Rheological Properties and Microstructures of Hydroxyethyl Cellulose/Poly(Acrylic Acid) Blend Hydrogels

A simple in-situ method was introduced to prepare hydroxyethyl cellulose/poly(acrylic acid) (HEC/PAA) blend hydrogels by forming an interpenetrating network (IPN). Storage modulus (G′) and loss modulus (G″) were improved dramatically compared to HEC. To prove that hydrogen bonds and chemical crosslinking played major roles in improving the hydrogel strength and toughening, and to optimize the components of HEC/PAA blend hydrogels, a series of blend hydrogels with different ratios of HEC to PAA were designed and the corresponding Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), rheological tests, and swelling properties were compared. Crosslinked HEC/PAA blend hydrogel (mol/mol = 1:1) showed the best properties appropriate for opening up biomedical applications of the hydrogel.     

Gelatin/Montmorillonite and Gelatin/Polyvinyl Alcohol/Montmorillonite Bionanocomposite Hydrogels: Microstructural,Swelling and Drying Properties

Abstract

Gelatin/montmorillonite bionanocomposite hydrogels containing 0, 5 and 10?wt.% of montmorillonite were prepared via two different techniques, either a cooling or drying method. In addition, gelatin/polyvinyl alcohol/montmorillonite bionanocomposite hydrogels having gelatin/polyvinyl alcohol ratios of 1/1, 1/2 and 2/1, loaded with 0, 5 and 10?wt.% of montmorillonite, were prepared via a cyclic freezing-thawing technique. The microstructural properties of both types of the prepared bionanocomposite hydrogels were investigated using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The gel fraction, swelling behavior and drying kinetics of all prepared bionanocomposite hydrogels were also studied. The XRD and SEM results showed a porous structure with a possible exfoliated morphology for both types of the prepared bionanocomposite hydrogels. In addition, the gel fraction of the bionanocomposite hydrogels increased and a more entangled and crosslinked network with a decreased pore size was obtained by increasing the loading level of montmorillonite for both types of the bionanocomposite hydrogels. The swelling ratio and drying rate of both types of the bionanocomposite hydrogels could be increased by decreasing the PVA portion or MMT loading level, while the swelling and drying ability of the gelatin/montmorillonite bionanocomposite hydrogels prepared via the cooling method was higher than those of the corresponding samples prepared via the drying method.     

Preparation and Swelling Behavior of Partially Hydrolyzed Polyacrylamide Nanocomposite Hydrogels in Electrolyte Solutions

In this research, nanocomposite hydrogels were prepared by cross‐linking of partially hydrolyzed polyacrylamide/sodium montmorillonite aqueous solutions with chromium triacetate. The gelation process and influence of nanoclay content and salt concentration on swelling behavior were investigated. Study of gelation behavior using dynamic rheometry method showed that increasing the nanoclay content decreases the storage modulus, due to the partial adsorption of polymer chains onto the clay surface and ionic interaction between negative layers of sodium montmorillonite and Cr.³⁺ By increasing the cross‐linker concentration of the gelation system, the viscous energy dissipation properties of the nanocomposite gel decreases. Swelling ratio of the nanocomposite gels in distilled water decreased as the concentration of the nanoclay increased. However, nanocomposite gels showed lower salt sensitivity in electrolyte media compared with unfilled gels.     

Encapsulation of small fullerenes into nitrogenated holey nanotubes: a density functional theory study

Encapsulation of fullerene into nanotubes based on a C₂N sheet, known as nitrogenated holey graphene, was investigated using density functional theory. The structural and electronic properties of these carbon hybrid materials, consisting of nitrogenated holey nanotubes and a small C₂₀ fullerene, were studied. The formation energies showed that encapsulation of the fullerene into the nitrogenated holey nanotube is an exothermic process. To characterise the electronic properties, the electronic band structure and density of states of armchair and zigzag nitrogenated holey nanotubes were calculated. Filling these nanotubes with the C₂₀ fullerene resulted in a p-type semiconducting character. The energy band gap of the nitrogenated holey nanotubes decreased with fullerene encapsulation. The results are indicative of the possibility of band gap engineering by encapsulation of small fullerenes into nitrogenated holey nanotubes.     

