Thermodynamic parameters of poly(lactic acid) solutions in dialkyl phthalate

Some of thermodynamic parameters for poly(lactic acid) (PLA)/dialkyl phthalate systems have been investigated. Both poly(dl-lactic acid) (PDLLA) and poly(l-lactic acid) (PLLA), which are stereoisomers of PLA, were used and a series of 1,2-dialkyl phthalates with different alkyl chain, from methyl to hexyl, was adopted as a solvent. Theta temperatures of PLA/dialkyl phthalate system were determined and subsequently the second virial coefficient and the interaction parameter were evaluated. Theta temperature was determined by the extrapolation of the highest liquid-liquid phase separation temperatures and Zimm plots were constructed by static light scattering to obtain second virial coefficient and z-average radius of gyration. Second virial coefficient and z-average radius of gyration was examined quantitatively as a function of temperature and solvent. Thermodynamic parameters that could not be obtained experimentally were calculated based on the Flory-Huggins theory.     

Studies on the preparation and dental properties of antibacterial polymeric dental restorative composites containing alkylated ammonium chloride derivatives

The preparation of antibacterial polymeric dental restorative composites (PDRC) was carried out using various alkylated ammonium chloride derivatives as the antibacterial compound. To improve the mechanical properties of PDRC, the surface of the silica filler was hydrophobically treated with γ-methacryloxypropyltrimethoxysilane. The diametral tensile strength, flexural strength, and Knoop hardness of PDRC were measured and the antibacterial effect was also investigated. The addition of alkylated ammonium chloride derivatives to the bisphenol-A glycerolate dimethacrylate/triethyleneglycol dimethacrylate resin matrix enhanced the antibacterial properties of PDRC. It was also discovered that alkylated ammonium chloride derivatives with a higher chain length between the ammonium and the acryl (or methacryl) functional groups reduced the mechanical properties of PDRC. In addition, it was found that the optimum concentration of the antibacterial compound was about 3 wt% based upon resin matrix, and the optimum chain length between functional groups of alkylated ammonium chloride derivatives was 2–3 carbons.     

Effect of hydrolysis on spatial inhomogeneity in poly(acrylamide) gels of various crosslink densities

The spatial inhomogeneity in poly(acrylamide) (PAAm) gels of various crosslink densities has been investigated with the static light scattering measurements. The gels were prepared using N,N′-methylenebis(acrylamide) (BAAm) as a crosslinker at a fixed initial monomer concentration but at various crosslink densities. Ammonium persulfate-N,N,N′,N′-tetramethylethylenediamine (TEMED) redox initiator system was used to initiate the polymerization reactions as well as to create charged groups in the aged gels. The gels were characterized by elasticity tests and by light scattering measurements at a gel state just after their preparation. Elasticity measurements show that 91-94% of the crosslinker molecules used in the hydrogel preparation were wasted in ineffective crosslinks. Debye-Bueche analysis of the light scattering data indicates frozen concentration fluctuations within the gel samples, which increase continuously with increasing crosslink density of the hydrogels. This phenomenon was explained with the multiple crosslinking reactions leading to the formation of highly crosslinked regions in the final hydrogel. The extent of concentration fluctuations was found to decrease drastically with increasing time of aging of gels in the synthesis reactor, indicating that the hydrolysis of amide groups into carboxylate anions facilitates the homogenization of the gel samples. A thermodynamic model was developed to explain the experimental observations in terms of the osmotic pressure of counterions in the aged gels.     

