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1.
Amphiphilic linear–hyperbranched polymer poly(ethylene glycol)–branched polyethylenimine–poly(?‐caprolactone) (PEG‐PEI‐PCL) was synthesized by progressively conjugating PEG (one chain) and PCL (multi‐chains) to PEI (hyperbranched architecture) with a yield of 87%. PEG‐PEI‐PCL forms nano‐sized uniform spherical micelles by self‐assembly in water. The micelles had an average diameter of 56 nm determined using dynamic light scattering and 35 nm observed from transmission electron microscopy images. PEG‐PEI‐PCL was used as a stabilizer of platinum nanoparticles (PtNPs) for the first time. The particle diameter of PEG‐PEI‐PCL‐stabilized PtNPs was 7.8 ± 1.4 nm. Amphiphilic (hydrophilic–hydrophilic–hydrophobic) and hyperbranched (linear–hyperbranched–grafted) structures enabled PtNPs to effectively stabilize and disperse in liquid‐phase synthesis. The highly disperse PtNPs in PEG‐PEI‐PCL micelles improved the catalytic activity for the reduction of 4‐nitrophenol with a catalytic yield of near 100%. © 2016 Society of Chemical Industry  相似文献   

2.
It is much importance to develop novel multifunctional delivery systems for the combination therapy of drug and gene. In this work, a novel conjugate, polyethylene glycol‐polyethylenimine‐tetrachloroplatinum (IV) (PEG‐PEI‐Pt), with good abilities of antitumor and gene delivery was proposed by combining PEG (Mw 3400 Da), low molecular weight PEI (Mw 800 Da), and tetrachloroplatinum (IV). The antitumoral and gene transfection activities of PEG‐PEI‐Pt were analyzed in many tumor (A549, A375, HepG‐2, HuH‐7, and B16 cells) and normal (COS‐7 cells) cell lines. Similar to cisplatin (one platinum anticancer drug), PEG‐PEI‐Pt showed much higher sensitivity in tumor cells than in normal cells. More importantly, PEG‐PEI‐Pt had a potential to treat drug‐resistant tumors. Almost no transfection efficiency was observed for PEI (Mw 800 Da) and PEG‐PEI. Very interestingly, PEG‐PEI‐Pt could condense plasmid DNA efficiently, and exhibited good transfection efficiency in B16, HepG‐2, A375 and COS‐7 cells, comparable to even higher than PEI 25 kDa. In addition, PEG‐PEI‐Pt could also effectively deliver siRNA into the cytoplasm of tumor cells. With the good antitumoral and gene delivery abilities, PEG‐PEI‐Pt may have a great potential for combination therapy of drug and gene. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

3.
Supramolecular assemblies with a bottle‐brush structure are obtained by inclusion complexation between β‐cyclodextrin and adamantane. β‐cyclodextrin‐modified chitosan is synthesized via the aldimine condensation reaction between β‐cyclodextrin monoaldehyde and chitosan as the host. The guest is prepared through the esterification reaction between methoxypoly(ethylene glycol) and 1‐adamantanecarboxylic acid chloride. The supramolecular assemblies are formed through the inclusion of adamantane‐modified methoxypoly(ethylene glycol) into the β‐cyclodextrin cavity on the chitosan chain. Fourier transform infrared and 1H NMR spectra were used to prove that the host, guest and assemblies were successfully obtained. UV?visible spectra were employed to confirm the formation of assemblies. Furthermore, the size of the particles in the assembled solution, the change before and after self‐assembly, and the effect of the addition of competitive molecules were studied by dynamic light scattering measurements. The results indicate that supramolecular assemblies have formed successfully which might be used to realize the biomimetic structure of the articular cartilage proteoglycan. © 2014 Society of Chemical Industry  相似文献   

4.
A supramolecular artificial glutathione peroxidase (PNIPAM‐CD‐g‐Te) was prepared based on a supramolecular graft copolymer. PNIPAM‐CD‐g‐Te was constructed by supramolecular host–guest self‐assembly. Significantly, PNIPAM‐CD‐g‐Te displayed noticeable temperature‐dependent catalytic activity and typical saturation kinetics behavior. It was also proved that the change in the self‐assembled structure of PNIPAM‐CD‐g‐Te during the temperature‐dependent process played a significant role in the temperature‐dependent catalytic behavior. The construction of PNIPAM‐CD‐g‐Te based on supramolecular graft copolymer endows artificial GPx with temperature‐dependent catalytic ability, enriched catalytic centers, and homogeneously distributed catalytic centers. This work bodes well for the development of other biologically related host–guest supramolecular biomaterials.  相似文献   

