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1.
A way to obtain macroscopic responsive materials from silicon‐oxide polymer core/shell microstructures is presented. The microparticles are composed of a 60 nm SiO2‐core with a random copolymer corona of the temperature responsive poly‐N‐isopropylacrylamide (PNIPAAm) and the UV‐cross‐linkable 2‐(dimethyl maleinimido)‐N‐ethyl‐acrylamide. The particles shrink upon heating and form a stable gel in both water and tetrahydrofuran (THF) at 3–5 wt% particle content. Cross‐linking the aqueous gel results in shrinkage when the temperature is increased above the lower critical solution temperature and it regains its original size upon cooling. By freeze drying with subsequent UV irradiation, thin stable layers are prepared. Stable fibers are produced by extruding a THF gel into water and subsequent UV irradiation, harnessing the cononsolvency effect of PNIPAAm in water/THF mixtures. The temperature responsiveness translates to the macroscopic materials as both films and fibers show the same collapsing behavior as the microcore/shell particle. The collapse and re‐swelling of the materials is related to the expelling and re‐uptake of water, which is used to incorporate gold nanoparticles into the materials by a simple heating/cooling cycle. This allows for future applications, as various functional particles (antibacterial, fluorescence, catalysis, etc.) can easily be incorporated in these systems.  相似文献   

2.
The fabrication of multifunctional polymeric Janus colloids that display catalytically driven propulsion, change their size in response to local variations in pH, and vary cargo release rate is demonstrated. Systematic investigation of the colloidal trajectories reveals that in acidic environments the propulsion velocity reduces dramatically due to colloid swelling. This leads to a chemotaxis‐like accumulation for ensembles of these responsive particles in low‐pH regions. In synergy with this chemically defined accumulation, the colloids also show an enhancement in the release rate of an encapsulated cargo molecule. Together, these effects result in a strategy to harness catalytic propulsion for combined autonomous transport and cargo release directed by a chemical stimulus, displaying a greater than 30 times local cargo‐accumulation enhancement. Lactic acid can be used as the stimulus for this behavior, an acid produced by some tumors, suggesting possible eventual utility as a drug‐delivery method. Applications for microfluidic transport are also discussed.  相似文献   

3.
In this study, thermally responsive alkyl end‐capped poly(N‐isopropylacrylamide‐co‐acrylic acid) amphiphilic copolymers were synthesized, and successfully utilized to fabricate reversed micelles and immobilize enzymes. Transmission electron microscopy (TEM) study showed that the reversed micelles were spherical in nature. The activity of Candida rugosa lipase immobilized in the reversed micelles towards catalyzing the esterification of lauric acid and 1‐propanol was analyzed in comparison with naked enzyme. Immobilized lipase provided much greater catalytic activity. In addition, the effects of pH, water content, polymer and enzyme concentration on the catalytic activity were investigated. The optimized fabrication conditions of lipase‐loaded reversed micelles, under which lipase gave the highest activity, were as follows: polymer concentration, 12 mg mL–1; enzyme concentration, 25 mg mL–1 phosphate buffered saline (PBS); pH, 7.4; W0 ([water]/[surfactant]), 83.3. Lipase immobilized in these micelles was much more stable than that in conventional sodium bis(2‐ethylhexyl) sulfosuccinate micelles. More importantly, the size of lipase‐immobilized micelles decreased, and the enzyme solution precipitated from the reaction mixture when the temperature increased to a value slightly higher than the lower critical solution temperature (LCST) of the polymer. The recovery rate of enzyme was about 75 %. The α‐helix structure of the recovered lipase remained intact. In addition, the enzymatic reaction was terminated after raising the environmental temperature slightly above the LCST. These thermally responsive micelles may make a promising system for enzyme immobilization.  相似文献   

