liang Cao, Yu-Dong Xue, Li-Chao Liu, Lei Xu, Yun Gao, Wei-An Zhang
Chinese Chemical Letters 2016 Volume 27(Issue 8) pp:1412-1420
Publication Date(Web):August 2016
DOI:10.1016/j.cclet.2016.07.011
In recent years, cancer has been one of the leading causes of death in the world. Much effort has been devoted to developing cancer treatments. Photodynamic therapy (PDT) is a noninvasive therapeutic modality by combining the light of a specific wavelength, a photosensitizer (PS) and oxygen, which has been widely applied for the treatment of cancers. However, the application of PDT in clinic is greatly limited due to lack of tumor selectivity and often causing skin photosensitivity. The use of organic nanoparticles (NPs) as an advanced technology in the field of PDT shows a great promise to overcome these shortcomings. Therefore, in this review, we summarize several functional organic NPs as PS carriers that have been developed to enhance the efficacy of PDT against cancers.Theranostic organic nanoparticles developed as photosensitizer carriers to enhance the efficacy of photodynamic therapy.
Co-reporter:Qiang Zhou, Lei Xu, Feng Liu, Weian Zhang
Polymer 2016 Volume 97() pp:323-334
Publication Date(Web):5 August 2016
DOI:10.1016/j.polymer.2016.04.056
•Reduction-responsive POEGMA-b-PTPPC6SAM block copolymers were synthesized via RAFT polymerization.•POEGMA-b-PTPPC6SAM block copolymers could self-assemble into spherical micelles and vesicles.•POEGMA-b-PTPPC6SAM micelles had a higher photo-toxicity with a lower IC50 (porphyrin concentration below 3 μg/mL).A novel reduction-responsive porphyrin monomer bearing a disulfide bond (TPPC6SAM) was synthesized, and then it was utilized to construct a series of POEGMA-b-PTPPC6SAM block copolymers via reversible addition–fragmentation transfer (RAFT) polymerization with water-soluble and biocompatible monomer, oligo(ethylene glycol) methyl ether methacrylate (OEGMA). POEGMA-b-PTPPC6SAM block copolymers could self-assemble into spherical micelles and vesicles by varying the mass ratio of hydrophilic block to hydrophobic block. Confocal laser scanning microscopy (CLSM) and flow cytometry showed that POEGMA-b-PTPPC6SAM micelles could effectively accumulate in A549 cells, compared to that of free porphyrin. In addition, minimal dark toxicity and efficacious photo-toxicity in vitro were also evaluated by MTT assay. According to the result of MTT assay, POEGMA-b-PTPPC6SAM block copolymers had a higher photo-toxicity with a lower IC50 (below 3 μg/mL). Thus, reduction-responsive POEGMA-b-PTPPC6SAM block copolymers could well improve the release of porphyrin photosensitizers and enhance the efficiency of PDT.Schematic illustration for formation of POEGMA-b-PTPPC6SAM aggregates including spherical micelles and vesicles, and their enhanced cellular internalization for PDT.Figure optionsDownload full-size imageDownload as PowerPoint slide
Co-reporter:Zhenghe Zhang, Yudong Xue, Pengcheng Zhang, Axel H. E. Müller, and Weian Zhang
Macromolecules 2016 Volume 49(Issue 22) pp:8440-8448
Publication Date(Web):November 11, 2016
DOI:10.1021/acs.macromol.6b02414
A novel amphiphilic diblock copolymer, PHEMAPOSS-b-P(DMAEMA-co-CMA), was prepared via reversible addition–fragmentation chain transfer (RAFT) polymerization, where PHEMAPOSS block was first synthesized using a methacrylate monomer based on polyhedral oligomeric silsesquioxane (HEMAPOSS), and PHEMAPOSS was further utilized to prepare the block copolymer via RAFT copolymerization of 2-(dimethylamino)ethyl methacrylate (DMAEMA) and reduction-cleavable coumarin methacrylate (CMA) monomer. PHEMAPOSS-b-P(DMAEMA-co-CMA) could self-assemble in water to form spherical micelles with POSS core and stimuli-responsive shell. The micelles were cross-linked by photodimerization of coumarin, and then hollow polymeric capsules could be finally obtained via etching the POSS core in the solution of hydrofluoric acid (HF). The morphologies of the micelles and hollow polymeric capsules were well characterized by TEM, SEM, and DLS. The hollow polymeric capsules are responsive to typical physiological stimuli such as pH, and redox potential, and could be further utilized in the encapsulation and release of tetraphenylporphyrin tetrasulfonic acid hydrate (TPPS) for photodynamic therapy (PDT). The in vitro release of TPPS-loaded polymeric capsules allowed a relatively low TPPS release at pH = 7.4. However, a burst release of TPPS was observed in the presence of 10 mM glutathione (GSH) at pH = 5.5. Confocal laser scanning microscopy (CLSM) confirmed that TPPS-loaded polymeric capsules could well improve the internalization rate in MCF-7 cells. According to the result of MTT assay, TPPS-loaded polymeric capsules demonstrated efficient PDT efficacy and low dark toxicity toward MCF-7 cells. Thus, TPPS-loaded polymeric capsules have presented potential application in PDT.
