Metal ion detection with oligo(ethylene glycol) monolayer-modified gold nanoparticles

Two colorimetric sensors of gold nanoparticles (AuNPs) modified with different oligo(ethylene glycol)-containing organic molecules have been developed to detect metal ions by ultraviolet-visible (UV-vis) extinction spectroscopy. These sensors display different responses to some metal ions. One exhibits high selectivity for Hg2+ over a variety of competitive metal ions and the other one can respond to a multitude of metal ions. These differences might result from the different functionalized end groups of the modified molecules. Coordination effect, pH response, and ionic strength were investigated to understand the mechanism of the responses to metal ions. The results suggested that the colorimetric responses were mainly induced by the coordination effect of the modified organic molecules and the removing of the modified organic molecules caused by metal ions.     

Thermo- and pH-sensitive IPN hydrogels based on PNIPAAm and PVA-Ma networks with LCST tailored close to human body temperature

Interpenetrating polymer network (IPN) hydrogels based on chemically modified poly(vinyl alcohol) (or PVA-Ma), with different degrees of substitution (DS), and poly(N-isopropylacrylamide) (or PNIPAAm) were obtained and characterized in this work. The PVA-Ma/PNIPAAm membrane hydrogels were prepared in two steps. In the first step the PVA-Ma hydrogels (with using PVA-Ma with different DS) were prepared by the reaction of double bonds on PVA-Ma, using the persulfate/TEMED pathway. In the second step the PNIPAAm network was prepared within the parent PVA-Ma network at different PVA-Ma/NIPAAm ratios using a photoreaction pathway. The studies show that degree of swelling of PVA-Ma/PNIPAAm IPN hydrogels is dependent on both temperature and pH of the soaking solution. The LCST of PVA-Ma/PNIPAAm IPN hydrogels, which was determined by measuring the intensity of light transmitted through the swollen hydrogels, can be tailored closer to human body temperature. Furthermore, SEM images showed that the IPN hydrogels present characteristic morphology as compared to parent PVA-Ma networks. IPN hydrogels presented lower cytotoxicity as compared to respective PVA-Ma hydrogels but the increase in the PVA-Ma/NIPAAm ratio allows the respective hydrogels being lesser cytocompatibles. The IPN hydrogels synthesized in this work presented characteristics that potentize their application as biomaterials, drug carriers, artificial muscles and treatment of wound.     

Grafting of poly(ethylene glycol) onto poly(acrylic acid)-coated glass for a protein-resistant surface

The surface of solid glass supports for samples in optical microscopy and for biosensors needs to be protein-resistant. A coating of a poly(ethylene glycol) monomethyl ether (mPEG) on the surface of the glass is one promising method for preventing the nonspecific adsorption of proteins. In this study, we have developed a novel technique for achieving an optimal coverage of a glass surface with mPEG to prevent protein adhesion. A clean glass substrate previously treated with (3-aminopropyl)dimethylethoxysilane (APDMES) was treated sequentially with poly(acrylic acid) and subsequently a primary amine derivative of mPEG in the presence of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide. The resultant glass surface was demonstrated to be highly protein-resistant, and the adsorption of bovine serum albumin decreased to only a few percentage points of that on a glass surface treated with APDMES alone. Furthermore, to extend the present method, we also prepared a glass substrate on which biotinylated poly(ethylene glycol) was cografted with mPEG, and biotinylated myosin subfragment-1 (biotin-S1) was subsequently immobilized on this substrate by biotin/avidin chemistry. Actin filaments were observed to glide on the biotin-S1-coated glass surface in the presence of ATP, and thus, the method is capable of immobilizing the protein specifically without any loss in its biological function.     

pH-sensitive photocatalytic activities of TiO2/poly(vinyl alcohol)/poly(acrylic acid) composite hydrogels

The pH-sensitive photocatalytic system was prepared by embedding TiO₂ into poly(vinyl alcohol)/poly(acrylic acid) hydrogel. Two different type TiO₂/hydrogel composites, such as matrix and nanofiber, were prepared to investigate the morphological effects on the photocatalytic activity. TiO₂ was distributed uniformly in the composite hydrogel and kept the original anatase structure without any structural change. The photocatalytic activity of TiO₂ was evaluated based on the efficiency of photobleaching of dye. The photobleaching of dye was improved greatly as the pH was changed into basic condition and the larger surface area of hydrogel was available for TiO₂ by using nanofiber supports.     

