Structure-Morphology-Antimicrobial and Antiviral Activity Relationship in Silver-Containing Nanocomposites Based on Polylactide

Green synthesis of silver-containing nanocomposites based on polylactide (PLA) was carried out in two ways. With the use of green tea extract, Ag⁺ ions were reduced to silver nanoparticles with their subsequent introduction into the PLA (mechanical method) and Ag⁺ ions were reduced in the polymer matrix of PLA-AgPalmitate (PLA-AgPalm) (in situ method). Structure, morphology and thermophysical properties of nanocomposites PLA-Ag were studied by FTIR spectroscopy, wide-angle X-ray scattering (WAXS), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC) methods. The antimicrobial, antiviral, and cytotoxic properties were studied as well. It was found that the mechanical method provides the average size of silver nanoparticles in the PLA of about 16 nm, while in the formation of samples by the in situ method their average size was 3.7 nm. The strong influence of smaller silver nanoparticles (3.7 nm) on the properties of nanocomposites was revealed, as with increasing nanosilver concentration the heat resistance and glass transition temperature of the samples decreases, while the influence of larger particles (16 nm) on these parameters was not detected. It was shown that silver-containing nanocomposites formed in situ demonstrate antimicrobial activity against gram-positive bacterium S. aureus, gram-negative bacteria E. coli, P. aeruginosa, and the fungal pathogen of C. albicans, and the activity of the samples increases with increasing nanoparticle concentration. Silver-containing nanocomposites formed by the mechanical method have not shown antimicrobial activity. The relative antiviral activity of nanocomposites obtained by two methods against influenza A virus, and adenovirus serotype 2 was also revealed. The obtained nanocomposites were not-cytotoxic, and they did not inhibit the viability of MDCK or Hep-2 cell cultures.     

Omniphobic Coatings Based on Amphiphilic Diblock Copolymers of 2-(Perfluorohexyl)ethyl Methacrylate and 2-Hydroxyethyl Methacrylate

Doklady Chemistry - Amphiphilic diblock copolymers of 2-(perfluorohexyl)ethyl methacrylate and 2-hydroxylethyl methacrylate have been synthesized for the first time by two-stage reversible...     

Effect of LiClO4 Salt on Dielectric Properties of Acrylonitrile-Methyl Methacrylate and Acrylonitrile-Isobutyl Methacrylate Copolymers

Poly(acrylonitrile-co-isobutyl methacrylate), PAN-co-PIBMA, and poly(acrylonitrile-co-methyl methacrylate), PAN-co-MMA copolymers are synthesized by emulsion polymerization. The structural characterization is done by FTIR and ¹H-NMR spectroscopy and thermal analyses are performed by thermogravimetric analysis (TGA). After various amounts of LiClO₄ salt loading into copolymer films, the dielectric properties of these films at different temperatures and frequencies are determined. The effects of different methacrylate groups and salt content on the dielectric properties of copolymers are investigated. It is found that the dielectric constant increases systematically with increasing MMA and IBMA content in the copolymer. The samples with higher salt content show higher ac-conductivities.     

聚合物存在下纳米银复合材料的制备与表征

以聚丙烯腈聚乙二醇嵌段共聚物PAN-b-PEG-b-PAN为稳定剂, 在超声辐照下成功地制备了分散性较好、尺寸均匀的纳米银颗粒. 用X射线衍射(XRD)、红外光谱(FTIR)、透射电镜(TEM)、紫外-可见吸收光谱(UV-Vis)和热分析(TGA)等对制备的纳米银复合材料进行了表征. 红外结果表明超声辐照并没有破坏聚合物的链结构. 聚合物的引入, 对纳米银颗粒起到了很好的分散保护作用. 用低浓度的硝酸银溶液, 得到粒径较小的纳米银颗粒; 随着硝酸银浓度增大, 纳米银颗粒粒径也增大. 而聚合物的浓度增大时, 所得银纳米颗粒粒径减小. 对银纳米颗粒的形成机理进行了讨论.     

A Recording Medium Based on Copolymer of 4-((1,5-Dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)diazenyl)phenyl Methacrylate with Nonyl Methacrylate for Polarization Holography

A recording medium based on a novel copolymer of 4-((4-hydroxyphenyl)diazenyl)-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one with nonyl methacrylate is created, and the possibility of its use for polarization holography is investigated. It is shown that, for films based on this copolymer, holograms can be recorded without special heating due to a fairly low softening temperature. The recorded holograms are characterized by low noisiness.     