Co-reporter:Lei Xu, Wenyan Zhang, Haibo Cai, Feng Liu, Yong Wang, Yun Gao and Weian Zhang
Journal of Materials Chemistry A 2015 vol. 3(Issue 37) pp:7417-7426
Publication Date(Web):19 Aug 2015
DOI:10.1039/C5TB01363A
A light-controlled porphyrinic photosensitizer release system was developed based on host–guest TPP–Azo/PEG–β-CD supramolecular amphiphiles, which could significantly enhance the efficiency of photodynamic therapy. TPP–Azo was prepared via esterification between TPP and Azo derivatives, and further used to construct supramolecular amphiphiles with PEG–β-CD. TEM images showed that TPP–Azo/PEG–β-CD amphiphiles can self-assemble into spherical micelles, and then disaggregate under irradiation with 365 nm UV light. The phototoxicity and bio-distribution of TPP–Azo/PEG–β-CD micelles against the MCF-7 cell line were also evaluated by MTT assay, flow cytometry and confocal scanning laser microscopy, respectively. According to MTT assay, the IC50 of the spherical micelle was 31.2 μg mL−1, but it became 20.6 μg mL−1 upon pre-irradiation with 365 nm UV light. This shows for the first time that UV light can well stimulate the release of porphyrin photosensitizers and improve the photodynamic therapy efficiency based on the system of host–guest supramolecular amphiphiles.
Co-reporter:Lei Xu, Lichao Liu, Feng Liu, Wen Li, Ruobin Chen, Yun Gao and Weian Zhang
Journal of Materials Chemistry A 2015 vol. 3(Issue 15) pp:3062-3071
Publication Date(Web):25 Feb 2015
DOI:10.1039/C5TB00276A
OEGylation of porphyrins via a disulfide linkage to form a novel class of dendritic porphyrin photosensitizers (PSs) is presented. These amphiphilic PSs possess precise molecular structures which could self-assemble into spherical aggregates in aqueous solutions. Their thermoresponsiveness was investigated using UV-Vis spectroscopy, and their reduction responsive properties were inspected using dynamic light scattering and TEM measurements. Moreover, the uptake of porphyrin-containing dendritic micelles by cells and release of reduction-sensitive PSs were investigated using flow cytometry and confocal laser scanning microscopy. The results showed that the cellular uptake of dendritic micelles was more than that of free porphyrin and the uptake process was time-dependent. Additionally, the phototoxicity of these dendritic PS micelles was investigated by MTT assay. It was found that dendritic micelles exhibited efficient phototoxicity to cancer cells while the free porphyrin had nearly no toxicity under light irradiation. All results indicate that these dendritic PSs are promising for photodynamic therapy.
Co-reporter:Bin Wu, Lei Xu, Shangfeng Wang, Yong Wang and Weian Zhang
Polymer Chemistry 2015 vol. 6(Issue 23) pp:4279-4289
Publication Date(Web):15 May 2015
DOI:10.1039/C5PY00390C
We herein reported a click strategy to fabricate two kinds of colorimetric and turn-on fluorescent dual-modal mercury sensors (PEG-DMS) based on the styryl BODIPY scaffold attached to a hydrophilic polymer PEG, where the PEG chain could effectively improve the water solubility of these two mercury sensors and mean that their Hg2+ detection could be performed in pure water, while their corresponding small molecular precursor DMS could only detect Hg2+ in the mixed medium with a large amount of organic solvent. It is interesting that PEG-DMS exhibits an excellent spectral response to Hg2+ by inhibiting the intramolecular charge transfer (ICT) effect from the Hg2+ specific ligand, dithia-dioxa-aza cyclopentadecane, to the BODIPY core. Upon addition of Hg2+, a significant fluorescence enhancing property in conjunction with a visible colorimetric change can be observed. These two sensors are highly selective for Hg2+ over other common cations, whereas PEG-DMS1 with one Hg2+ binding ligand exhibits higher sensitivity than PEG-DMS2 with two Hg2+ binding ligands. Additionally, the sensor could be used as a potential imaging reagent for the detection of Hg2+ uptake in HeLa cells as revealed by confocal laser scanning microscopy (CLSM).
Co-reporter:Shangfeng Wang, Bin Wu, Feng Liu, Yun Gao and Weian Zhang
Polymer Chemistry 2015 vol. 6(Issue 7) pp:1127-1136
Publication Date(Web):24 Oct 2014
DOI:10.1039/C4PY01298D
We herein report a new strategy to fabricate novel well-defined alternating copolymers of poly(VBCDEG-alt-SaAEMI)s which were synthesized via alternating RAFT copolymerization of para-methoxydiethylene glycol-substituted styrenes (VBCDEG) and N-(2-salicylaldehyde-aminoethyl)maleimides (SaAEMI). 1H NMR, 13C NMR, FTIR and GPC results indicate that poly(VBCDEG-alt-SaAEMI) copolymers have well-defined alternating structures and narrow polydispersity (Mw/Mn < 1.35). It is interesting that poly(VBCDEG-alt-SaAEMI) alternating copolymers exhibit an excellent selective fluorescence “OFF–ON” response to Zn2+ by inhibiting the photoinduced electron transfer (PET) effect through copolymerization, while the monomer SaAEMI almost has no fluorescence response to Zn2+ due to the PET process. The sensors based on poly(VBCDEG-alt-SaAEMI) alternating copolymers have very fast response (30 s) to Zn2+, 62-fold fluorescence enhancement in aqueous solution and a detection limit of about 0.25 μM. Additionally, the poly(VBCDEG-alt-SaAEMI) alternating copolymers also show a remarkable green fluorescence “OFF–ON” switch (230∼fold) when the pH turns from 11 to 12, thus these copolymers have potential application in dual-color detection.