Synthesis and Characterization of pH- and Temperature-sensitive Hydrogels of Poly (Styrene-alt-Maleic Anhydride)-co-Pluronic for Drug Release

A pH- and temperature-sensitive hydrogel of poly(styrene-alt-maleic anhydride) -co-Pluronic P123 (PSMA-P123) was prepared by the reaction of anhydride groups (MA) on PSMA with the hydroxyl groups on Pluronic (triblock polyethylene oxide-co-polypropylene oxide-co-polyethylene oxide, HO(CH₂CH₂O)₂₀(CH₂CH(CH₃)O)₇₀ (CH₂CH₂O)₂₀OH). The effect of proportions between PMSA and P123 on the gel fraction was determined. The effects of pH value and temperature on swelling ratio of the hydrogels were evaluated. Scanning electron microscopy was used to observe the morphology of the hydrogels. Differential scanning calorimetry was employed to characterize the thermo-sensitivity of the hydrogel. The drug-release behavior of the hydrogels was investigated by using chloromycetin as a model drug. The effect of temperature and pH on the release of chloromycetin from the hydrogels was studied. These results showed that PSMA-P123 hydrogels, being pH- and temperature-sensitive and reversible, appeared to be of potential for biomedical materials, especially for drug release applications.     

Preparation and Characterization of Biopolymers Chitosan/Alginate/Gelatin Gel Spheres Crosslinked by Glutaraldehyde

Twelve different samples of gel spheres were prepared from the biopolymers chitosan, alginate, and gelatin via polyion complex formation in aqueous solution with crosslinking by glutaraldehyde. Dropwise addition of a chitosan/gelatin solution into a solution containing alginate and glutaraldehyde gave the gel spheres. The effects of different ratios of glutaraldehyde (0.25%, 0.50%, 1.0%, and 2.0%), and gelatin (2.5%, 5.0%, and 10.0%) on the characteristics of the gel spheres were evaluated. An increase in the concentration of the glutaraldehyde led to forming true spheres in rigid form. By scanning electron microscopy (SEM), the gel spheres showed fibrous network propagation along the gel membrane surface. Fourier transform infrared (FT-IR) spectroscopy confirmed the crosslinking of the amino groups by the glutaraldehyde and the presence of crosslinking bonds between the amino groups of chitosan and the carboxyl groups in the alginate molecule. Swelling studies showed that increasing the degree of crosslinking increased the density of the polymer network, which led to a decrease in the degree of swelling. The characteristics of the gel spheres will be useful for immobilization and prolonged release of biologically active substances.     

Study on the Dynamic Rheometry and Swelling Properties of the Polyacrylamide/Laponite Nanocomposite Hydrogels in Electrolyte Media

Polyacrylamide/laponite/chromium triacetate nanocomposite (NC) hydrogels were prepared by incorporation of the laponite nanoparticles in partially hydrolyzed polyacrylamide followed by cross-linking of their aqueous solutions with chromium triacetate. Influence of nanoparticle, cross-linker, polymer concentrations, and gelation media (water) temperature, salinity, and rheometer frequency on the viscoelastic behavior of the NC hydrogels were studied by probing the network properties. In addition, swelling behaviors of these NC gels in tap and oil reservoir water were evaluated. According to dynamic rheometry of the gelation process, the limiting storage modulus of the NC gels increased with increasing laponite content. The addition of laponite into the polyacrylamide gelling system increased their viscous properties more strongly than the elastic properties. The ultimate elastic modulus of the NC gels increased with increasing water salinity and temperature. Increasing rheometer frequency during gelation retarded the sol–gel transition and decreased the ultimate elastic modulus. The equilibrium swelling ratio of the NC hydrogels in tap water decreased with increasing laponite content. The salt sensitivity of the NC gels in oil reservoir water slightly decreased with increasing laponite content. These results suggest the superiority of the hydrolyzed polyacrylamide (HPAM)/chromium acetate/laponite NC hydrogels for water shut-off applications in oil reservoirs as compared with unfilled HPAM gels.     

Facile Functionalization of Gold Nanoparticles with PLGA Polymer Brushes and Efficient Encapsulation into PLGA Nanoparticles: Toward Spatially Precise Bioimaging of Polymeric Nanoparticles

Nanocarriers prepared from poly(lactide‐co‐glycolide) (PLGA) have broad biomedical applications. Understanding their cellular uptake and distribution requires appropriate visualization in complex biological compartments with high spatial resolution, which cannot be offered by traditional imaging techniques based on fluorescent or radioactive probes. Herein, the encapsulation of gold nanoparticles (GNPs) into PLGA nanoparticles is proposed, which should allow precise spatial visualization in cells using electron microscopy. Available protocols for encapsulating GNPs into polymeric matrices are limited and associated with colloidal instability and low encapsulation efficiency. In this report, the following are described: 1) a facile protocol to functionalize GNPs with PLGA polymer followed by 2) encapsulation of the prepared PLGA‐capped GNPs into PLGA nanocarriers with 100% encapsulation efficiency. The remarkable encapsulation of PLGA‐GNPs into PLGA matrix obeys the general rule in chemistry “like dissolves like” as evident from poor encapsulation of GNPs capped with other polymers. Moreover, it is shown that how the encapsulated gold nanoparticles serve as nanoprobes to visualize PLGA polymeric hosts inside cancer cells at the spatial resolution of the electron microscope. The described methods should be applicable to a wide range of inorganic nanoprobes and provide a new method of labeling pharmaceutical polymeric nanocarriers to understand their biological fate at high spatial resolution.     