4.
In this study, we report on a novel composite membrane system for pH‐responsive controlled release, which is composed of a porous membrane with linear grafted, positively pH‐responsive polymeric gates acting as functional valves, and a crosslinked, negatively pH‐responsive hydrogel inside the reservoir working as a functional pumping element. The proposed system features a large responsive release rate that goes effectively beyond the limit of concentration‐driven diffusion due to the pumping effects of the negatively pH‐responsive hydrogel inside the reservoir. The pH‐responsive gating membranes were prepared by grafting poly(methacrylic acid) (PMAA) linear chains onto porous polyvinylidene fluoride (PVDF) membrane substrates using a plasma‐graft pore‐filling polymerization, and the crosslinked poly(N,N‐dimethylaminoethyl methacrylate) (PDM) hydrogels were synthesized by free radical polymerization. The volume phase‐transition characteristics of PMAA and PDM were opposite. The proposed system opens new doors for pH‐responsive “smart” or “intelligent” controlled‐release systems, which are highly attractive for drug‐delivery systems, chemical carriers, sensors, and so on.  相似文献   

5.
Double stimuli‐responsive membranes are prepared by modification of pH‐sensitive integral asymmetric polystyrene‐b‐poly(4‐vinylpyridine) (PS‐b‐P4VP) diblock copolymer membranes with temperature‐responsive poly(N‐isopropylacrylamide) (pNIPAM) by a surface linking reaction. PS‐b‐P4VP membranes are first functionalized with a mild mussel‐inspired polydopamine coating and then reacted via Michael addition with an amine‐terminated pNIPAM‐NH2 under slightly basic conditions. The membranes are thoroughly characterized by nuclear magnetic resonance (1H‐NMR), Fourier transform infrared spectroscopy and X‐ray‐induced photoelectron spectroscopy. Additionally dynamic contact angle measurements are performed comparing the sinking rate of water droplets at different temperatures. The pH‐ and thermo‐double sensitivities of the modified membranes are proven by determining the water flux under different temperature and pH conditions.  相似文献   

6.
Asymmetric membranes are prepared via the non‐solvent‐induced phase separation (NIPS) process from a polystyrene‐block‐poly(N,N‐dimethylaminoethyl methacrylate) (PS‐b‐PDMAEMA) block copolymer. The polymer is prepared via sequential living anionic polymerization. Membrane surface and volume structures are characterized by scanning electron microscopy. Due to their asymmetric character, resulting in a thin separation layer with pores below 100 nm on top and a macroporous volume structure, the membranes are self‐supporting. Furthermore, they exhibit a defect‐free surface over several 100 µm2. Polystyrene serves as the membrane matrix, whereas the pH‐ and temperature‐sensitive minority block, PDMAEMA, renders the material double stimuli‐responsive. Therefore, in terms of water flux, the membranes are able to react on two independently applicable stimuli, pH and temperature. Compared to the conditions where the lowest water flux is obtained, low temperature and pH, activation of both triggers results in a seven‐fold permeability increase. The pore size distribution and the separation properties of the obtained membranes were tested through the pH‐dependent filtration of silica particles with sizes of 12–100 nm.  相似文献   

7.
A photoresponsive molecularly imprinted polymer (MIP) material is successfully fabricated from an azobenzene‐based functional monomer, 4‐[(4‐methacryloyloxy)phenylazo]benzoic acid (MPABA), using caffeine as a molecular template. The trans–cis photoisomerization properties of MPABA are retained after incorporation into the rigid 3D crosslinked polymer matrix. Substrate affinity of the MIP receptor sites is photoswitchable. This can be attributed to the photoisomerization of azobenzene chromophores within the MIP receptors, resulting in the alteration of their geometry and the spatial arrangement of their binding functionalities. The favorable binding constant of the MIP receptors for caffeine is 5.48 × 104 M –1 in dimethylsulfoxide. The density of the caffeine‐specific receptor sites in the MIP material is 0.95 μmol (g MIP)–1. Upon irradiation at 365 nm, 58.3 % of receptor‐bound caffeine is released from the MIP material. Subsequent irradiation at 440 nm causes 96.4 % of the released caffeine to be rebound by the MIP material. This near‐quantitative uptake of the released caffeine is evidence of the reversibility of the receptor‐site configuration and substrate affinity during the photoswitching of the azobenzene chromophores. Although the photoregulated substrate release and uptake processes are generally repeatable, a gradual reduction in the extent of substrate release and rebinding is observed. This may be caused by the slow deformation of MIP receptors during the course of repetitive photoswitching. The results of this work demonstrate the potential of stimuli‐responsive MIP materials as smart chemicals and as drug‐delivery systems.  相似文献   