Co-reporter:Lichao Liu, Leilei Rui, Yun Gao and Weian Zhang
Polymer Chemistry 2015 vol. 6(Issue 10) pp:1817-1829
Publication Date(Web):12 Dec 2014
DOI:10.1039/C4PY01289E
Stimuli-responsive block copolymer micelles have recently emerged as promising drug delivery systems with controllable drug release. Herein, we report well-defined redox-responsive ferrocene-containing amphiphilic block copolymers PEG-b-PMAEFc, which were synthesized by the atom transfer radical polymerization (ATRP) of 2-(methacryloyloxy) ethyl ferrocene-carboxylate (MAEFc) using a PEG-based macro-ATRP agent. These block copolymers can self-assemble into various interesting nanostructures in aqueous solution. The self-assembled morphology of amphiphilic block copolymers is influenced by the nature of the common solvents used, the polymer composition and concentration, and the addition of β-cyclodextrin (β-CD) and redox agents (H2O2 and KMnO4), the effects of which were investigated by transmission electron microscopy (TEM) and dynamic light scattering (DLS). Furthermore, the redox agent H2O2 can be used to trigger the release of encapsulated cargo (Rhodamine B) in the polymeric nanocarriers. This redox behavior of the amphiphiles could open up an approach for redox-controlled drug delivery systems.
Co-reporter:Lei Xu, Lichao Liu, Feng Liu, Haibo Cai and Weian Zhang
Polymer Chemistry 2015 vol. 6(Issue 15) pp:2945-2954
Publication Date(Web):25 Feb 2015
DOI:10.1039/C5PY00039D
Amphiphilic PNIPAM-b-PTPPC6MA block copolymers were first synthesized using porphyrin-containing monomers. The mono-hydroxylphenyl-triphenylporphyrin photosensitizer, TPP-OH, was modified into a porphyrin monomer, and it was further used to construct the amphiphilic PNIPAM-b-PTPPC6MA block copolymers using RAFT polymerization. PNIPAM-b-PTPPC6MA block copolymers can self-assemble into a plethora of morphologies ranging from spheres to vesicular aggregates and further to a single large vesicle. The PNIPAM-b-PTPPC6MA micelles exhibited a high singlet oxygen quantum yield. Moreover, confocal laser scanning microscopy (CLSM) and flow cytometry analysis confirmed that PNIPAM-b-PTPPC6MA micelles could effectively enhance the internalization rate in MCF-7 cells. According to the MTT assay, PNIPAM-b-PTPPC6MA micelles exhibited low dark toxicity and efficient PDT efficacy towards MCF-7 cells. Thus PNIPAM-b-PTPPC6MA block copolymers have the potential application for photodynamic therapy.
Co-reporter:Feng Liu, Yufei Ma, Lei Xu, Lichao Liu and Weian Zhang
Biomaterials Science 2015 vol. 3(Issue 8) pp:1218-1227
Publication Date(Web):28 May 2015
DOI:10.1039/C5BM00045A
A supramolecular photosensitizer delivery system has been established through the self-assembly of supramolecular amphiphiles constructed by the host–guest interaction between poly(ethylene glycol)-β-cyclodextrin (PEG-β-CD) and adamantane-terminated porphyrin derivatives bearing a disulfide bond (TPPC6-SS-Ada). TPPC6-SS-Ada/PEG-β-CD supramolecular amphiphiles can self-assemble into spherical micelles in water, and the assembled morphology was respectively characterized by transmission electron microscopy (TEM) and dynamic light scattering (DLS). Intracellular uptake and localization of supramolecular photosensitizers were further investigated by flow cytometry and confocal laser scanning microscopy (CLSM), and the result indicated that TPPC6-SS-Ada/PEG-β-CD micelles could be effectively up-taken by MCF-7 cells. Furthermore, the phototoxicity evaluated by an MTT assay showed that TPPC6-SS-Ada/PEG-β-CD micelles have very low dark toxicity but greater photo-toxicity compared to free porphyrin. Thus, TPPC6-SS-Ada/PEG-β-CD micelles would provide the potential application for photosensitizer delivery.
Co-reporter:Zhenghe Zhang, Lizhi Hong, Jinxia Li, Feng Liu, Haibo Cai, Yun Gao and Weian Zhang
RSC Advances 2015 vol. 5(Issue 28) pp:21580-21587
Publication Date(Web):06 Feb 2015
DOI:10.1039/C4RA15492D
Poly(maleimide isobutyl polyhedral oligomeric silsesquioxane-alt-vinylbenzyl polyethylene glycol) (P(MIPOSS-alt-VBPEG)) amphiphilic copolymer brushes with a sequence of alternating MIPOSS and polyethylene glycol (PEG) side chains were synthesized via ordinary radical polymerization and reversible addition–fragmentation transfer (RAFT) polymerization. A series of alternating copolymer brushes prepared by RAFT polymerization had a low polydispersity index (PDI) of less than 1.25. The thermal properties of these copolymers were evaluated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The results displayed that the MIPOSS units could effectively enhance the thermal properties of the hybrid copolymers. The self-assembly behavior of the P(MIPOSS-alt-VBPEG) amphiphilic copolymer brushes in aqueous media was also studied by fluorescence spectrophotometry (FS), transmission electron microscopy (TEM) and dynamic light scattering (DLS). The results showed that these alternating copolymer brushes could form spherical aggregates in water.