Synthesis,Antimicrobial Activity and Semi-conducting Properties of Novel 2-(4-Chloro-1-Naphtyloxy)-2-Oxoethyl Methacrylate with 2-(Diethylamino)Ethyl Methacrylate Copolymers

The free-radical initiated copolymerization of 2-(4-chloro-1-naphtyloxy)-2-oxoethyl methacrylate (ClNOEMA) with 2-(diethylamino) ethyl methacrylate (DEAEMA) was carried out in 1,4-dioxane solution at 70 ± 1°C using 2,2′-azobisisobutyronitrile (AIBN) as an initiator with different monomer-to-monomer ratios (ranging from 0.15 to 0.85) in the feed. The copolymer composition obtained by elemental analysis led to the determination of reactivity ratios employing Fineman-Ross (F-R) and Kelen-Tüdös (KT) linearization methods. These parameters were also estimated using a non-linear computational fitting procedure, known as reactivity ratios error in variable model (RREVM). The prepared homo and copolymers were tested for their antimicrobial activity against bacteria and yeast. These copolymers have been converted into novel salts by reaction with the iodemethane (CH₃I). The copolymers and the corresponding salts have been characterized fully by a range of spectroscopic analysis techniques. The electrical conductivity dependence of temperature of the polymers were measured and the polymers exhibit the semi-conducting behavior, confirming that the electrical conductivity increases with increasing temperature. The poly(CINOEMA-co-DEAEMA) polymer doped by CH₃I for 15 min shows the highest conductivity. The optical band gap, activation energy and room temperature conductivity values of these polymers were obtained. These electronic parameters suggest that the poly(CINOEMA-co-DEAEMA)s doped by CH₃I for 15 min is an organic semiconductor with the thermally activated conduction mechanism.     

Preparation and Properties of Layered Silicate Nanocomposites Based on Ethylene Vinyl Acetate Copolymers

(Nano)composites based on ethylene vinyl acetate copolymers (EVA) and montmorillonite modified by various alkylammonium cations were processed by mechanical kneading. Polymer intercalation and filler exfoliation were evidenced by X‐ray diffraction and transmission electron microscopy, respectively. Nanocomposites tensile properties showed that Young's modulus increases significantly even at very low content of the organo‐modified filler while preserving high ultimate elongation and tensile stress. The matrix thermal stability in air was increased by 40°C and, interestingly, the obtained nanocomposites present flame retardant properties.     

聚甲基丙烯酸2,2,3,3-四氟丙酯及其单体与甲基丙烯酸甲酯共聚物的合成与表征

含氟甲基丙烯酸酯聚合物中的氟原子可使其折光指数n_D很低。这是光导纤维皮材的首要条件^[1]。这类材料的大分子主链与作为芯材使用的聚甲基丙烯酸甲酯(PMMA)具有相同的结构,因此其间的相容性和粘结性好,有利于光的全反射;其热稳定性也好^[2,3],可用于共挤出法制造塑料光导纤维.     

Mechanical Properties of Copolymers from Methacrylate Functionalized Silanes and Bifunctional Methacrylate Monomers

Sol gel derived composite materials were prepared from methacryloxypropyltrimethoxysilane (MPTS) and tetraethyleneoxidedimethacrylate (TEGDMA). The amount of MPTS in the composites was varied from 0 to 50 mole%. MPTS was prehydrolyzed at room temperature with 0,1 mole/l HCl/H₂O. After complete removal of solvent calculated amounts of TEGDMA were added to the reaction mixture of the prehydrolyzed MPTS. Thermically initiated free radical copolymerization of the methacrylate endgroups was performed in the resulting mixture under nitrogen atmosphere using azobisisobutyronitril (AIBN) as initiator. The composites were investigated by high resolution transmission electronmicroscopy in order to investigate the morphology. The thermomechanical properties as storage, loss modulus, tan as well as the glass transition temperature (T _g ) of the composites were estimated by dynamic mechanical thermal analysis (DMTA).     

Multicomponent Polymers of Poly(Lactic Acid) Macromonomers with Methacrylate Terminal and Copolymers of Poly(2-Hydroxyethyl Methacrylate)

Abstract

Poly(lactic acid) macromonomers with methacrylate terminal functionality have been synthesized from the cyclic dimer of lactic acid (referred to as lactide) with 2-hydroxyethyl methacrylate (HEMA) as initiator and stannous 2-ethyl hexanoate as catalyst. The macromonomers were characterized with FT-IR, NMR, GPC, DSC, WAXS, and CD. The molecular weights of the macromonomers ranging from M _n 1425 to 19,169 are predictable from the lactide/HEMA ratio in the polymerization feeds. The properties of the macromonomers vary with the stereochemistry of the lactide and the composition. Circular dichroism measurements demonstrate that there is little racemization during polymerization.     