8.
Inorganic nanoparticles (NPs) are promising drug delivery carriers owing to their high drug loading efficiency, scalable preparation, facile functionalization, and chemical/thermal stability. However, the clinical translation of inorganic nanocarriers is often hindered by their poor biodegradability and lack of controlled pH response. Herein, a fully degradable and pH‐responsive DOX@ACC/PAA NP (pH 7.4–5.6) is developed by encapsulating doxorubicin (DOX) in poly(acrylic acid) (PAA) stabilized amorphous calcium carbonate (ACC) NPs. The DOX‐loaded NPs have small sizes (62 ± 10 nm), good serum stability, high drug encapsulation efficiency (>80%), and loading capacity (>9%). By doping proper amounts of Sr2+ or Mg2+, the drug release of NPs can be further modulated to higher pH responsive ranges (pH 7.7–6.0), which enables drug delivery to the specific cell domains of tissues with a less acidic microenvironment. Tumor inhibition and lower drug acute toxicity are further confirmed via intracellular uptake tests and zebrafish models, and the particles also improve pharmacokinetics and drug accumulation in mouse xenograft tumors, leading to enhanced suppression of tumor growth. Owing to the excellent biocompatibility, biodegradability, and tunable drug release behavior, the present hybrid nanocarrier may find broad applications in tumor therapy.  相似文献   

9.
Nanometer‐sized surfactant‐templated materials are prepared in the form of stable suspensions of colloidal mesoporous silica (CMS) consisting of discrete, nonaggregated particles with dimensions smaller than 200 nm. A high‐yield synthesis procedure is reported based on a cationic surfactant and low water content that additionally enables the adjustment of the size range of the individual particles between 50 and 100 nm. Particularly, the use of the base triethanolamine (TEA) and the specific reaction conditions result in long‐lived suspensions. Dynamic light scattering reveals narrow particle size distributions in these suspensions. Smooth spherical particles with pores growing from the center to the periphery are observed by using transmission electron microscopy, suggesting a seed‐growth mechanism. The template molecules could be extracted from the nanoscale mesoporous particles via sonication in acidic media. The resulting nanoparticles give rise to type IV adsorption isotherms revealing typical mesopores and additional textural porosity. High surface areas of over 1000 m2 g–1 and large pore volumes of up to 1 mL g–1 are obtained for these extracted samples.  相似文献   

10.
The synthesis of double‐hydrophilic core/shell cylindrical polymer brushes (CPBs), their hybrids with magnetite nanoparticles, and the directed alignment of these magnetic hybrid cylinders by a magnetic field are demonstrated. Consecutive grafting from a polyinitiator poly(2‐(2‐bromoisobutyryloxy)ethyl methacrylate) (PBIEM) of tert‐butyl methacrylate (tBMA) and oligo(ethylene glycol) methacrylate (OEGMA) using atom‐transfer radical polymerization (ATRP) and further de‐protection yields core/shell CPBs with poly(methacrylic acid) (PMAA) as the core and POEGMA as the shell, which is evidenced by 1H NMR, gel permeation chromatography (GPC), and dynamic and static light scattering (DLS and SLS). The resulting core/shell brush is well soluble in water and shows a pH responsiveness because of its weak polyelectrolyte core. Pearl‐necklace structures are observed by cryogenic transmission electron microscopy (cryo‐TEM) at pH 4, while at pH 7, these structures disappear owing to the ionization of the core. A similar morphology is also found for the polychelate of the core/shell CPBs with Fe3+ ions. Superparamagnetic magnetite nanoparticles have also been prepared and introduced into the core of the brushes. The hybrid material retains the superparamagnetic property of the magnetite nanoparticles, which is verified by superconducting quantum interference device (SQUID) magnetization measurements. Large‐scale alignment of the hybrid cylinders in relatively low magnetic fields (40–300 mT) can easily be performed when deposited on a surface. which is clearly revealed by the atomic force microscopy (AFM) and TEM measurements.  相似文献   