Co-reporter: Feng Liu;Yuan Zhang;Lei Xu ; Weian Zhang
Chemistry - A European Journal 2015 Volume 21( Issue 14) pp:5540-5547
Publication Date(Web):
DOI:10.1002/chem.201405334
Abstract
An organic/inorganic hybrid porphyrin derivative, namely, metal-free tetrakisphenyl porphyrin–polyhedral oligomeric silsesquioxanes (H2TPP-POSS) was synthesized by azide–alkyne click chemistry. The self-assembly behavior of H2TPP-POSS was systematically studied in CHCl3 at different concentrations and in solvents with different polarities. Novel nanovesicles could be obtained through the self-assembly of H2TPP-POSS in CHCl3 at a concentration lower than 10−4 m. Diffuse microrods formed at a concentration higher than 10−4 M. Additionally, the polarity of the solvent also greatly influenced the assembled morphologies, and a series of assembled morphologies, including crescent-shaped micelles, spherical micelles, doughnut-shaped vesicles, and ordered square sheets, could form in solvents with different polarities.
Co-reporter:Zhenghe Zhang, Lizhi Hong, Yun Gao and Weian Zhang
Polymer Chemistry 2014 vol. 5(Issue 15) pp:4534-4541
Publication Date(Web):07 Apr 2014
DOI:10.1039/C4PY00302K
The poly(styrene-alt-maleimide isobutyl POSS) (PSMIPOSS) alternating copolymer is one-pot synthesized via reversible addition-fragmentation transfer (RAFT) polymerization. The results show that a POSS-containing alternating copolymer with a high degree of polymerization (DP) and a low polydispersity index (PDI) is successfully constructed by alternating copolymerization of maleimide isobutyl POSS with styrene, and the molecular weight of the PSMIPOSS alternating copolymer can be well controlled by the amount of RAFT agent. Poly(styrene-alt-maleimide isobutyl POSS)-block-polystyrene (PSMIPOSS-b-PS) block copolymers are also one-pot prepared by RAFT polymerization, and their self-assembly behavior in the bulk is investigated by transmission electron microscopy (TEM) and small angle X-ray scattering (SAXS), which exhibit a series of short-range order phase transitions from the POSS sphere, POSS cylinder to lamella structures with the weight fraction of MIPOSS ranging from 13% to 64%. The thermal properties of POSS-containing copolymers are evaluated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), respectively. The results display that MIPOSS units can enhance the thermal properties of copolymers effectively.
Co-reporter:Lichao Liu, Leilei Rui, Yun Gao and Weian Zhang
Polymer Chemistry 2014 vol. 5(Issue 18) pp:5453-5460
Publication Date(Web):27 Jun 2014
DOI:10.1039/C4PY00645C
Self-assembly of stimuli-responsive block copolymers in aqueous solution has attracted considerable attention in the past few decades. Herein, we report a supramolecular modular synthetic approach for the fabrication of photo-responsive block-controllable supramolecular polymers (BSPs) based on the assembly of two homopolymers in water. The homopolymers, namely, the polystyrene modified with adamantane and azobenzene as the end groups (Ad–PS–Azo) and poly(ethylene glycol) modified with β-CD (PEG–β-CD), were successfully synthesized via atom transfer radical polymerization (ATRP) and click chemistry, respectively. The supramolecular triblock copolymer (STP) was constructed through host–guest interactions between β-CD and Ad/Azo moieties, and further self-assembled into micelles in aqueous solution, which were investigated by transmission electron microscopy (TEM) and dynamic light scattering (DLS). This well-defined supramolecular triblock copolymer can reversibly disassemble into a supramolecular diblock copolymer (SDP) by alternating irradiation of UV/visible light, which was revealed by TEM, UV-vis and 1H NMR.
Co-reporter:Feng Wang, Lei Xu, Mian Hasnain Nawaz, Feng Liu and Weian Zhang
RSC Advances 2014 vol. 4(Issue 106) pp:61378-61382
Publication Date(Web):10 Nov 2014
DOI:10.1039/C4RA10087E
We synthesized (5,10,15,20-tetrakisphenyl-porphine) zinc (ZnTPP), and investigated its self-assembly behaviour with 4,4′-bipyridine (Bipy) via different self-assembly protocols. The self-assembly experiments were performed in organic solvents and on a carbon-coated copper grid, which gave well-defined nanospheres and microrings, respectively.
Co-reporter:Lizhi Hong, Zhenghe Zhang, and Weian Zhang
Industrial & Engineering Chemistry Research 2014 Volume 53(Issue 26) pp:10673-10680
Publication Date(Web):2017-2-22
DOI:10.1021/ie501517m
Polyhedral oligomeric silsesquioxane (POSS)-containing homopolymers (PHEMAPOSS) with a high degree of polymerization (DP) were synthesized via reversible addition–fragmentation chain transfer (RAFT) polymerization. PHEMAPOSS was used as a macro-RAFT agent to construct a series of amphiphilic diblock copolymers, PHEMPOSS-b-PMAA (poly (methyl methacrylate)), which possessed a different length of hydrophilic chains. The self-assembly behavior of PHEMPOSS-b-PMAA in aqueous solution was studied by transmission electron microscopy (TEM), atomic force microscopy (AFM), and dynamic light scattering (DLS), respectively. The results showed that PHEMAPOSS45-b-PMAA523 forms typical core–shell spherical micelles where the hydrophobic PHEMAPOSS blocks as the core and hydrophilic PMAA blocks as the shell. With increasing PMAA chain length, PHEMAPOSS45-b-PMAA1173 with a longer PMAA chain self-assembled into irregular aggregates with POSS moieties dispersed in the aggregates. On the other hand, PHEMAPOSS45-b-PMAA308 with a shorter hydrophilic PMAA chain could self-assemble into a dendritic cylinder structure.