Effect of swelling on spatial inhomogeneity in poly(acrylamide) gels formed at various monomer concentrations

The effect of swelling on the spatial inhomogeneity in poly(acrylamide) (PAAm) gels has been investigated with the static light scattering measurements. Four sets of gels were prepared using N,N′-methylenebis(acrylamide) (BAAm) as a crosslinker at various initial monomer concentrations. The crosslinker ratio X (the mole ratio of BAAm to the monomer acrylamide) was fixed at 1/50, 1/61.5, 1/66, and 1/100 in each set of gels. The gels, both at the state of preparation and at the equilibrium swollen state in water, exhibit a maximum degree of spatial gel inhomogeneity at a critical monomer concentration (ν_2,cr⁰). ν_2,cr⁰ shifts toward smaller concentrations as X is decreased or, as the gel swells beyond its swelling degree after preparation. Swelling enhances the extent of spatial inhomogeneity in PAAm gels and, this enhancement mainly occurs at low crosslinker ratios. The theoretical prediction of the Panyukov-Rabin theory was found to be in qualitative agreement with the experimental findings. It was also shown that three different effects, namely crosslinker, concentration, and swelling effects determine the extent of inhomogeneities in gels formed at various monomer concentrations.     

Synthesis and characterization of polysaccharide-maghemite composite nanoparticles and their antibacterial properties

The aim of this study was to obtain saccharide (dextran and sucrose)-coated maghemite nanoparticles with antibacterial activity. The polysaccharide-coated maghemite nanoparticles were synthesized by an adapted coprecipitation method. X-ray diffraction (XRD) studies demonstrate that the obtained polysaccharide-coated maghemite nanoparticles can be indexed into the spinel cubic lattice with a lattice parameter of 8.35 Å. The refinement of XRD spectra indicated that no other phases except the maghemite are detectable. The characterization of the polysaccharide-coated maghemite nanoparticles by various techniques is described. The antibacterial activity of these polysaccharide-coated maghemite nanoparticles (NPs) was tested against Pseudomonas aeruginosa 1397, Enterococcus faecalis ATCC 29212, Candida krusei 963, and Escherichia coli ATCC 25922 and was found to be dependent on the polysaccharide type. The antibacterial activity of dextran-coated maghemite was significantly higher than that of sucrose-coated maghemite. The antibacterial studies showed the potential of dextran-coated iron oxide NPs to be used in a wide range of medical infections.     

Aggregation in dilute solutions of high molar mass poly(ethylene) oxide and its effect on polymer turbulent drag reduction

We apply methods of dynamic light scattering (DLS) and fluid mechanics to quantitatively establish the role of aggregation in the turbulent drag reduction of high molar mass poly(ethylene oxide) (PEO) solutions. By means of DLS, we show that the dilute aqueous solutions of high molar mass PEO (M_w ∼ 4 × 10⁶ g/mol) are aggregated and that this aggregate structure can be manipulated by addition of the chaotropic salt guanidine sulfate (GuS) or the divalent salt magnesium sulfate (MgSO₄). In aqueous solution, we find Γ ∼ q^2.8±0.1, where Γ is the DLS correlation function relaxation rate and q is the scattering vector. This scaling is consistent with internal motions of a large coil or aggregate. Addition of salt progressively decreases the scaling to Γ ∼ q^2.0±0.1 (at 0.5 M of MgSO₄) consistent with center-of-mass diffusion of isolated coils. We further find that manipulating the aggregation state of PEO with MgSO₄ shifts the critical condition for onset of turbulent drag reduction at dilute concentrations in pipe flow by a factor of 2.5. Because this critical condition is inversely proportional to the viscoelastic relaxation time of the polymer solution, we conclude that the aggregation state and the turbulent drag reduction behavior of PEO are strongly correlated. This correlation definitively confirms prior speculation (Cox et al. Nature 1974;249; Vlachogiannis et al. Physics of Fluids 2003;15(12)) that the high molar mass PEO commonly used in literature studies of turbulent drag reduction is in a state of aggregation. Furthermore, the quantitative differences in quiescent DLS characterization and turbulent flow pressure drop measurements suggest that high molar mass PEO undergoes flow-induced de-aggregation in transport systems with shear stresses as low as 0.5 Pa.     