Alternating Copolymers of Limonene with Methyl Methacrylate: Kinetics and Mechanism

The radical copolymerization of limonene (optically active) with methyl methacrylate in xylene at 80±0.1°C for 1 hr, initiated by benzoyl peroxide (BPO) yield alternating copolymer(s), under the inert atmosphere of nitrogen, as evidenced by reactivity ratios r₁ (MMA)=0.07 and r₂ (limonene)=0.012 using the Kelen–Tüdos method. The kinetic expression is Rα[I]^0.5[MMA]^1.0[Lim.]^?1.0. The decrease in the rate of polymerization with increase in concentration of limonene is due to penultimate unit effect. The overall energy of activation is calculated as 49 kJ/mole. FTIR of the copolymer(s) shows the characteristic frequencies at 1732.40 and 2951.40 cm^?1 due to –OCH₃ of MMA and aromatic C–H stretching of limonene, respectively. ¹H NMR spectra shows peak at 3.8–4.1 δ and 5.3–5.6 δ due to –OCH₃ of MMA and trisubstituted olefinic protons [–CH=CH–CH₂–] of limonene, respectively.     

新型含硫高折光指数光学树脂单体MPSDMA的合成及其共聚树脂的性能研究

通过氯磺化反应,还原反应和低温相转移仙化反应合成了一种新型光学树脂单体合成 4,4′-二巯基二苯硫醚双甲基丙烯酸酯（MPSDMA）,。成功地将苯环、含硫基团和双键引入光学树脂单体结构中,将MPSDMA分别与甲基丙烯酸甲酯（MMA）和苯乙烯（St)通过自由基共聚制成透明树脂,共聚树脂性能的研究表明该类新型光学树脂具有高折光指数,高表面硬度等特点。     

Self-assembled and Nanostructured Copolymer Aggregations of the Tertiary Amine Methacrylate Based Triblock Copolymers

The micellization behavior of novel tertiary amine methacrylate-based ABA type triblock copolymers formed by poly[2-(dimethylamino)ethyl methacrylate] [PDMA] middle block and poly[2-(diethylamino)ethyl methacrylate] [PDEA] or poly[2-(diisopropylamino)ethyl methacrylate] [PDPA] side blocks, PDPA_m-b-PDMA_n-b-PDPA_l, and PDEA_m-b-PDMA_n-b-PDEA_l was investigated. Both types of triblock copolymers were water-soluble and had potential for various applications due to their self-assembled and the bottom-up nanoscale micellar construction. The micellar aggregations of the triblock copolymers in aqueous solutions with varying comonomer ratios, molecular weights, temperatures, and pH values were investigated by small-angle X-ray scattering and dynamic light scattering. Compact micellar aggregations were obtained as 0.5 weight percent solutions at 20–21°C and pH 8.67 to 9.05, and characterized as polydispersed spherical core-shells. One group of triblock copolymer micelles had PDPA-cores with radii from 18 to 21 Å and PDMA-shell thicknesses of 89–105 Å, whereas the other group had PDEA-core spherical micelles with core radii of 60–62 Å and a PDMA-shell thicknesses of 64–66 Å.     

甲基丙烯酸缩水甘油酯大孔共聚物的合成、结构及性能研究

以甲基丙烯酸缩水甘油酯为单体,二乙烯苯/三烯丙基异氰脲酸酯作为混合交联剂,甲苯和正庚烷为混合致孔剂,通过悬浮聚合,合成了一系列GMA-DVB-TAIC大孔共聚物,考察了不同反应阶段共聚物的孔结构,通过调节交联剂的用量、致孔剂的用量和比例,可以得到具有较大孔容和孔径、较高热稳定性和性能优良的GTD大孔共聚物.     

Synthesis and Gas Permeability of Cyclotetrasiloxane-Containing Methacrylate Copolymers

Abstract

Synthesis and gas permeability of random and block copolymers of a cyclotetrasiloxane-containing methacrylate have been studied in comparison with those of tris(trimethylsiloxy)silane-containing methacrylate (MTTS) copolymers. Random and block copolymers of 3-(heptamethyl cyclotetrasiloxanyl) propyl methacrylate (HCPM) and methyl methacrylate (MMA) were prepared by radical copolymerization using 2,2′-azobisisobutyronitrile and a poly(azoinitiator), poly(1,6-hexamethylene 4,4′-azobiscyanopentanoate), respectively. Differential scanning calorimetry (DSC) revealed that HCPM-MMA block copolymers exhibited heterogeneous phases, as evidenced by two distinct glass transition temperatures due to poly-HCPM (PHCPM) block and PMMA block, while the single glass transition temperatures in the homogeneous phases in HCPM-MMA random copolymers lowered with HCPM content. The oxygen and nitrogen gas permeability coefficients of HCPM-MMA random copolymer films measured at 23°C were found to steeply increase with HCPM contents, although those of HCPM-MMA block copolymers slightly increased. The permeability coefficients of MTTS-MMA random copolymers prevailed over those of HCPM-MMA random copolymers despite the same four Si atoms, probably because of its free volume effect. Further, the HCPM content dependency on the diffusion and solubility coefficients, and the effect of crosslinking on their gas permeability were also discussed.     