Co-reporter:Weian Zhang;Lizhi Hong;Patrick C. McGowan
Macromolecular Chemistry and Physics 2014 Volume 215( Issue 9) pp:900-905
Publication Date(Web):
DOI:10.1002/macp.201400012
Co-reporter:Qiongxia Shen, Lichao Liu, and Weian Zhang
Langmuir 2014 Volume 30(Issue 31) pp:9361-9369
Publication Date(Web):2017-2-22
DOI:10.1021/la500792v
A novel surface-modification strategy has been developed for the construction of a photocontrolled silicon wafer surface with switchable wettability based on host–guest inclusion complexation. The silicon wafer was first modified by guest molecule azobenzene (Azo) via a silanization reaction. Subsequently, a series of polymers with different polarities were attached to host molecule β-cyclodextrin (β-CD) to prepare β-CD-containing hemitelechelic polymers via click chemistry. Finally, a photocontrolled silicon wafer surface modified with polymers was fabricated by inclusion complexation between β-CD and Azo, and the surface properties of the substrate are dependent on the polymers we used. The elemental composition, surface morphology, and hydrophilic/hydrophobic property of the modified surfaces were characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscope, and contact angle measurements, respectively. The antifouling property of the PEG-functionalized surface was evaluated by a protein adsorption assay using bovine serum albumin, which was also characterized by XPS. The results demonstrate that the surface modified with PEG possesses good protein-resistant properties.
Co-reporter:Lizhi Hong;Zhenghe Zhang;Yuan Zhang
Journal of Polymer Science Part A: Polymer Chemistry 2014 Volume 52( Issue 18) pp:2669-2683
Publication Date(Web):
DOI:10.1002/pola.27287
ABSTRACT
A novel POSS-containing methacrylate monomer (HEMAPOSS) was fabricated by extending the side chain between polyhedral oligomeric silsesquioxane (POSS) unit and methacrylate group, which can efficiently decrease the steric hindrance in free-radical polymerization of POSS-methacrylate monomer. POSS-containing homopolymers (PHEMAPOSS) with a higher degree of polymerization (DP) can be prepared using HEMAPOSS monomer via reversible addition–fragmentation chain transfer (RAFT) polymerization. PHEMAPOSS was further used as the macro-RAFT agent to construct a series of amphiphilic POSS-containing poly(N, N-dimethylaminoethyl methacrylate) diblock copolymers, PHEMAPOSS-b-PDMAEMA. PHEMAPOSS-b-PDMAEMA block copolymers can self-assemble into a plethora of morphologies ranging from irregular assembled aggregates to core-shell spheres and further from complex spheres (pearl-necklace-liked structure) to large compound vesicles. The thermo- and pH-responsive behaviors of the micelles were also investigated by dynamic laser scattering, UV spectroscopy, SEM, and TEM. The results reveal the reversible transition of the assembled morphologies from spherical micelles to complex micelles was realized through acid-base control. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 2669-2683
Co-reporter:Weian Zhang, Axel H.E. Müller
Progress in Polymer Science 2013 Volume 38(Issue 8) pp:1121-1162
Publication Date(Web):August 2013
DOI:10.1016/j.progpolymsci.2013.03.002
Well-defined hybrid polymers based on polyhedral oligomeric silsequioxane (POSS) with a variety of architectures have been developed, including telechelic polymers, block copolymers and star-shaped polymers. The synthesis, self-assembly and properties of this kind of materials are reviewed. Well-defined POSS-containing hybrid polymers can be constructed by living polymerization techniques, such as ring-opening polymerization and living free-radical polymerization or the combination of living polymerization and coupling reactions, such as click chemistry and hydrosilylation. The self-assembly behavior of well-defined POSS-containing hybrid polymers is also described in detail. The POSS-containing hybrid polymers can self-assemble into nano-scaled aggregates in selective solvents, and form nanostructures in bulk. Some of the interesting self-assembly morphologies are remarkably different from those formed from the conventional purely organic amphiphilic polymers. Well-defined POSS-containing hybrid polymers have shown the unexpected properties, which lead to unlimited possibilities for promising applications, such as biomedicine, electronic, optical, magnetic nanodevices, sensors and stimulated catalysts. We highlight several recent examples of these applications.
Co-reporter:Shaohua Wang, Qiongxia Shen, Mian Hasnain Nawaz and Weian Zhang
Polymer Chemistry 2013 vol. 4(Issue 6) pp:2151-2157
Publication Date(Web):04 Feb 2013
DOI:10.1039/C3PY21148G
The double hydrophobic block copolymer, poly[6-(4-(phenyldiazenyl)phenoxy)hexyl acrylate]-b-polystyrene (PAzo-b-PS), was synthesized by reversible addition–fragmentation chain transfer (RAFT) polymerization. This hydrophobic block copolymer can self-assemble into spherical micelles through β-cyclodextrin–azobenzene (β-CD–Azo) host–guest inclusion. Furthermore, the spherical micelles can be dissociated and reassembled by alternating irradiation of UV/visible light. These supramolecular self-assembly and disassembly procedures were studied by dynamic light scattering (DLS), atomic force microscopy (AFM), transmission electron microscopy (TEM) and UV-Vis spectra.