Studies on the annealing and antibacterial properties of the silver-embedded aluminum/silica nanospheres

Substantial silver-embedded aluminum/silica nanospheres with uniform diameter and morphology were successfully synthesized by sol-gel technique. After various annealing temperatures, the surface mechanisms of each sample were analyzed using scanning electron microscope, transmission electron microscope, and X-ray photoelectron spectroscopy. The chemical durability examinations and antibacterial tests of each sample were also carried out for the confirmation of its practical usage. Based on the result of the above analyses, the silver-embedded aluminum/silica nanospheres are eligible for fabricating antibacterial utensils.     

Solvents effect on the physical properties of semi-dilute poly(N-isopropyl acryl amide) solutions

The physical properties of 5 wt% poly(NIPAM) (M_v=3.22×10⁵) semi-dilute solutions in H₂O, D₂O, and THF (tetrahydrofuran) solvents were studied using dynamic light scattering (DLS) and dynamic shear viscosity (DSV) measurements. The DLS data showed that there were poly(NIPAM) slow mode inter-polymer chains associations in H₂O and D₂O solvents. However, no DLS slow mode was observed in poly(NIPAM)/THF solutions. The DSV data showed that there are shear thickening behavior in these three poly(NIPAM) solutions, resulting in a maximum shear viscosity η_peak in the viscosity η′(ω) versus shear frequency ω curve. The slow mode hydrodynamic radius 〈R_hs〉 of DLS measurements and the zero shear rate viscosity η₀ and maximum viscosity η_peak data of DSV measurements from poly(NIPAM)/H₂O and poly(NIPAM)/D₂O solutions show two critical transition temperatures with T_cr1=30-32 °C and T_cr2=32-34 °C. Poly(NIPASM)/D₂O has higher T_cr1 and T_cr2 than poly(NIPASM)/H₂O. However, no transition temperatures of poly(NIPAM)/THF solution were observed. The different temperature dependencies of these three solutions were attributed to the ‘solubility’ and ‘hydrogen bonding’ effects between poly(NIPAM) with H₂O, D₂O, and THF solvents. Without considering the polymer-solvent hydrogen bonding, the solubility of poly(NIPAM) in solvents decreases in the following sequence: THF>H₂O>D₂O and the degree of polymer-solvent hydrogen bonding increases in the following sequence: THF<H₂O<D₂O. The effects of the degree of ‘hydrogen bonding’ and the ‘solubility’ of polymer in solvents on the physical properties of poly(NIPAM) solutions are discussed.     

氯化银纳米粒子散射光谱的应用研究

研究了氯化银纳米粒子的散射光谱及其应用,与透射光谱相比,用散射光谱法测定微量银离子,具有更好的线性关系、更宽的线性范围和更高的灵敏度。     

3-氯-2-羟丙基三甲基氯化铵的合成进展与应用

介绍了3-氯-2-羟丙基三甲基氯化铵的几种合成方法———常规法、水相法和有机溶剂法,重点对以无水乙醇为溶剂、以三甲胺盐酸盐和环氧氯丙烷为原料的有机溶剂法进行了研究。综述了3-氯-2-羟丙基三甲基氯化铵在石油开采、环保和造纸中的应用。     

Solution properties of xanthan. Light scattering and viscometry on dilute and moderately concentrated solutions

Elastic and quasi-elastic light-scattering, viscometric and rheological studies are given for solutions of the microbial polysaccharide Xanthomonas campestris (xanthan) in aqueous 0.62N NaCl for polymer concentrations from 0.03 to 2.2 g kg⁻¹. The observed negative ∂ln[η]/∂ln T is interpreted as a decrease of the persistence length with increasing T. The behaviour in moderately concentrated solutions (2<[η]c<25) reveals intermolecular association, leading to gel formation in the extreme case. The effect of the association on the viscometric and light-scattering data is discussed. It is concluded that the early stages of association involve structure with the chain axes nearly parallel, but that larger, particulate-like structures develop with increasing c, eventually leading to gel formation under certain conditions.     