11.
Hydrogen‐bonding interactions are an important alternative to electrostatic interactions for assembling multilayer thin films of uncharged components. Herein, a new method is reported for rendering such films stable at pH values close to physiological conditions. Multilayer films based on hydrogen bonding are assembled by the alternate deposition of poly[(styrene sulfonic acid)‐co‐(maleic acid)] (PSSMA) and poly(N‐isopropylacrylamide) (PNiPAAm) at pH 2.5. The use of PSSMA results in multilayers that contain free styrene sulfonate groups, as these moieties do not interact with the PNiPAAm functional groups. Subsequent infiltration of a multivalent ion (Ce4+ or Fe3+) leads to an increase in the total film mass, with little impact on the film morphology, as determined by using atomic force microscopy. To examine the film stability, the resulting films have been exposed to elevated pH (7.1). While there is substantial swelling of the multilayers (25 % and 55 % for Ce4+‐ and Fe3+‐stabilized films, respectively), film loss is negligible. This provides a stark contrast with non‐stabilized films, which disassemble almost immediately upon exposure to pH 7.1. This method represents a simple and effective strategy for stabilizing hydrogen‐bonded structures non‐covalently. Further, the multivalent ions also render the films responsive to changes in the local redox environment, as demonstrated by film disassembly after exposure of Fe3+‐treated films to iodide solutions.  相似文献   

12.
The surface properties and self‐adhesion mechanism of self‐healing poly(butyl acrylate) (PBA) copolymers containing comonomers with 2‐ureido‐4[1H]‐pyrimidinone quadruple hydrogen bonding groups (UPy) are investigated using a surface forces apparatus (SFA) coupled with a top‐view optical microscope. The surface energies of PBA–UPy4.0 and PBA–UPy7.2 (with mole percentages of UPy 4.0% and 7.2%, respectively) are estimated to be 45–56 mJ m?2 under dry condition by contact angle measurements using a three probe liquid method and also by contact and adhesion mechanics tests, as compared to the reported literature value of 31–34 mJ m?2 for PBA, an increase that is attributed to the strong UPy–UPy H‐bonding interactions. The adhesion strengths of PBA–UPy polymers depend on the UPy content, contact time, temperature and humidity level. Fractured PBA–UPy films can fully recover their self‐adhesion strength to 40, 81, and 100% in 10 s, 3 h, and 50 h, respectively, under almost zero external load. The fracture patterns (i.e., viscous fingers and highly “self‐organized” parallel stripe patterns) have implications for fabricating patterned surfaces in materials science and nanotechnology. These results provide new insights into the fundamental understanding of adhesive mechanisms of multiple hydrogen‐bonding polymers and development of novel self‐healing and stimuli‐responsive materials.  相似文献   

13.
Multi‐stimuli‐responsive fluorescent molecule tetraphenylethylene (TPE) derivative 1 is synthesized, which contains a TPE skeleton and peripheries of two methoxyl groups and one carboxyl group. It shows a typical aggregation‐induced emission behavior and also exhibits fluorescence responses to pH change and amine vapors, and multicolored mechanochromic properties. The emission of 1 can be reversibly switched among blue (1p‐f, 462 nm, Φf = 7.4%), bright cyan (1p‐h, 482 nm, Φf = 82.3%), and yellow (1p‐g, 496 nm, Φf = 10.5%) with high contrast through solvent fuming, heating, or grinding. Molecule 1 occurs in four crystalline states (1c‐a, 1c‐b, 1c‐c, and 1c‐d) after crystallization from different solvents. The multicolored mechanochromic property is related to the different interactions and packing modes of molecules in the crystals. The crystals with weak fluorescent emission have characteristic porous structures and corresponding intensive XRD diffraction peaks, which are absent in the crystal with intensive fluorescent emission. The porous structures are critical for the fluorescence intensity of the molecules. Upon heating, the porous structures of crystals are damaged and fluorescence is significantly enhanced.  相似文献   