Co-reporter:Mian Hasnain Nawaz, Lei Xu, Feng Liu and Weian Zhang
RSC Advances 2013 vol. 3(Issue 24) pp:9206-9209
Publication Date(Web):01 May 2013
DOI:10.1039/C3RA41812J
We synthesized monochelic porphyrinic polystyrene (MPPS) and investigated its self-assembly with PEGylated fullerene (F-PEO) and pristine fullerene (C60), separately. Continuous fibrils and spherical aggregates were observed on complexation of MPPS with F-PEO and pristine C60 respectively.
Co-reporter:Mian Hasnain Nawaz, Jin Liu, Feng Liu, Xiaosong Wang, Weian Zhang
Materials Letters 2013 Volume 91() pp:71-74
Publication Date(Web):15 January 2013
DOI:10.1016/j.matlet.2012.09.053
Four-arm porphyrinic polystyrenes (TPP-PS) were prepared with well controlled and low dispersity, by reversible addition fragmentation chain transfer (RAFT) polymerization, and their self-assembly morphology with fullerene (C60) was investigated. Monodisperse nanospheres of porphyrin–fullerene complexes were obtained in organic solvents, which showed morphological changes (shrinkage–swelling) under different parameters (concentration, solvent and polymeric chain length). The optimized parameters gave well controlled and convenient fabrication of monodisperse nanospheres which were confirmed in both solution and dry phases. Optical studies (UV/Vis and fluorescence) confirmed the inter-molecular interactions between porphyrin and fullerene, while transmission electron microscopy gave insight into the morphology of monodisperse nanospheres.Graphical abstractFour-arm porphyrinic polystyrenes were prepared by RAFT polymerization with different chain lengths, which were further studied for their self-assembly behavior with fullerene. The monodisperse nanospheres were obtained, showing morphological changes under different parameters, which were characterized by spectroscopic techniques.Highlights► Four-arm porphyrin polystyrenes were synthesized and self-assembled with C60. ► Monodisperse nanospheres were obtained in organic solvents. ► Effects of different parameters on morphology were studied. ► Nanospheres showed swelling-shrinkage properties under different solvents. ► Molecular interactions and morphology were studied by UV/fluorescence and TEM studies.
Co-reporter:Weian Zhang, Shaohua Wang, Xiaohui Li, Jiayin Yuan, Shaolei Wang
European Polymer Journal 2012 Volume 48(Issue 4) pp:720-729
Publication Date(Web):April 2012
DOI:10.1016/j.eurpolymj.2012.01.019
The star-shaped organic/inorganic hybrid poly(l-lactide) (PLLA) based on polyhedral oligomeric silsesquioxane (POSS) was prepared using octa(3-hydroxypropyl) polyhedral oligomeric silsesquioxane as initiator via ring-opening polymerization (ROP) of l-lactide (LLA). The molecular weight of POSS-containing star-shaped hybrid PLLA (POSSPLLA) can be well controlled by the feed ratio of LLA to initiator. The POSSPLLA was further functionalized into the macromolecular reversible addition-fragmentation transfer (RAFT) agent for the polymerization of N-isopropylacrylamide (NIPAM), leading to the POSS-containing star-shaped organic/inorganic hybrid amphiphilic block copolymers, poly(l-lactide)–block–poly(N-isopropylacrylamide) (POSS(PLLA–b–PNIPAM)). The self-assembly behavior of POSS(PLLA–b–PNIPAM) block copolymers in aqueous solution was investigated by dynamic light scattering (DLS), transmission electron microscopy (TEM) and atomic force microscopy (AFM). DLS showed the PNIPAM block in the aggregates is temperature-responsive and its phase-transition is reversible. TEM proved that the star-shaped POSS(PLLA–b–PNIPAM) amphiphilic block copolymers can self-assemble into the vesicles in aqueous solution. The vesicular wall and coronas are composed of the hydrophobic POSS core and PLLA, and hydrophilic PNIPAM blocks, respectively. Therefore, POSSPLLA and POSS(PLLA–b–PNIPAM) block copolymers, as a class of novel organic–inorganic hybrid materials with the advantageous properties, can be potentially used in biological and medical fields.The star-shaped PLLA–b–PNIPAM block copolymers with a polyhedral oligomeric silsesquioxane (POSS) core was prepared via a combination of ring-opening polymerization (ROP) and RAFT polymerization. The PLLA–b–PNIPAM block copolymers can self-assemble into the vesicles in aqueous solution. PNIPAM block as the vesicular wall is temperature-responsive.
Co-reporter:Weian Zhang, Shaolei Wang, Jie Kong
Reactive and Functional Polymers 2012 72(9) pp: 580-587
Publication Date(Web):September 2012
DOI:10.1016/j.reactfunctpolym.2012.04.001
Co-reporter:Weian Zhang, Axel H.E. Müller
Polymer 2010 Volume 51(Issue 10) pp:2133-2139
Publication Date(Web):4 May 2010
DOI:10.1016/j.polymer.2010.03.028
Copper-catalyzed alkyne-azide “click chemistry” is applied in the preparation of tadpole-shaped (“monochelic”) POSS-end functional hybrid polymers by combining with ATRP and RAFT polymerization. Alkyne-functionalized ATRP initiator and RAFT agent were respectively synthesized and applied in the preparation of alkyne-terminal poly(methyl methacrylate) and polystyrene. The tadpole-shaped POSS-containing hybrid polymers are easily obtained by the click reaction with an azido-functional POSS molecule. This presents a novel and effective method to prepare POSS-containing hybrid polymers.