鱼明胶作为卤化银纳米粒子载体的研究

采用的鱼明胶样品是从深海鱼的鱼皮提取而得,在成份和物理性质方面鱼明胶与通常使用的动物明胶有显著的差别。研究表明,鱼明胶的蛋白成分中α组分占绝对优势,且其中分子量较小的α2组分又比分子量较大的α1组分含量高得多,在鱼明胶中几乎没有分子量最大的γ组分。其氨基酸残基中,脯氨酸和羟脯氨酸的含量比动物胶低,而收氨酸含量却明显高于后者。鱼明胶还具有较低的胶凝温度,这些特点可能使之适宜作为分散介质来制备AgBrI纳米粒子乳剂,此外,鱼明胶中含有较多含硫物质,而且杂质铁主要以三价形式存在,并且进一步利用鱼明胶作为保护载体,在广泛的胶银比（即明胶量与银量之比值）范围（从8：1到4：1）获得了平均粒径为14nm的AgBrI纳米粒子乳剂。该乳剂具有良好的单分散性和热稳定性。对纳米粒子乳剂进行硫一金协同敏化可以提高其感光度。若适当增加敏化剂用量和适当延长敏化时间这种协同敏化作用的效果更好。     

基于FTIR,ICP-MS的仿生Mg-Ag-HA/明胶抗菌生物涂层的制备与表征

目前,傅里叶变换红外光谱（FTIR）技术具有待测样品数量少、对特征基团灵敏度高、样品制备和分析简单等优点;电感耦合等离子体质谱（ICP-MS）的优势也较为显著：微量元素的高灵敏度检出率,低检测限和多元素的同时分析;协同上述两种方法,可快速对功能医用材料的化学元素和基团进行鉴定,从而为仿生医用抗菌材料的研发提供新的设计思路和理论依据。羟基磷灰石(HA)因其优异的骨传导和骨诱导特性被用于薄膜材料,钛植入表面HA薄膜已进入临床应用阶段。但是,HA的本真脆性和缺乏抗菌性,常常导致植入失败。因此,开发一种耐磨性好且抑菌性优的促成骨功能涂层成为当前急需要解决的难题。研究目的在于在钛表面制备耐磨性好且抑菌性优的促成骨功能涂层,初步探讨了涂层的抗菌离子缓释规律和生物活性。开拓性地在工业纯钛表面制备了明胶、银和镁离子改性的羟基磷灰石(Mg-Ag-HA/明胶)抗菌涂层。将银(Ag)引入羟基磷灰石涂层(HA)以改善其抗菌性能,镁(Mg)作为第二元素以提高生物相容性,明胶可以同时提高HA的生物相容性和力学性能。ICP-MS测定涂层中镁和银元素的释放量和可持续性。所得到的新型Mg-Ag-HA/明胶的SEM结果、Ca/P比值、化学特征峰和晶相通过FTIR, SEM,EDAX和XRD进行表征。结果表明：明胶的羧基与HA的钙离子之间已形成Ca-COO化学键,明胶和Mg-Ag-HA构成了有机-无机复合涂层;Mg和Ag元素被成功地引入到了HA晶格中,且分布均匀。模拟体液浸泡后,Mg-Ag-HA/明胶涂层试样表面有新的缺钙型的HA生成,且球形磷灰石中检测到新的Mg,Na和Cl元素;结果表明,新型复合涂层样品具有良好的生物活性。SEM和LSCM实验结果观察发现,小鼠颅骨成骨细胞在Mg-Ag-HA/明胶上粘附良好,细胞伸展大量伪足,未见细胞毒性。明胶的加入大大降低了复合镀层中Mg2+和Ag+的释放速率,提高了复合镀层的生理稳定性,为镀层保持长期抗菌功能提供了保证。Mg-Ag-HA/明胶作为钛基涂层材料具有良好的抗菌离子释放能力和优异的生物相容性,为新型抗感染外科植入体的研发提供了新思路。     