14.
Macroscopic vanadium oxide fibers have been fabricated by an extrusion process. By varying the shear rate associated with the gel extrusion process we have been able to tune the diameter and transversal geometry of the fibers at macroscopic length scales. At the mesoscopic length scale, small‐angle X‐ray scattering (SAXS) analysis provides evidence for the possibility of fine tuning the degree of alignment of the V2O5 ribbons inside the fibers; this alignment is clearly improved upon increasing the shear rate. Nitrogen physisorption measurements (Brunauer–Emmett–Teller (BET)) indicate that the as‐synthesized fibers exhibit poor mesoporosity, largely due to the presence of remaining poly(vinyl alcohol) (PVA) entities. Microscopically, from XRD measurements, the fiber structure appears to be semi‐crystalline. 51V magic angle spinning NMR (MAS NMR) spectroscopy reveals that the local environment of 51V is typical of the structure of a V2O5·1.8 H2O xerogel. We demonstrate here that the alignment of the nanoribbon subunits can be tuned via the shear rate applied during the extrusion process, which provides a good handle for tuning the mechanical and sensing properties of the as‐synthesized fibers.  相似文献   

15.
A new class of materials that are capable of color tunability over 300 nm with a 15 °C temperature change is introduced. The materials are assembled from thermoresponsive poly (N‐isopropylacrylamide)‐co‐acrylic acid (pNIPAm‐co‐AAc) microgels, which are deposited on Au coated glass substrates. The films are also pH responsive; the temperature‐induced color change was suppressed at high pH and is consistent with the behavior of a solution of suspended microgels. The mechanism proposed to account for the observed optical properties suggests that they result from the two Au layers being separated from each other by the “monolithic” microgel film, much like a Fabry‐Pérot etalon or interferometer. It is the modulation of the distance between these two layers, facilitated by the microgel collapse transition at high temperature, that allows the color to be tuned. The sensitivity of the system presented here will be used for future sensing and biosensing applications, as well as for light filtering applications.  相似文献   

16.
A novel positively K+‐responsive membrane with functional gates driven by host‐guest molecular recognition is prepared by grafting poly(N‐isopropylacrylamide‐co‐acryloylamidobenzo‐15‐crown‐5) (poly(NIPAM‐co‐AAB15C5)) copolymer chains in the pores of porous nylon‐6 membranes with a two‐step method combining plasma‐induced pore‐filling grafting polymerization and chemical modification. Due to the cooperative interaction of host‐guest complexation and phase transition of the poly(NIPAM‐co‐AAB15C5), the grafted gates in the membrane pores could spontaneously switch from “closed” state to “open” state by recognizing K+ ions in the environment and vice versa; while other ions (e.g., Na+, Ca2+ or Mg2+) can not trigger such an ion‐responsive switching function. The positively K+‐responsive gating action of the membrane is rapid, reversible, and reproducible. The proposed K+‐responsive gating membrane provide a new mode of behavior for ion‐recognizable “smart” or “intelligent” membrane actuators, which is highly attractive for controlled release, chemical/biomedical separations, tissue engineering, sensors, etc.  相似文献   

