45 resultados para CROSS-LINKED CHAINS
Resumo:
Gelatin is widely used in food, pharmaceutical, and photographic industries due to the coil-helix transition, whereas the structural inhomogeneity considerably affects its essential properties closely connecting with the industrial applications. The spatially structural inhomogeneity of the gelatin caused by the uneven and unstable temperature field is analyzed by the finite element method during the cooling-induced coil-helix transition process. The helix conversion and the crosslinking density as functions of time and spatial grid are calculated by the incremental method. A length distribution density function is introduced to describe the continuous length distributions of two kinds of triple helices.
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Two novel of tri- and tetra-functional biphenyl acid chloride: 3,4',5-biphenyl triacyl chloride (BTRC) and 3,3',5,5'-biphenyl tetraacyl chloride (BTEC), were synthesized, and used as new monomers for the preparations of the thin film composite (TFC) reverse osmosis (RO) membranes. The TFC RO membranes were prepared on a polysulfone supporting film through interfacial polymerization with the two new monomers and m-phenylenediamine (MPD). The membranes were characterized for the permeation properties, chemical composition, d-space between polymer chains, hydrophilicity, membrane morphology including top surface and cross-section. Permeation experiment was employed to evaluate the membranes performance including salt rejection and water flux. The surface structure and chemical composition of membranes were analyzed by attenuated total reflectance infrared (ATR-IR) and X-ray photoelectronic spectroscopy (XPS). The results revealed that the active layer of membranes was composed of highly cross-linked aromatic polyamide with the functional acylamide (-CONH-) bonds. The TFC membranes prepared from biphenyl acid chloride exhibit higher salt rejection compared with that prepared from trimesoyl chloride (TMC) at the expanse of some flux.
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A PEO-tethered layer on a PDMS (polydimethylsiloxane) cross-linked network has been prepared by a swelling-deswelling process. During swelling, the PDMS block of a PDMS-b-PEO diblock copolymer penetrates into the PDMS substrate and interacts with PDMS chains because of the van der Waals force and hydrophobic interaction between them. Upon deswelling, the PDMS block is trapped in the PDMS matrix while the PEO, as a hydrophilic block, is tethered to the surface. The PEO-tethered layer showed stability when treated in water for 16 h. The surface fraction of PEO and the wetting property of the PEO-tethered PDMS surface can be controlled by the cross linking density of the PDMS matrix. A patterned PEO-tethered layer on a PDMS network was also created by microcontact printing and water condensation figures (CFs) were used to study the patterned surface with different wetting properties.
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The compounds (het)(PtCl6)2H(2)O 1, (het)(HgI4).H2O 2 (het = 2-(alpha-hydroxyethyl)thiamine) and (hpt)(Hg2Br6) 3 (hpt = 2-(alpha-hydroxypropyl)thiamine) have been prepared and structurally characterized by X-ray crystallography in order to study the influence of the anion and molecular conformation on the formation of supramolecular architectures that adsorb anionic species. Both het and hpt molecules adopt the usual S conformation for C2-substituted thiamine but differ from the F conformation for C2-free thiamine derivatives. Two types of characteristic ligand-anion complexation are observed, being of the forms C(6')-H...anion...thiazolium-ring (in 1 and 2) and N(4'1)-H...anion...thiazolium-ring (in 3). The reaction of het with PtCl62- or HgI42- gives a 1-D double-chain in 1, consisting of two hydrogen-bonded het chains, which are cross-linked by anions through hydrogen bonding and anion...aromatic-ring interactions, or a cationic 3-D framework in 2 formed by the stacking of hydrogen-bonded sheets with anion-and-water-filled channels. In the case of 3, hydrogen-bonded hpt dimers and HgBr62- anions form alternate cation-anion columns. A comparison with the cases of C2-free thiamine-anion complexes indicates that the change in molecular conformation results in novel supramolecular assemblies in 1 and 2 and an analogous architecture in 3, which also depends on the nature of the anions.