Thermal Behaviour of Glycidyl Methacrylate Homopolymers and Copolymers

The paper describes the effect of molecular mass and copolymer composition on thermal behaviour of homopolymers and copolymers of glycidyl methacrylate and methyl methacrylate. The polymerisation was done by using group transfer polymerization (GTP) and free radical techniques. A multistep decomposition was observed in polymers prepared by free radical technique indicating the presence of weak linkages in the backbone. Copolymers prepared by GTP had fewer weak sites and degraded in single step by a random chain scission.This revised version was published online in November 2005 with corrections to the Cover Date.     

梳状丙烯酸酯类共聚物凝胶电解质的传输性能与自由体积

用三种分子量大小不等的聚乙二醇单甲醚(PEGME)与甲基丙烯酸甲酯-马来酸酐共聚物[P(MMA-co-MAh)]反应,制备了三种支链长度不等的梳状共聚物(MMA/MAh-g-PEGME), 并以此为基体, 加入增塑剂碳酸丙烯酯(PC)和高氯酸锂(LiClO₄), 采用溶剂浇铸法制备了三种凝胶聚合物电解质(GPE)膜, 研究了其离子传输性能, 发现该聚合物凝胶电解质的离子传输机理符合VTF (Vogel-Tamman-Fulcher)方程, 即离子传输性能与凝胶体系自由体积的大小有关; 采用正电子湮没寿命谱仪(PALS)研究了GPE 体系的自由体积特性, 获得了各支链长度不同的共聚物凝胶电解质的自由体积分数, 分析各自由体积与离子传输性能之间的关系, 建立了共聚物结构、凝胶聚合物自由体积及其传输性能之间的关系. 发现梳状共聚物支链长度越长, 凝胶电解质的自由体积越大, 离子传输性能越高.     

Copolymers from Castor Oil Prepolymers (COP). 4. Copolymerization of Methyl Methacrylate with COP

The copolymerization of castor oil prepolymer (COP) with methyl methacrylate (MMA) has been accomplished at 75°C using a free radical initiator. The monomer reactivity ratios of MMA (r₁) and COP (r₂) were determined to be r₁ = 3.04 and r₂ = 0.605. With an increasing concentration of COP in the binary mixture, copolymers with decreasing molecular weight were obtained. The copolymers obtained were powdery substances soluble in many organic solvents.     

Copolymerization and Copolymers of 2,4,5-Tribromostyrene with Methyl Acrylate and Methyl Methacrylate

Abstract

2,4,5-Tribromostyrene (TBSt) was copolymerized with methyl acrylate (MA) or methyl methacrylate (MMA) in a toluene solution using 2,2′-azobisisobutyronitrile as free radical initiator. The copolymerization reactivity ratios were found to be for the system TBSt / MA r₁= 7.4 ± 1.2 (TBSt) and r₂= 0.1 ± 1.4 (MA) and for the system TBSt / MMA r₁ = 1.8 ± 0.2 (TBSt) and r₂ = 0.1 ± 0.2 (MMA). The e and Q values were also calculated. The initial rate of copolymerization, as well as molecular weight of the obtained copolymers for both system linearly increase as the content of TBSt in the monomer mixture increases. Similar behavior has also been established for the course of the copolymerization reactions to high conversions. The resulting copolymers rapidly decompose at temperatures 20–800°C above the decomposition of corresponding (metha)crylate hompolymers. However, the glass transition temperature increases markedly with increasing TBS content.     

Copolymers of 3-Methoxy-4-Acryloyloxy-Benzal Phenylimine with Methyl Methacrylate: Synthesis,Characterization and Monomer Reactivity Ratios

Abstract

Copolymers of 3-methoxy-4-acryloyloxybenzal phenylimine and methyl methacrylate with different feed ratios are synthesized in ethyl methyl ketone using benzoyl peroxide as a free radical initiator at 70 ± 1°CC. The polymers were characterized by IR and ¹H-NMR spectroscopic techniques. Copolymer compositions were determined by ^lH-NMR analysis of the polymers. The monomer reactivity ratios were determined by the application of conventional linearization methods such as Fineman-Rose and Kelen-Tüdös. The molecular weights M_n and M_w of the polymers and the poly-dispersity index were determined by gel permeation chroma-tography. The intrinsic viscosities and the thermal properties of the homo-and copolymers are also discussed.