Co-reporter:Weian Zhang, Xiaodong Zhuang, Xiaohui Li, Ying lin, Jinrui Bai, Yu Chen
Reactive and Functional Polymers 2009 69(2) pp: 124-129
Publication Date(Web):February 2009
DOI:10.1016/j.reactfunctpolym.2008.11.009
Co-reporter:Weian Zhang;Li Liu;Xiaodong Zhuang;Xiaohui Li;Jinrui Bai;Yu Chen
Journal of Polymer Science Part A: Polymer Chemistry 2008 Volume 46( Issue 21) pp:7049-7061
Publication Date(Web):
DOI:10.1002/pola.23010
Abstract
Aminopropylisobutyl polyhedral oligomeric silsesquioxane (POSS) was used to prepare a POSS-containing reversible addition-fragmentation transfer (RAFT) agent. The POSS-containing RAFT agent was used in the RAFT polymerization of N-isopropylacrylamide (NIPAM) to produce tadpole-shaped organic/inorganic hybrid Poly(N-isopropylacrylamide) (PNIPAM). The results show that the POSS-containing RAFT agent was an effective chain transfer agent in the RAFT polymerization of NIPAM, and the polymerization kinetics were found to be pseudo-first-order behavior. The thermal properties of the organic/inorganic hybrid PNIPAM were also characterized by differential scanning calorimetry. The glass transition temperature (Tg) of the tadpole-shaped inorganic/organic hybrid PNIPAM was enhanced by POSS molecule. The self-assembly behavior of the tadpole-shaped inorganic/organic hybrid PNIPAM was investigated by atomic force microscopy and dynamic light scattering. The results show the core-shell nanostructured micelles with a uniform diameter. The diameter of the micelle increases with the molecular weight of the hybrid PNIPAM. Surprisingly, the micelle of the tadpole-shaped inorganic/organic hybrid PNIPAM with low molecular weight has a much bigger and more compact core than that with high molecular weight. © Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7049–7061, 2008
Co-reporter:Chaochao Wang, Lichao Liu, Hongliang Cao and Weian Zhang
Biomaterials Science (2013-Present) 2017 - vol. 5(Issue 2) pp:NaN284-284
Publication Date(Web):2016/12/12
DOI:10.1039/C6BM00482B
Ligand-targeted cancer therapeutics has been developed to minimize non-specific cytotoxicity via ligand–drug conjugates during the past few decades. We present here the design and synthesis of a GSH-activated amphiphilic photosensitizer conjugated with galactose (TPP-S-S-Gal) for targeted photodynamic therapy. Furthermore, the galactoside photosensitizer as supramolecular amphiphiles can self-assemble into micelles, which can be applied in integrative cancer treatment with chemotherapy drugs such as camptothecin (CPT) encapsulated in the hydrophobic core of micelles. Upon reaction with free thiol GSH that is relatively abundant in tumor cells, disulfide bond cleavage occurs as well as the active photosensitizer TPP and chemotherapy drug CPT release, which can cause cell apoptosis. The in vitro biological assessment of TPP-S-S-Gal micelles against the A549 cell line was evaluated by MTT assay, flow cytometry and confocal scanning laser microscopy, respectively. According to the MTT assay, TPP-S-S-Gal micelles exhibited low dark toxicity and efficient integrative efficacy of PDT and chemotherapy towards A549 cells after light irradiation.
Co-reporter:Hang Pan, Shangfeng Wang, Yudong Xue, Hongliang Cao and Weian Zhang
Chemical Communications 2016 - vol. 52(Issue 99) pp:NaN14211-14211
Publication Date(Web):2016/11/10
DOI:10.1039/C6CC07569J
A selenium-containing anticancer compound DSeMTTG was prepared, which could be self-assembled into a unimolecular amphiphilic drug nanoassembly (UADN) with good biocompatibility. The resulting UADN was sensitive to singlet oxygen produced by encapsulated porphyrin photosensitizers. Thus, the toxicity of DSeMTTG could be retrieved after visible light irradiation, which significantly inhibited the proliferation of A549 cells without using extra chemotherapeutic drugs.
Co-reporter:Weian Zhang ; Jiayin Yuan ; Stephan Weiss ; Xiaodong Ye ; Chunliang Li ;Axel H. E. Müller
Macromolecules () pp:
Publication Date(Web):August 10, 2011
DOI:10.1021/ma201152t
Telechelic (“dumbbell-shaped”) POSS-containing inorganic/organic hybrid poly(tert-butyl acrylate) (POSS-PtBA-POSS) was prepared by the combination of ATRP and the copper-catalyzed azide–alkyne “click” reaction. Telechelic bromoterminated PtBAs with different molecular weights were first prepared via ATRP using a dibromo-functionalized ATRP initiator; subsequently, the bromo groups were transformed to azido groups using sodium azide in DMF via nucleophilic substitution. The “click” coupling between azido-terminated PtBA and alkyne-functionalized POSS was successfully accomplished to afford telechelic POSS-PtBA-POSS, which is confirmed by NMR and GPC. The telechelic POSS-PtBA-POSS was then hydrolyzed to amphiphilic telechelic POSS-functional poly(acrylic acid) (POSS-PAA-POSS). The self-assembly behavior of POSS-PAA-POSS with three different molecular weights in aqueous solution at pH 8.5 was investigated by transmission electron microscopy, scanning electron microscopy, and light scattering (SLS, DLS). The results show that POSS-PAA40-POSS and POSS-PAA82-POSS can self-assemble in water into ellipsoidal aggregates with a moderately uniform size, whereas POSS-PAA140-POSS with a long PAA chain only self-assembles into aggregates with a broad size distribution. We discuss the formation of layered crystals of POSS within these aggregates.