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Recent research carried out at the Chinese Institute of Applied Chemistry has contributed significantly to the understanding of the radiation chemistry of polymers. High energy radiation has been successfully used to cross-link fluoropolymers and polyimides. Here chain flexibility has been shown to play an important role, and T-type structures were found to exist in the cross-linked fluoropolymers. A modified Charlesby-Pinner equation, based upon the importance of chain flexibility, was developed to account for the sol-radiation dose relationship in systems of this type. An XPS method has been developed to measure the cross-linking yields in aromatic polymers and fluoropolymers, based upon the dose dependence of the aromatic shake-up peaks and the F/C ratios, respectively. Methods for radiation cross-linking degrading polymers in polymer blends have also been developed, as have methods for improving the radiation resistance of polymers through radiation cross-linking.
Resumo:
Four novel polymeric lanthanide(III) complexes of two new double betaine derivatives have been synthesized and structurally determined. In [{La-2(L-1)(2)(H2O)(9)}(n)]Cl-6n. 2nH(2)O (1) and [{Tb(L-1)(H2O)(4)}(n)]Cl-3n. nH(2)O (2) (L-1 =4,4'-trimethylenedipyridinio-N,N'-diacetate), the lanthanide(III) ions form a two-dimensional layer in which each pair of lanthanide(III) ions is bridged by two syn-anti mu-carboxylato-O,O' groups. Adjacent layers are cross-linked through hydrogen bonds among aqua ligands, lattice water molecules and chloride ions, to form a three-dimensional network. Isomorphous [{Ln(L-1)(H2O)(4)}(n)]Cl-3n. 5nH(2)O (Ln=La, 3; Ln=Tb, 4; L-2=1,3 bis(pyridinio-4-carboxylato)-propane) each contain a centrosymmetric paddle-wheel-like dimeric unit in which each pair of adjacent metal atoms is bridged by four syn-syn mu-carboxylato-O,O' groups that are oriented nearly perpendicular to each other about the metal-metal axis. Neighboring dimeric subunits are bridged by a pair of flexible LL ligands into a polymeric chain. Adjacent chains are inter-linked by hydrogen bonds among aqua ligands, lattice water molecules and chloride ions into a three-dimensional network. (C) 1999 Elsevier Science Ltd. All rights reserved.
Resumo:
A novel europium(III) coordination polymer with a new double betaine derivative, {[Eu(L')(NO3)(H2O)(3)](NO3)(2). 3.5H(2)O}(n) (L-1 = 1,3-bis(pyridinio-4-carboxylato)-propane) has been synthesized and its structure determined. Its luminescence properties have also been studied. The title metal carboxylate coordination polymer contains centrosymmetric dimeric units in which each pair of metal ions is linked by a pair of syn-anti carboxylato-O,O' groups, and each pair of such dimeric units is bridged by the backbones of L-1 ligands to form infinite double chains in the b direction. These metal carboxylate chains are further cross-linked by hydrogen bonds among both coordinated and discrete nitrate anions, aqua ligands and lattice water molecules to form a three-dimensional network. Luminescent data show that the L-1 ligand is a good energy donor and the complex has a relatively long luminescent lifetime.
Resumo:
Four new polymeric lanthanide(III) complexes of nicotinic acid N-oxide and isonicotinic acid N-oxide have been synthesized and structurally determined. In the isomorphous compounds [(Ln(L-1)(3) (H2O)(2))(n)]. 4nH(2)O(HL1 = nicotinic acid N-oxide; Ln = Eu, 1; Ln = Er, 2) the lanthanide(III) ions form infinite double chains along the b direction through the coordination of bridging carboxylate and N-oxide groups. The chains are cross-linked through hydrogen bonds between aqua ligands and uncoordinated N-oxide groups and between aqua ligands and lattice water molecules, to form a three-dimensional network. [(Eu(L-2)(2)-(H2O)(4))(n)](NO3)(n). nH(2)O (HL2 = isonicotinic acid N-oxide, 3) has a polymeric structure in which the europium (III) ions are connected into infinite chains by pairs of syn-syn carboxylate groups. Adjacent chains are interlinked by hydrogen bonds between aqua ligands and N-oxide groups to form a layer parallel to the (100) plane, and such layers are connected by hydrogen bonds between nitrate anions and aqua ligands, and between oxide groups and lattice water molecules, into a three-dimensional network. In [(Er-2(L-2)(4)(H2O)(10))](NO3)(2). H2O, 4, dinuclear units are inter-linked into a three-dimensional network through hydrogen bonding between aqua ligands and N-oxide groups of both bidentate bridging and unidentate L-2 ligands. Factors affecting the formation of coordination chains and dinuclear units are discussed. Luminescence properties of 1 and 3 have also been studied. (C) 1998 Elsevier Science Ltd. All rights reserved.