5.
6.
Stability of polyplex and safety are key factors to achieve stable gene transfection and high transfection efficiency. In this report, a star‐like amphiphilic biocompatible cyclodextrin‐poly(ε‐caprolactone)‐poly(2‐(dimethylamino) ethyl methacrylate), β‐CD‐g‐(PCL‐b‐PDMAEMA) x copolymer, consisting of biocompatible cyclodextrin core, biodegradable and stable poly(ε‐caprolactone) PCL segments, cationic and hydrophilic PDMAEMA blocks, is synthesized to achieve high efficiency of gene transfection with enhanced stability, due to the micelle formation by hydrophobic PCL segments. In comparison with polyethylenimine (PEI‐25k), a golden standard for nonviral vector gene delivery, this copolymer shows higher encapsulated plasmid desoxyribose nucleic acid (pDNA) ability and the persistence of transgene expression. More interestingly, this gene delivery platform by β‐CD‐g‐(PCL‐b‐PDMAEMA) x shows lower toxicity but better gene transfection efficiency at low N/P ratios, indicating high potential in gene therapy applications.  相似文献   

7.
A novel amino‐cyclodextrin was synthesized, and it was covalently attached to multiwalled carbon nanotubes (MWNTs). The functionalized MWNTs (f‐MWNTs) have very good aqueous dispersibility. Bovine serum albumin (BSA) was adsorbed onto f‐MWNTs through noncovalent interactions, including the hydrophobic interaction of the residues of BSA with the wall of MWNT and the guest–host interaction of the residues with the cyclodextrin (CD) moieties of f‐MWNTs. The ultraviolet–visible (UV–vis) absorption of the f‐MWNT‐BSA hybrid was measured with UV–vis spectrometer, and the absorbance can be described well with the Beer–Lambert law. The X‐ray diffraction patterns have indicated that the crystalline form of BSA has been changed after the adsorption of BSA on f‐MWNTs. The circular dichroism spectra have shown that a high percentage of α‐helical content can be retained for BSA adsorbed on f‐MWNTs. The results also indicate that the change of secondary structure of BSA is mainly due to the hydrophobic interaction of the residues of BSA with the wall of f‐MWNT, whereas the secondary structure is much less affected by the interaction of the CD moieties with BSA. © 2011 American Institute of Chemical Engineers AIChE J, 2011  相似文献   

8.
PEG oligomers were covalently attached to nonequilibrium, low‐pressure, RF‐plasma‐functionalized silicone medical‐ and industrial‐grade silicon rubber surfaces, in the absence and presence of linear and branched polyglycidol spacer‐chain molecules. All surface‐modification reactions were carried out in a two‐step process involving an initial argon–plasma activation of the surface, followed by “in situ” reaction with dichlorosilane in the absence of the discharge, and the attachment of PEG molecules or the graft polymerization of polyglycidol structures, and the attachment of PEG molecules. The surface of substrates was analyzed after each reaction step, using ESCA, ATR‐FTIR, and AFM. It was found that PEG molecules directly attached to medical‐grade silicone rubber surface as brush‐type structures, and generate stronger antifouling characteristics in comparison to similar structures generated on food‐grade substrates. The presence of additives on the food‐grade silicon rubber surfaces that might be etched and removed during the postplasma washing cycles could contribute to a less efficient attachment of PEG molecules. Surfaces resulting from PEG molecules attached through intermediate, linear, and branched polyglycidol molecules did not reduce bacterial attachment. It is suggested that macromolecular entanglement might be responsible for this behavior. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:2324–2337, 2006  相似文献   

9.
Fluorescent 2‐naphthol (NOH)‐containing β‐cyclodextrin (β‐CD)–epichlorohydrin (EP) copolymers were synthesized. Polymerization was confirmed through viscosity and FT‐IR spectroscopic measurements. Under certain conditions, the copolymers were water‐soluble (molar ratio of EP/β‐CD <22:1), while under other conditions water‐insoluble gels were formed (EP/β‐CD ≥ 22:1). Increase of the EP content to EP/β‐CD ≤ 39:1 increased the fluorescence intensity of the copolymer and shifted the emission maximum from 422 nm toward 352 nm (measured at pH ≥ 12). Further increases in the EP content resulted in a slight decrease in the fluorescence intensity. The fluorescence properties of our system at EP/β‐CD < 22 were sensitive to pH variation, while at EP/β‐CD ≥ 22 no pH effect was observed. These variations can be explained in terms of the exposure of the fluorophore to solvent in soluble versus insoluble polymers, as well as changes in the mode of association (host–guest complexation, trapping within the polymer network, covalent bonding, etc) of NOH with the polymers. Crystallographic studies on a single crystal grown in the absence of EP, but under basic conditions, suggest that host–guest complexation is not an important mode for NOH incorporation. Copyright © 2005 Society of Chemical Industry  相似文献   