17.
Antibacterial efficiency can be effectively improved by applying targeting antibacterial materials and strategies. Herein, the successful synthesis of uniform pH‐responsive Ag nanoparticle clusters (AgNCs) is demonstrated, which can collapse and reassemble into nonuniform Ag NPs upon exposure to the acidic microenvironment of bacterial infections. This pH triggered reassembly contributes greatly to the improved antibacterial activities of AgNCs against both methicillin‐resistant Staphylococcus aureus (MRSA) and Escherichia coli (E. coli). The minimum inhibitory concentration and minimum bactericidal concentration against MRSA are as low as 4 and 32 µg mL?1 (which are 8 and 32 µg mL?1 for E. coli), respectively. In vivo skin wound healing experiments confirm AgNCs can serve as an effective wound dressing to accelerate the healing of MRSA infection. The development of responsive AgNCs offers new materials and strategies in targeting antibacterial applications.  相似文献   

18.
This article presents the synthesis and physicochemical behavior of dual‐responsive plasmonic nanoparticles with reversible optical properties based on protein‐coated gold nanoparticles grafted with thermosensitive polymer brushes by means of surface‐initiated atom transfer radical polymerization (SI‐ATRP) that exhibit pH‐dependent thermo‐responsive behavior. Spherical gold NPs of two different sizes (15 nm and 60 nm) and with different stabilizing agents (citrate and cetyltrimethylammonium bromide (CTAB), respectively) were first capped with bovine serum albumin (BSA). The resulting BSA‐capped NPs (Au@BSA NPs) exhibited not only extremely high colloidal stability under physiological conditions, but also a reversible U‐shaped pH‐responsive behavior, similar to pure BSA. The ?‐amine of the L‐lysine in the protein coating was then used to covalently bind an ATRP‐initiator, allowing for the SI‐ATRP of thermosensitive polymer brushes of oligo(ethylene glycol) methacrylates with an LCST of 42 °C in pure water and around 37 °C under physiological conditions. Such protein coated nanoparticles grafted with thermosensitive polymers exhibit a smart pH‐dependent thermosensitive behavior.  相似文献   

19.
Improving the sensitivity of magnetic resonance imaging (MRI), a powerful non‐invasive medical imaging technique, requires the development of novel contrast agents with a higher efficiency than gadolinium chelates such as DTPA:Gd (DTPA: diethylenetriaminepentaacetic acid) that are currently used for clinical diagnosis. To achieve this objective, the strategy that we have explored involves the use of gold nanoparticles as carriers for gadolinium chelates. These nanoparticles are obtained by reducing a gold salt in the presence of a dithiolated derivative of DTPA. Characterization of these particles by transmission electron microscopy (TEM), X‐ray diffraction (XRD), thermogravimetric analysis (TGA), colorimetric titration, and X‐ray photoelectron spectroscopy (XPS) reveals the presence of a multilayered shell containing about 150 ligands on 2–2.5 nm sized particles. These particles exhibit a high relaxivity (r1 = 585 mM –1 s–1 as compared to 3.0 mM –1 s–1 for DTPA:Gd), rendering them very attractive as contrast agents for MRI.  相似文献   

20.
Surface‐initiated photoiniferter‐mediated photopolymerization (SI‐PMP) in presence of tetraethylthiuram disulfide is used to directly synthesize surface‐grafted poly(methacrylic acid)‐block‐poly(N‐isopropylacrylamide) (PMAA‐b‐PNIPAM) layers. The response of these PMAA‐b‐PNIPAM bi‐level brushes to changes in pH, temperature and ionic strength is investigated by using in‐situ multi‐angle ellipsometry to measure changes in solvated layer thickness. As expected for a block copolymer architecture, PMAA blocks swell as pH is increased, with the maximum change in the thickness occurring near pH = 5, and PNIPAM blocks exhibit lower critical solution temperature (LCST) behavior, marked by a broad transition between swollen and collapsed states. The response of the bi‐level brushes to changes in added salt at constant pH is complex, as the swelling behaviors of both the weak polyelectrolyte, PMAA, and thermoresponsive PNIPAM are affected by changes in ionic strength. This work demonstrates not only the robustness of SI‐PMP for making novel, bi‐level stimuli‐responsive brushes, but also the complex links between synthesis, structure, and response of these materials.  相似文献   

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