Preparation and Characterization of the Fluorescent Carbon Dots Derived from the Lithium‐Intercalated Graphite used for Cell Imaging

Zero‐dimensional fluorescent carbon dots (CDs) that are used as a cell‐imaging reagent are prepared by using a simple and effective route employing lithium‐intercalated graphite from lithium‐ion batteries as a carbon source. Under ultrasonic exfoliation, the interlayer space increases, while the layer distortion and remaining lithium of the lithium‐intercalated graphite are utilized to disrupt the graphitic structure and produce the CD suspension. Subsequently, after concentration and purification, the obtained colloidal CD suspension has a fluorescent yield of up to 1.2% and is therefore comparable to the CDs prepared in previous reports. These CD products are water‐soluble, nanosized (approximately 3.5 nm), and biocompatible and can easily enter into HeLa cells to act as a cell‐imaging reagent without any further functionalization. In addition, these CDs do not impose toxicity against HeLa cells and have high photostability with low photobleaching and demonstrate potential applications for bio‐labeling as well as solution state optoelectronics.     

Preparation and Characterization of Composites Based on Poly (Butylene Succinate) and Poly (Lactic Acid) Grafted Tetracalcium Phosphate

Tetracalcium phosphate (TTCP, Ca₄(PO₄)₂O) was functionalized by poly (l-lactic acid) (PLLA) in order to improve the dispersion of TTCP particles in poly (butylene succinate) (PBS) matrices, and then a series of the PLLA grafted TTCP/PBS (g-TTCP/PBS) composites were prepared via melt processing. Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), tensile analysis, differential scanning calorimetry (DSC), thermogravimetric analysis (DTG/TGA) and melt rheological analysis were used to investigate the structure and properties of the g-TTCP/PBS composites. The results revealed that l-lactide could be grafted onto the surface of TTCP, and the g-TTCP/PBS composites showed the best mechanical properties when the content of g-TTCP was 10 wt%. The crystallization temperature of g-TTCP/PBS composites tended to increase with the increase of g-TTCP contents. The functionalized particles played an important role in augmenting the thermal degradation rate and the complex viscosity of the composites due to their unique structure and the reasonable interfacial interaction between the particles and PBS matrix.     

强悬浮性纳米TiO2的制备、表征及光催化活性研究(Ⅰ)制备与表征

以热分解方法制备纳米TiO2,后续处理采用甲基硅油淬火改性和自然冷却,对改性前后的产物进行了XRD,TEM,FTIR等表征。结果表明,两种后续处理方法对所制备的纳米TiO2的物相、晶粒度、结晶度影响不大;但经硅油改性后的纳米TiO2的团聚程度降低。进一步的研究表明,经硅油改性后的纳米TiO2可长期悬浮于水的表面及浅层,这可能有利于直接用阳光有效光催化降解污水和光催化剂的回收再利用。     

Preparation and Characterization of Chemically Crosslinked Polyvinyl Alcohol/Carboxylated Nanocrystalline Cellulose Nanocomposite Hydrogel Films with High Mechanical Strength

Chemically crosslinked polyvinyl alcohol (PVA)/carboxylated nanocry-stalline cellulose (PVA/CNCC) nanocomposite hydrogel films were fabricated by film-casting of PVA/CNCC mixture solutions and subsequent thermal-curing of the PVA with the CNCC. Gel fractions of the hydrogel films were measured to confirm the occurrence of crosslinking. Morphologies of the hydrogel films were characterized by polarized light microscopy and scanning electron microscopy (SEM). Thermal properties, swelling behavior and mechanical properties of the hydrogel films were investigated to evaluate the influence of CNCC content (10～30% of PVA mass). Equilibrium water content of the hydrogel films was in the range of 40～49%. At swelling equilibrium, the hydrogel films could be stretched to 3～3.4 times their original length, and their tensile strength was in the range of 7.9～11.6 MPa. The results show that the PVA/CNCC nanocomposite hydrogel films were both extensible and highly tough.     