Superior antibacterial activity against seed-borne plant bacterial disease agents and enhanced physical properties of novel green synthesized nanostructured ZnO using Thymbra spicata plant extract

An easy and eco-friendly approach using Thymbra spicata var. spicata L. (TS) plant extract was developed for the formation of nanostructured ZnO. TS aqueous leaf extract was used for the green synthesis of nanostructured ZnO via the Successive ionic layer adsorption and reaction (SILAR) method. Electron microscope images exhibit the morphological adjustments of the samples with respect to change in TS concentration in the growth solution. The nanostructured ZnO grown by SILAR was observed to be polycrystalline with hexagonal crystal structure. The optical energy bandgap value of the samples varies from 3.21 to 3.09 eV as the content of TS increases from 2.5 to 5.0%. Also, the effect of TS additive to ZnO on electrical properties was investigated. It was determined by Van der Pauw measurements that TS contribution to ZnO significantly increased electrical resistance. In addition, impedance analyzes of the produced films were carried out in the frequency range of 20Hz ?1 MHz. Nyquist plots showed the single semicircle for all samples, and the values of capacitance and resistance were calculated. Its antibacterial activities was investigated against economically important Gram-positive (Clavibacter michiganensis subsp. Michiganensis) and negative (Pseudomonas syringae pv. Phaseolicola, Pseudomonas cichorii and Pectobacterium carotovorum subsp. Carotovorum) seed-borne plant bacterial disease agents by using paper disc diffusion assay for the first time. In vitro laboratory screenings of green synthesized nanostructured ZnO have given encouraging results, indicating their potential use in the management of seed-borne bacterial diseases.     

Modification of polyacrylonitrile (PAN) fiber by blending with N‐(2‐hydroxy)propyl‐3‐trimethyl‐ ammonium chitosan chloride

N‐(2‐Hydroxy)propyl‐3‐trimethylammonium chitosan chloride (HTCC) was synthesized by the reaction of glycidyltrimethylammonium chloride (GTMAC) and chitosan. The reaction product was a water‐soluble chitosan derivative, and showed excellent antimicrobial activity. HTCC was blended with polyacrylonitrile (PAN) using an NaSCN aqueous solution as a common solvent. The blend solution was transparent and stable up to 6 months without phase separation. The PAN/HTCC blend fibers were prepared via a wet spinning and drawing process. Thermal, electrical, and mechanical properties as well as antimicrobial activity were investigated. It was found that the antistatic property and antimicrobial activity of the blend fibers could be achieved by adding only a small amount of HTCC. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2258–2265, 1999     

Studies of electrical properties of some fire-retarding poly(vinyl chloride) compositions

Several fire-resistant formulations were prepared from a sample of poly(vinyl chloride) (PVC), small variable proportions of chloroorganic adducts [1,2,3,4,7,7-hexachloro-5-carboxy,bicyclo(2,2,1)heptene-2] or [1,2,3,4,7,7-hexachloro-5-carboxy,5-methyl-bicyclo(2,2,1)heptene-2] as fire-retarding modifiers, plasticizers (dibutylphthalate and a chlorinated paraffin), and a heat stabilizer (dibutyltindilaurate). The fire-resistance and electrical properties of the obtained formulations were studied to obtain a fire-retarding plasticized PVC of good electrical insulation character. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 27–35, 1997     

Dynamic light scattering and small-angle neutron scattering studies on phenolic resin solutions

Solution properties of unfractionated phenolic resins prepared by polycondensation of phenol and formaldehyde using oxalic acid as a catalyst were investigated by dynamic light scattering (DLS) and small-angle neutron scattering (SANS). The hydrodynamic radius, obtained by DLS experiments with 1 vol % solution in acetone, and the correlation length, ξ, of the Ornstein-Zernike equation, obtained by SANS experiments with 10 vol % solution in tetrahydrofuran, obey a power-law relation as a function of z-average molecular weight estimated by gel permeation chromatography, with scaling exponents of 0.57 and 0.27, respectively. These behaviors are unaffected by polymerization conditions, such as initial phenol-to-formaldehyde molar ratio in the range from 0.9 to 1.5, catalyst concentration with oxalic acid-to-phenol molar ratio from 0.01 to 0.1, and reaction time within the period in which the polymer remains soluble. SANS curves for polymers prepared under different conditions are sufficiently superimposed onto a single curve with the reduced variables, ξ⁻²I(q) and ξq. These results indicate that unfractionated phenolic resins have a self-similar structure with respect to the molecular weight.     