10.
The aim of research is to develop potential tumor‐targeted circulation‐prolonged macromolecular magnetic resonance imaging (MRI) contrast agents without the use of low molecular gadolinium (Gd) ligands. The contrast agents were based on polymer–metal complex nanoparticles with controllable particle size to achieve the active and passive tumor‐targeted potential. In particular, poly (amidoamine) (PAMAM) dendrimer with 32 carboxylic groups was modified with folate‐conjugated poly (ethyleneglycol) amine (FA‐PEG‐NH2, Mw: 2 k and 4 kDa). FA‐PEG‐PAMAM‐Gd macromolecular MRI contrast agents were prepared by the complex reaction between the carboxylic groups in PAMAM and GdCl3. The structure of FA‐PEG‐PAMAM‐COOH was confirmed by nuclear magnetic resonance (1H‐NMR), Fourier transform infrared (FTIR) spectra, and electrospray ionization mass spectra (ESI‐MS). The mass percentage content of Gd (III) in FA‐PEG‐PAMAM‐Gd was measured by inductively coupled plasma‐atomic emission spectrometer (ICP‐AES). The sizes of these nanoparticles were about 70 nm measured by transmission electron microscopy, suggestion of their passive targeting potential to tumor tissue. In comparison with clinically available small molecular Gadopentetate dimeglumine, FA‐PEG‐PAMAM‐Gd showed comparable cytotoxicity and higher relaxation rate, suggestion of their great potential as tumor‐targeted nanosized macromolecular MRI contrast agents due to the overexpressed FA receptor in human tumor cell surfaces. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

11.
Functionalized poly(ethylene glycol) (PEG) containing four chloride end functional groups (PEG‐Cl4) was synthesized through reaction between cyanuric chloride and PEG‐(OH)2. Chloride end functional groups of PEG‐Cl4 were able to initiate the ring opening polymerization of 2‐ethyl‐2‐oxazoline and star copolymers containing a PEG core, and poly(2‐ethyl‐2‐oxazoline) (POX) arms were obtained. Polymerization was quenched using diethanolamine, and star copolymers containing hydroxyl end functional groups (PEG‐POX‐OH) were obtained. ε‐Caprolactone was then polymerized using the hydroxyl end functional groups of star copolymers and amphiphilic linear‐dendritic copolymers containing PEG and POX, and poly(caprolactone) (PCL) blocks were synthesized. Linear‐dendritic copolymers were able to load the organic and inorganic guest molecules. Application of host‐guest systems such as nanocatalyst for Heck chemical reaction was also investigated. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

12.
Macromonomer initiators behave as macro cross‐linkers, macro initiators, and macromonomers to obtain branched and cross‐linked block/graft copolymers. A series of new macromonomer initiators for atom transfer radical polymerization (MIM‐ATRP) based on polyethylene glycol (Mn = 495D, 2203D, and 4203D) (PEG) were synthesized by the reaction of the hydroxyl end of mono‐methacryloyl polyethylene glycol with 2‐bromo propanoyl chloride, leading to methacryloyl polyethylene glycol 2‐bromo propanoyl ester. Poly (ethylene glycol) functionalized with methacrylate at one end was reacted with 2‐bromopropionyl chloride to form a macromonomeric initiator for ATRP. ATRP was found to be a more controllable polymerization method than conventional free radical polymerization in view of fewer cross‐linked polymers and highly branched polymers produced from macromonomer initiators as well. In another scenario, ATRP of N‐isopropylacrylamide (NIPAM) was initiated by MIM‐ATRP to obtain PEG‐b‐PNIPAM branched block/graft copolymers. Thermal analysis, FTIR, 1H NMR, TEM, and SEM techniques were used in the characterization of the products. They had a thermo‐responsive character and exhibited volume phase transition at ~ 36°C. A plasticizer effect of PEG in graft copolymers was also observed, indicating a lower glass transition temperature than that of pure PNIPAM. Homo and copolymerization kinetics were also evaluated. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