Co-reporter:Lei Xu, Wenyan Zhang, Haibo Cai, Feng Liu, Yong Wang, Yun Gao and Weian Zhang
Journal of Materials Chemistry A 2015 - vol. 3(Issue 37) pp:NaN7426-7426
Publication Date(Web):2015/08/19
DOI:10.1039/C5TB01363A
A light-controlled porphyrinic photosensitizer release system was developed based on host–guest TPP–Azo/PEG–β-CD supramolecular amphiphiles, which could significantly enhance the efficiency of photodynamic therapy. TPP–Azo was prepared via esterification between TPP and Azo derivatives, and further used to construct supramolecular amphiphiles with PEG–β-CD. TEM images showed that TPP–Azo/PEG–β-CD amphiphiles can self-assemble into spherical micelles, and then disaggregate under irradiation with 365 nm UV light. The phototoxicity and bio-distribution of TPP–Azo/PEG–β-CD micelles against the MCF-7 cell line were also evaluated by MTT assay, flow cytometry and confocal scanning laser microscopy, respectively. According to MTT assay, the IC50 of the spherical micelle was 31.2 μg mL−1, but it became 20.6 μg mL−1 upon pre-irradiation with 365 nm UV light. This shows for the first time that UV light can well stimulate the release of porphyrin photosensitizers and improve the photodynamic therapy efficiency based on the system of host–guest supramolecular amphiphiles.
Co-reporter:Lei Xu, Lichao Liu, Feng Liu, Wen Li, Ruobin Chen, Yun Gao and Weian Zhang
Journal of Materials Chemistry A 2015 - vol. 3(Issue 15) pp:NaN3071-3071
Publication Date(Web):2015/02/25
DOI:10.1039/C5TB00276A
OEGylation of porphyrins via a disulfide linkage to form a novel class of dendritic porphyrin photosensitizers (PSs) is presented. These amphiphilic PSs possess precise molecular structures which could self-assemble into spherical aggregates in aqueous solutions. Their thermoresponsiveness was investigated using UV-Vis spectroscopy, and their reduction responsive properties were inspected using dynamic light scattering and TEM measurements. Moreover, the uptake of porphyrin-containing dendritic micelles by cells and release of reduction-sensitive PSs were investigated using flow cytometry and confocal laser scanning microscopy. The results showed that the cellular uptake of dendritic micelles was more than that of free porphyrin and the uptake process was time-dependent. Additionally, the phototoxicity of these dendritic PS micelles was investigated by MTT assay. It was found that dendritic micelles exhibited efficient phototoxicity to cancer cells while the free porphyrin had nearly no toxicity under light irradiation. All results indicate that these dendritic PSs are promising for photodynamic therapy.
Co-reporter:Feng Liu, Yufei Ma, Lei Xu, Lichao Liu and Weian Zhang
Biomaterials Science (2013-Present) 2015 - vol. 3(Issue 8) pp:NaN1227-1227
Publication Date(Web):2015/05/28
DOI:10.1039/C5BM00045A
A supramolecular photosensitizer delivery system has been established through the self-assembly of supramolecular amphiphiles constructed by the host–guest interaction between poly(ethylene glycol)-β-cyclodextrin (PEG-β-CD) and adamantane-terminated porphyrin derivatives bearing a disulfide bond (TPPC6-SS-Ada). TPPC6-SS-Ada/PEG-β-CD supramolecular amphiphiles can self-assemble into spherical micelles in water, and the assembled morphology was respectively characterized by transmission electron microscopy (TEM) and dynamic light scattering (DLS). Intracellular uptake and localization of supramolecular photosensitizers were further investigated by flow cytometry and confocal laser scanning microscopy (CLSM), and the result indicated that TPPC6-SS-Ada/PEG-β-CD micelles could be effectively up-taken by MCF-7 cells. Furthermore, the phototoxicity evaluated by an MTT assay showed that TPPC6-SS-Ada/PEG-β-CD micelles have very low dark toxicity but greater photo-toxicity compared to free porphyrin. Thus, TPPC6-SS-Ada/PEG-β-CD micelles would provide the potential application for photosensitizer delivery.
Co-reporter:Leilei Rui, Yudong Xue, Yong Wang, Yun Gao and Weian Zhang
Chemical Communications 2017 - vol. 53(Issue 21) pp:NaN3129-3129
Publication Date(Web):2017/02/16
DOI:10.1039/C7CC00950J
A mitochondria-targeting supramolecular photosensitizer system TPP-QAS/WP5/DTAB was constructed based on a host–guest inclusion complex. The supramolecular system could efficiently release and activate TPP-QASs in an acidic environment, which have been demonstrated to preferentially accumulate in mitochondria. Singlet oxygen (1O2) could be in situ generated in mitochondria under light irradiation, further enhancing the PDT efficacy.
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