微乳化对ECH和TMAC反应的影响及动力学

在微乳化和非微乳化条件下研究了环氧氯丙烷(ECH)和三甲胺盐酸盐(TMAC)的反应。采用液相色谱和气相色谱分析相结合的方法,分别测定两种条件下随反应时间变化的各物质的量。实验结果表明,反应温度在20~40℃时,微乳条件下10 min时ECH的转化率接近60%,是非微乳条件时转化率的3倍以上;微乳条件下1,3-二氯-2-丙醇(DCP)的生成量比非微乳条件下的高出1个数量级。由此证明微乳条件下生成DCP反应的速率远高于非微乳体系。并根据实验结果建立了微乳化条件下ECH和TMAC反应的动力学方程。     

聚硅酸聚合氯化铁复合型絮凝剂的制备及性能研究

以盐酸酸洗废液和废铁屑为原料,制备了聚硅酸聚合氯化铁复合型絮凝剂(PSPFC),研究了聚铁中铁浓度、聚合硅酸浓度、聚合硅酸pH值、n(Fe)：n(Si)及复合熟化时间等因素对絮凝性能的影响。正交试验结果表明,当制备条件为：Fe／Si物质的量比为1：2,聚铁中铁浓度为0．6mol／L,复合熟化时间为40min时,研制的PSPFC对低浊污水(浊度10～20NTU)具有最佳处理效果,并具有较宽的pH适用范围。     

Facile synthesis and promising antibacterial properties of a new guaiacol-based polymer

A new acrylamide-type monomer (N-(4-hydroxy-3-methoxy-benzyl)-acrylamide) derived from guaiacol was successfully synthesized. Polymers containing guaiacol moiety were obtained via conventional radical polymerization of this monomer with AIBN as initiator. The influence of reaction time, initiator concentration and temperature on polymers characteristics was studied. Evaluation of the termination mode in free-radical polymerization was performed by MALDI-TOF mass spectrometry. Termination occurs mainly by disproportionation reaction. Additional peaks in the spectrum were attributed to side chain reactions implying phenoxy radicals. This new polymer exhibits a potential antibacterial activity against Bacillus subtilis by using anti-adhesion and anti-biofilm tests. After an adhesion time of 3 h, compared to a non-coated glass slide, there was a decrease of bacteria of 99% on the polymer coated glass slide. After three days of culture in a bacterial suspension, no biofilm was observed on the polymer coated surface.     

侧链结晶PVC的结构和热性能

通过亲核取代反应制备了可侧链结晶的梳型接枝聚氯乙烯(PVC),利用傅里叶变换红外光谱、核磁共振氢谱和凝胶渗透色谱表征了梳型接枝PVC的结构,采用差示扫描量热法研究了接枝率与侧链长度对侧链结晶行为、熔融行为及玻璃化转变温度(tg)的影响。本研究方法可有效地将长链烷基接枝到PVC骨架上,并形成侧链结晶。侧链结晶的熔融焓和熔融温度随接枝率的增大而增大,随侧链的增长而减小。tg随接枝率的增大先降后增,连接含有较长侧链的PVC的tg明显高于不含侧链的PVC。     

磺化聚氯乙烯的催化活性

研究了磺化聚氯乙烯在酯化、缩醛或缩酮的合成以及频呐重排反应中的应用。结果表明,此催化剂的催化活性和重复性良好。