13.
A novel vector for gene delivery was synthesized. Here the ovalbumin (OVA) acts as a core and low‐molecular‐weight PEI600 was grafted to its surface. The finally product was characterized (1H‐NMR, UV, and TGA) and its biophysical properties such as DNA condensing, particle size, and zeta potential were determined. The agarose gel assay indicated that OVA‐PEI600 could efficiently condense plasmid DNA. Its particle size was about 150 nm and zeta potential was around +20 mV. The MTT assay showed that the cytotoxicity of OVA‐PEI600 was less than PEI25 kDa. Its transfection efficiency in SKOV‐3 and HepG2 cell lines was higher than that of PEI600 and comparable to PEI25 kDa. In vivo, luciferase activity could be tested in liver, spleen, kidney, lung, and blood serum, respectively, in mice. The core‐shell structure of OVA‐PEI600 provided a novel strategy for nonviral gene delivery. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

14.
A rigid assembly of alginates is formed in aqueous media primarily via hydrogen bonding between guluronic units. A flow of aqueous alginate solution in a co‐flow capillary can form alginate gel fibers by contact with Ca2+ ions in sheath flow. Mixing with polyols [e.g., polyethylene glycol (PEG)] facilitates the shaping of the alginate assembly because PEG disrupts the assembly of the extended alginate chains to instead form alginate–PEG complexes that exhibit shear‐thinning behavior. The shear‐induced fibrous domains of the globular alginate–PEG complexes can be partitioned by a PEG‐rich phase, resulting in multiple parallel alginate gel filaments when the strong ionic‐field‐induced PEG‐rich phase is adjusted and an alginate–PEG complex phase is used as the aqueous two‐phase separation system.  相似文献   

15.
A polyethylenimine‐poly(hydroxyethyl glutamine) copolymer (PEI‐PHEG) was designed and synthesized as a gene delivery system. The molecular structure of PEI‐PHEG was characterized using nuclear magnetic resonance. Moreover, PEI‐PHEG/pDNA complexes were fabricated and characterized by gel retardation assay, particle size analysis, and zeta potential analysis. The transfection efficiency and cytotoxicity of PEI‐PHEG were evaluated using human cervical carcinoma (HeLa), human embryonic kidney (HEK293), and murine colorectal adenocarcinoma (CT26) cells in vitro. The results show that PEI‐PHEG could effectively form positively charged nano‐sized particles with pDNA; the particle size was in a range of 130.2 to 173.0 nm and the zeta potential was in a range of 27.6 to 41.0 mV. PEI‐PHEG exhibited much lower cytotoxicity and higher gene transfection efficiency than PEI‐25K with different cell lines in vitro. An animal test was also conducted on a Lewis Lung Carcinoma tumor model in C57/BL6 mice by using subcutaneous intratumoral administration. The results show that in vivo transfection efficiency of PEI‐PHEG was improved greatly compared with that of commercial PEI‐25K. These results demonstrate that PEI‐PHEG can be a potential nonviral vector for gene delivery systems both in vitro and in vivo. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

16.
A facile and well‐controlled pathway was introduced to obtain optimal pH‐sensitive luteinizing hormone‐releasing hormone—functionalized poly(ethylene glycol)‐block‐poly(l ‐histidine) (LHRH‐PEG‐PHIS) micelles in this paper. The influence of block‐selective solvent, the weight ratio of the selective solvent to common solvent and initial polymer concentration on the self‐assembly of LHRH‐PEG‐PHIS micelles were studied. These factors exerted remarkable influence on the morphology of the resulting micelles. The micelles showed a spherical geometry and an uniform appearance under the following optimal experimental conditions: LHRH‐PEG/PHIS ratio of 1.0 by molar, DMF as the selective solvent and 3.0 mg/mL as initial concentration, 100 W of ultrasonic power. These micelles had a small diameter (about 90 nm), low CMC (10 μg/mL), and pH‐sensitive switch in surface charge and micelles' size. As the pH of the micellar solution decreased from pH 7.4 to 5.5, the zeta potential of the LHRH‐PEG‐PHIS micelles increased from ?0.02 mV to 20.7 mV and the diameter of the nanoparticles decreased from 137 nm to 76 nm. After 30 h of incubation at pH 5.0, 6.0, and 7.4 the released free Doxorubicin (DOX) was about 83.18%, 81.26%, and 30.35%, respectively. The LHRH‐PEG‐PHIS micelles could combine the characteristics of active targeting with pH‐triggered drug release promising as intracellular drug delivery carriers. POLYM. ENG. SCI., 55:277–286, 2015. © 2014 Society of Plastics Engineers  相似文献   