Sorption of zinc by novel pH-sensitive hydrogels based on chitosan, itaconic acid and methacrylic acid

Novel pH-sensitive hydrogels based on chitosan, itaconic acid and methacrylic acid were applied as adsorbents for the removal of Zn²⁺ ions from aqueous solution. In batch tests, the influence of solution pH, contact time, initial metal ion concentration and temperature was examined. The sorption was found pH dependent, pH 5.5 being the optimum value. The adsorption process was well described by the pseudo-second order kinetic. The hydrogels were characterized by spectral (Fourier transform infrared—FTIR) and structural (SEM/EDX and atomic force microscopy—AFM) analyses. The surface topography changes were observed by atomic force microscopy, while the changes in surface composition were detected using phase imaging AFM. The negative values of free energy and enthalpy indicated that the adsorption is spontaneous and exothermic one. The best fitting isotherms were Langmuir and Redlich-Peterson and it was found that both linear and nonlinear methods were appropriate for obtaining the isotherm parameters. However, the increase of temperature leads to higher adsorption capacity, since swelling degree increased with temperature.     

Swelling and aspirin release study: cross-linked pH-sensitive vinyl acetate-co-acrylic acid (VAC-co-AA) hydrogels

The objective of this work was to develop new pH-sensitive hydrogels to deliver gastric mucosal irritating drugs to the lower part of the gastrointestinal tract. For this purpose, cross-linked vinyl acetate-co-acrylic acid (VAC-co-AA) hydrogels were synthesized by using N, N, methylene bisacrylamide (MBAAm) as a cross-linking agent. Different ratios of 90:10, 70:30, 50:50, 30:70, and 10:90 of VAC-co-AA were synthesized. All of the compositions were cross-linked using 0.15, 0.30, 0.45, and 0.60 mol percent MBAAm. Swelling and aspirin release were studied for 8 hour period. The drug release data were fitted into various kinetic models like the zero-order, first-order, Higuchi, and Peppas. Hydrogels were characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. In addition to the above, these hydrogels were loaded with 2%, 8% and 14% w/v aspirin solutions, keeping the monomeric composition and degree of cross-linking constant. In conclusion, it can be said that aspirin can be successfully incorporated into cross-linked VAC/AA hydrogels and its swelling and drug release can be modulated by changing the mole fraction of the acid component in the gels.     

DNA directed protein immobilization on mixed ssDNA/oligo(ethylene glycol) self-assembled monolayers for sensitive biosensors

A stable and versatile biosensor surface is prepared by site-directed immobilization of protein-DNA conjugates onto a mixed self-assembled monolayer (SAM) composed of ssDNA thiols and oligo(ethylene glycol) (OEG) terminated thiols. The protein conjugates consist of an antibody chemically linked to a ssDNA target with a sequence complementary to the surface-bound ssDNA probes and are immobilized on the surface via sequence-specific hybridization. Compared to standard antibody immobilization techniques, this approach offers many advantages. The exceptional specificity of DNA hybridization combined with the diversity of potential sequences makes this platform perfect for multichannel sensors. Once a surface is patterned with the appropriate probe sequences, sequence-specific hybridization will sort out the target conjugates and direct them to the appropriate spots on the surface. In addition, the DNA SAMs are very stable and well suited to recycling by dehybdridization of the conjugates from the surface-bound probes. In this work, we demonstrate the specificity, sensitivity, and convenience of using protein-DNA conjugates to convert a DNA/OEG SAM surface into a biosensor surface and apply this platform to the detection of human chorionic gonadotropin using surface plasmon resonance.     

Albumin adsorption on Cibacron Blue F3G-A immobilized onto oligo(ethylene glycol)-terminated self-assembled monolayers

Self-assembled monolayers can be tailored with specific ligands to a certain protein and at the same time prevent the non-specific adsorption of other proteins. Cibacron Blue F3G-A (CB-thiol) was successfully immobilized onto tetra(ethylene glycol)-terminated alkanethiol (CB-thiol). The affinity of human serum albumin (HSA) to immobilized Cibacron Blue F3G-A was studied using mixed thiolate self-assembled monolayers on gold with different n-alkyl chain lengths and functional terminal groups (CH₃-; OH- and tetra(ethylene glycol)). Surfaces were characterized using X-ray photoelectron spectroscopy and water contact angle measurements. Albumin adsorption and exchangeability of the adsorbed albumin molecules with other albumin molecules in solution were evaluated using ¹²⁵I-radiolabeled HSA. Competitive adsorption between albumin and fibrinogen to the different self-assembled monolayers (SAMs) was also investigated. Results showed that the incorporation of CB-thiol on the monolayers does not increase the HSA adsorption and reversibility on the SAMs. However, although specific adsorption of HSA to the immobilized Cibacron Blue F3G-A was not demonstrated, the presence of CB-thiol decreases the affinity of fibrinogen to the OH-terminated SAMs.     