关于黄铁矿做太阳能电池材料可行性实验研究

本文通过对黄铁矿紫外、可见、近红外光谱的分析,获得黄铁矿对太阳光全光谱的吸收率数据。重点对染料敏化太阳能电池的光阴极进行了实验探究。本人制备了黄铁矿薄膜太阳能电池和以石墨为光阴极的太阳能电池,对各个薄膜形貌进行表征。最后,对各个电池的性能进行了测量比较。并预期在制备太阳电池时,它可能代替硅,而成为今后主要的光伏半导体材料。     

Preparation,Properties and Applications of Chitosan-Based Biocomposites/Blend Materials: A Review

Taking inspiration from many published chitosan (Cs)-based biocomposites, this article is written to highlight the significant effect of reinforcing and/or blending Cs polymer with the different constituents to increase various properties (mechanical, hydrophilic, thermal, adsorption ability and stability) of Cs without sacrificing any of its positive properties. It is concluded that the properties of Cs biocomposites with a synthetic constituent have contributed to its rigidity since only mechanical interaction occurred at the interfacial region. Instead of physical interactions, the addition of an organic constituent also promoted the chemical interactions at the interfacial region of the Cs biocomposites. This consequently produced Cs biocomposites with synthetic constituents with relatively low strength and stiffness but high resistance to fracture, whereas the ones with an organic constituent have high strength and stiffness but are very brittle. This review also screens the current applications of Cs-based biocomposites in the field of drug delivery, tissue engineering, antibacterial, food packaging, biomedical, metal adsorption and dye removal.     

Preparation and Characterization of Two Types of Cyanate Ester-epoxy Resin Interpenetrating Network Matrix/Butadiene-acrylonitrile Rubber Composites

Two types of butadiene-acrylonitrile rubbers (i.e., carboxyl randomized butadiene-acrylonitrile rubber (CRBN) and hydroxyl terminated butadiene-acrylonitrile rubber (HTBN)) have been used for modifying an interpenetrating network of cyanate ester (CE)/epoxy resin (EP) (70/30). The toughness of the matrix can be improved effectively with addition of rubbers. The values of impact strength (11.6 KJ/m²) show a maximum for the CE/EP/HTBN (70/30/8) blend. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) results show that CRBN and HTBN have a different dispersion state in the CE/EP matrix. CRBN aggregates to form regular spheres with a size of about 1 μm. HTBN disperse homogeneously with its size of the nano-level (about 10 nm). Fourier transform infrared spectrum (FTIR) and differential scanning calorimetric (DSC) analysis shows that the CRBN has higher reactivity than HTBN. The thermal gravimetric analysis (TGA) results shows that T ₁₀ (temperature of 10% weight loss) of the CE/EP system decreases with the addition of rubbers. For the CE/EP/CRBN system, both T ₃₀ (temperature of 30% weight loss) and T ₅₀ (temperature of 50% weight loss) are lower than neat CE/EP. However, for the CE/EP/HTBN system, both T ₃₀ and T ₅₀ are near to neat CE/EP. Different reactivity and compatibility between the rubbers and CE/EP matrix is the main determining factor for the thermal stability of the blends.     

Preparation and Characterization of BPO Film as Electrode for Using of FeRAM

Conductive perovskite BaPb03 （BPO） films as a potential electrode material of PZT capacitors used in ferroelectric random access memory are prepared by rf magnetron sputtering. An x-ray diffractometer and standard four probe method are employed to investigate the dependence of growth conditions on crystal structure and conductivity of BPO films. It is found that BPO films with perovskite phase can be obtained at substrate temperatures above 425℃, and the sample with the lowest resistivity is obtained at 450℃ under pure argon atmosphere. Using this BPO film as electrode, ferroelectric properties of BPO/PZT/BPO and Pt/PZT/BPO sandwiched structures are evaluated. Their remanent polarization and coercive field are 36.6 ℃/cm^2 （81.3 k V/cm） and 36.9℃/cm^2 （89.1 kV/cm）, respectively. The coercive field of the former structure is lower than that of the latter, but remanent polarizations are almost the same. In addition, the results imply that BPO electrode is helpful to improve the fatigue resistance of PZT. The reasons are discussed.     

Entropy production in a cell and reversal of entropy flow as an anticancer therapy

The entropy production rate of cancer cells is always higher than healthy cells in the case where no external field is applied. Different entropy production between two kinds of cells determines the direction of entropy flow among cells. The entropy flow is the carrier of information flow. The entropy flow from cancerous cells to healthy cells takes along the harmful information of cancerous cells, propagating its toxic action to healthy tissues. We demonstrate that a low-frequency and lowintensity electromagnetic field or ultrasound irradiation may increase the entropy production rate of a cell in normal tissue than that in cancer and consequently reverse the direction of entropy current between two kinds of cells. The modification of the PH value of cells may also cause the reversal of the direction of entropy flow between healthy and cancerous cells. Therefore, the biological tissue under the irradiation of an electromagnetic field or ultrasound or under the appropriate change of cell acidity can avoid the propagation of harmful information from cancer cells. We suggest that this entropy mechanism possibly provides a basis for a novel approach to anticancer therapy.