17.
Poly(ethylene glycol)‐block‐poly(N‐isopropylacrylamide) (PEG‐b‐PNIPAM) block copolymers were synthesized by atom transfer radical polymerization, and the α‐cyclodextrin (α‐CD) induced self‐assembly characteristics of the system were elucidated. Below the lower critical solution temperature (LCST) of PNIPAM, CD threaded onto the PEG segments and induced micellization to form rod‐shaped nanostructures comprising of a PEG/α‐CD condensed phase and a PNIPAM shell. Increasing the temperature of system above the LCST caused the PNIPAM segments to collapse, which resulted in the dethreading of the CD. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

18.
Amorphous poly(ethylene isophthalate) (PEI) was synthesized, and was used for preparing an inclusion compound (IC) with γ‐cyclodextrin (γ‐CD). Coalesced polymer was produced by washing the PEI‐γ‐CD‐IC with hot water. Wide angle X‐ray diffraction, Fourier transform infrared, and differential scanning calorimetry analyses were employed to verify formation of PEI‐γ‐CD‐IC and to compare the as‐synthesized and coalesced PEI samples. These observations suggested that the conformations and morphology/chain‐packing of PEI were changed via coalescence from its γ‐CD inclusion compound. The glass‐transition temperature of the amorphous coalesced PEI is 15–20°C higher than the Tg observed for the as‐synthesized sample, even when observed in the second heat after cooling from well above Tg at 260°C. The amorphous as‐synthesized PEI retains its randomly‐coiling structure, while coalesced PEI has at least partially retained, the highly extended and parallel chains from the narrow channels of the inclusion compound, resulting in better/tighter packing among the PEI chains manifested by a higher Tg. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 6049–6053, 2006  相似文献   

19.
A novel host–guest system was developed by the encapsulation of simple organic guest molecules in the hydrophilic molecular architecture of crosslinked polyacrylamide hydrogels. The crosslinking agents used for the preparation of the host systems were hexanediol dimethacrylate (HDDMA) and divinyl benzene (DVB). This enabled us to construct hydrogels with different hydrophobic–hydrophilic equilibria. The model guest system used for the studies was benzoic acid. The selections gave simple but excellent host–guest systems with fine polar–apolar balancing. Polyacrylamide hydrogels with encapsulated benzoic acid were prepared with varying crosslink densities (5, 10, 15, and 20 mol %) by the solution polymerization technique. The rate of release of the host from the host–guest assembly was studied in different swelling conditions. The rate of release depended on the interaction forces between the polymer and the solvents. Polar forces, dispersion forces, and hydrogen bonding all played a vital role. The swelling behavior of the host‐polymer system and the host–guest assembly was analyzed and compared by the Flory–Rehner method. The amount of benzoic acid encapsulated in the DVB‐crosslinked polymer was higher than in the HDDMA‐crosslinked polymer, and the rate of release was in the order 5 > 15 > 10 > 20% for the DVB‐crosslinked polymer. The rate of release for the HDDMA‐crosslinked host–guest assembly was in the order 10 > 5 > 15 > 20%. These results were in excellent agreement with those of the Flory–Rehner analysis of the swelling properties. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1816–1824, 2004  相似文献   

20.
In this work, a brushed polycationic polymer with primary and tertiary amino groups was designed and synthesized for gene delivery. The backbone polymer was poly(N‐hydroxyethylacrylamide) (PHEAA) by the atom transfer radical polymerization (ATRP), and then 3,3′‐diaminodipropylamine (DPA) was grafted onto the PHEAA by the reaction between hydroxyl and the secondary amine. A brushed PHEAA‐DPA cationic polymer was achieved with primary and tertiary amino groups and the ratio was 2 : 1. The PHEAA100‐DPA and PHEAA200‐DPA could effectively condense plasmid DNA (pDNA) at the weight ratio of vector/DNA of 0.6 and 0.4, respectively. The cytotoxicity of PHEAA‐DPA/pDNA to COS‐7 cells and HepG‐2 cells within the weight ratio of vector/DNA of 16 : 1 was lower than that of PEI25k, and cell viability decreased with the increment of the weight ratio. Although the cytotoxicity of PHEAA100‐DPA/pDNA was lower than PHEAA200‐DPA/pDNA, the latter possessed higher transfection efficiency at the same weight ratio both in COS‐7 cells and HepG‐2 cells, compared with PEI25k, the transfection efficiency of PHEAA200‐DPA/pDNA was better in COS‐7 cells and HepG‐2 cells with the weight ratio of 12 : 1 and 10 : 1, respectively. These results showed that the PHEAA‐DPA with less cytotoxicity and higher gene transfection efficiency has a broad perspective in gene therapy. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40468.  相似文献   

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