pH-sensitive hydrogels based on semi-interpenetrating network (semi-IPN) of chitosan and polyvinyl pyrrolidone for clarithromycin release

The aim of this study was to develop a pH-sensitive chitosan/polyvinyl pyrrolidone (PVP) based controlled drug release system for clarithromycin. The hydrogels were synthesized by cross-linking chitosan and PVP blend with glutaraldehyde to form a semi-interpenetrating polymer network (semi-IPN). These semi-IPNs were studied for their content uniformity, swelling index (SI), mucoadhesion, wettability, in vitro release and their release kinetics. The hydrogels showed more than 97% content of clarithromycin. These hydrogels showed high swelling and mucoadhesion under acidic conditions. The swelling may be due to the protonation of a primary amino group on chitosan. In acidic condition, chitosan would be ionized, and adhesion could have occurred between the positively charged chitosan and the negatively charged mucus. In the alkaline condition, less swelling and mucoadhesion was noticed. In vitro release study revealed that formulation containing chitosan (2% w/v) and PVP (4% w/v) in the ratio of 21:4 showed complete drug release after 12?h. Release profile showed that all the formulations followed non-Fickian diffusion mechanism. The cross-linking and compatibility of clarithromycin in the formulation was studied by Fourier transform infrared (FTIR) spectroscopic analysis, differential scanning calorimetry (DSC) and powder X-ray diffraction (p-XRD) study, which confirmed proper formation of semi-IPN and stability of clarithromycin in the formulations. The surface morphology of semi-IPN was studied before and after dissolution in simulated gastric fluid (SGF, pH 1.2) which revealed pores formation in membrane after dissolution. The results of study suggest that semi-IPNs of chitosan/PVP are potent candidates for delivery of clarithromycin in acidic environment.     

pH-sensitive hydrogels based on semi-interpenetrating network (semi-IPN) of chitosan and polyvinyl pyrrolidone for clarithromycin release

The aim of this study was to develop a pH-sensitive chitosan/polyvinyl pyrrolidone (PVP) based controlled drug release system for clarithromycin. The hydrogels were synthesized by cross-linking chitosan and PVP blend with glutaraldehyde to form a semi-interpenetrating polymer network (semi-IPN). These semi-IPNs were studied for their content uniformity, swelling index (SI), mucoadhesion, wettability, in vitro release and their release kinetics. The hydrogels showed more than 97% content of clarithromycin. These hydrogels showed high swelling and mucoadhesion under acidic conditions. The swelling may be due to the protonation of a primary amino group on chitosan. In acidic condition, chitosan would be ionized, and adhesion could have occurred between the positively charged chitosan and the negatively charged mucus. In the alkaline condition, less swelling and mucoadhesion was noticed. In vitro release study revealed that formulation containing chitosan (2% w/v) and PVP (4% w/v) in the ratio of 21:4 showed complete drug release after 12 h. Release profile showed that all the formulations followed non-Fickian diffusion mechanism. The cross-linking and compatibility of clarithromycin in the formulation was studied by Fourier transform infrared (FTIR) spectroscopic analysis, differential scanning calorimetry (DSC) and powder X-ray diffraction (p-XRD) study, which confirmed proper formation of semi-IPN and stability of clarithromycin in the formulations. The surface morphology of semi-IPN was studied before and after dissolution in simulated gastric fluid (SGF, pH 1.2) which revealed pores formation in membrane after dissolution. The results of study suggest that semi-IPNs of chitosan/PVP are potent candidates for delivery of clarithromycin in acidic environment.     

聚乙二醇-碳纳米管(PEG-CNTs)共聚物膜的制备及其微摩擦行为的研究

制备了聚乙二醇接枝碳纳管共聚物(PEG-CNTs)。通过红外光谱(FT-IR)。荧光光谱(FS)和透射电子显微镜(TEM)对共聚物进行了表征。利用旋涂技术以云母为基片制备了共聚物薄膜,采用原子力显微镜／摩擦力显微镜(AFM／FFM)研究了薄膜表面的形貌及微摩擦学行为。复合薄膜内的聚合物组分保证了膜的表面平整,坚硬的碳纳米管组分增强了薄膜的承载能力。     

熔融缩聚合成聚乳酸-聚乙二醇共聚物及其性能研究

采用羧基封端乳酸预聚物与聚乙二醇熔融缩聚合成了聚乳酸-聚乙二醇共聚物,并用GPC、FTIR、1H-NMR等方法表征了预聚物与共聚物,结果表明,预聚物的羧基封端率高于95%,预聚物的相对分子质量可由投料比(物质的量比)控制.热分析结果表明,共聚物中聚乳酸链段呈无规分布,而聚乙二醇链段能够形成结晶微区.力学性能测试结果表明,共聚物的断裂伸长率达371%,有望在聚乳酸韧性改性方面得到应用.     

Synthesis and characterization of polyester copolymers based on poly(butylene succinate) and poly(ethylene glycol)

A series of polyester copolymers was synthesized from 1,4-succinic acid with 1,4-butanediol and poly(ethylene glycol) through a two-step process of esterification and polycondensation in this article. The composition and physical properties of copolyesters were investigated via GPC, ¹HNMR, DSC and PLM. The copolymer composition was in good agreement with that expected from the feed composition of the reactants. The melting temperature (T_m), crystallization temperature (T_c), and crystallinity (X_c) of these copolyesters decreased gradually as the content of PEG unit increased. Otherwise, experimental results also showed that the contents of PEG in copolymers had an effect on the molecular weight, distribution, thermal properties, hydrolysis degradation properties, and crystalline morphology of polyester copolymers.     

Mussel-inspired adhesive hydrogels based on biomass-derived xylan and tannic acid cross-linked with acrylic acid with antioxidant and antibacterial properties

Journal of Materials Science - Inspired by mussel chemistry, adhesive hydrogels represented by polydopamine (PDA) have been widely studied in many fields such as biomedical applications and...     

Swelling behavior of polyacrylamide/laponite clay nanocomposite hydrogels: pH-sensitive property

In this study, an investigation is carried out on the influence of varying clay contents (25–43%), pH values (2–11 buffer solutions), heat treatment, temperatures (25–60 °C) and ionic strengths (saline solution, 10^?7–0.1 M) on the water absorbency of polyacrylamide (PAAm)/laponite nanocomposite (NC) hydrogels in the absence of polyelectrolyte. For the influence of pH value on swelling behaviors, a maximum swelling ratio occurs at pH 11. Heat treatment of the hydrogels significantly improved the swelling capacity and created an obvious pH sensitive area (pH 3–4). The swelling capacity of the hydrogels was enhanced by increasing the temperature of the absorbing media. The results of swelling at different ionic strengths also indicate that the ionic strength can considerably weaken the swelling abilities of the NC hydrogels.     

新型聚乙二醇接枝聚乳酸及其降解特性研究

通过直接酰胺化反应,以马来酸酐本体改性聚乳酸(MPLA)和氨基封端聚乙二醇(H2N-PEG-NH2)为原料,合成了聚乙二醇本体改性聚乳酸(PPLA).通过红外、核磁共振技术对改性聚合物的结构进行了表征;采用FITC标记牛血清白蛋白(FITC-BSA)为模型蛋白质,测试了聚合物对蛋白质的非特异性吸附;利用吸水率表征了聚合物的亲水性;利用聚合物在12周降解过程中pH值、失重率的变化评价了它们的降解特性.结果表明:H2N-PEG-NH2已成功接枝到MPLA上;与聚乳酸(PLA)、MPLA相比,PPLA明显降低了对FITC-BSA的吸附;其亲水性和降解性增加.预计该材料将是一种更适合组织工程和药物缓释应用的聚乳酸类可降解材料.     

聚丙烯酸改性膨润土吸附铜离子性能研究

用硫酸酸化钙基膨润土为原料,通过丙烯酸原位聚合制备了聚丙烯酸改性膨润土(PAA/HB)无机/有机高分子改性剂.采用IR、TG、XRD、SEM对其结构与形貌进行了表征,发现膨润土与丙烯酸很好地复合,呈现出层状结构和粗糙的表面.考察了该新型吸附剂对Cu2+的吸附性能,最佳条件下对Cu2+去除率可达98%以上.并探讨了PAA...