Resumo:
A new Er(III)-Na(I) coordination polymer of stoichiometry [NaEr2L5(H2O)(6)(NO3)](NO3). 3.5H(2)O (HL = picolinic acid N-oxide) has been synthesized and characterized by single-crystal X-ray analysis. Crystals are triclinic, P (1) over bar with a = 9.823(2), b = 12.453(2), c = 20.643(4) Angstrom; alpha = 98.49(3), beta = 101.40(3), gamma = 108.69(3)degrees; V = 2284(1) Angstrom(3); Z = 2. Of the two independent eight-coordinate erbium(III) ions in this complex, one is surrounded by four bidentate chelating L ligands, and the other by one bidentate chelating L ligand, four aqua ligands and two anti-carboxylate oxygen atoms from two neighboring [ErL4] units. The sodium(I) ion is in a distorted octahedral environment, being coordinated by a unidentate nitrate anion, three aqua ligands and two anti-carboxylate oxygen atoms from two adjacent [ErL4] units. The complex is built from zigzag chains of syn-anti carboxylate-bridged erbium(III) moieties directed in the a direction, which are cross-linked pairwise by aqua-bridged dimeric sodium(I) units. The resulting composite polymeric chains are further connected by hydrogen bonds to form a three-dimensional network.
Resumo:
A novel polymeric Pr(III) complex with a new double betaine, namely [{Pr(L-1)(1.5)(H2O)(2)}(n)] [ClOli4]3(n). nH(2)O (1) (L-1= 1,4-diazoniobicyclo[2,2,2]octane- 1,4-dipropionate), has been synthesized and characterized by X-ray analysis. In the title complex, the Pr(III) atom is nine-coordinated by seven oxygen atoms from five L-1 ligands and two aqua ligands. Each pair of adjacent praseodymium(III) atoms is linked by a pair of mu(3) chelating and bridging carboxylate groups, thus forming an infinite metal metal chain running parallel to the a direction, and such chains are cross-linked by flexible backbones of L-1 ligands into a three-dimensional network with the perchlorate anions and lattice water molecules accommodated in the interstitial space. The title complex crystallizes in the monoclinic space group P2(1)/n with a = 8.085(2), b = 14.316(3), c = 29.775(6) Angstrom, beta = 103.04(3)degrees and Z = 4.
Resumo:
本文以过氧化物为引发剂,采用反应挤出的方法,制备了甲基丙烯酸缩水甘油酷官能化聚丙烯,采用化学滴定法和红外光谱法均证实了接枝共聚物的存在,并研究了反应条件对PP-g-GMA接枝率、接枝效率和熔体流动速率的影响,结果表明:1.当DCP含量一定时,随着单体含量的增加,接枝产物的接枝率出现了一个峰值。这表明一味地增加单体浓度未必有利于接枝率的提高;2.当GMA单体浓度一定时,PP-g-GMA的接枝率和熔融指数均随着引发剂含量的增加而逐渐增大,这表明引发剂浓度的增加在促进接枝反应的同时也引入了更多的副反应;3.助剂苯乙烯的加入大大地提高了PP-g-GMA的接枝率和接枝效率,且产物的熔融指数与纯聚丙烯相比变化很小,这表明助剂苯乙烯的加入有效地抑制了副反应的发生,且促进了接枝反应的发生。研究了官能化聚丙烯PP-g-GMA的形态、结构与性能,结果表明:1.官能化对聚丙烯的结晶行为有显著的影响,不仅结晶温度和熔融温度有显著的增加,而且结晶度也有一定程度的增加;2.纯聚丙烯的结晶结构为典型的a型结晶,而接枝聚丙烯的结晶则以a型结晶为主,并出现了少量的Y型结晶;3.采用Avrami方程可以很好的描述官能化聚丙烯的初级结晶行为,纯聚丙烯和官能化聚丙烯的 tl几和tmax均随着结晶温度的增加而增加,这表明它们的结晶过程由成核控制;4.采用Jeziornn法研究了官能化聚丙烯的非等温结晶动力学,非等温结晶过程可以分为初级结晶和次级结晶两部分,在次级结晶阶段,曲线偏离了初级结晶部分的直线,表明在次级结晶阶段,官能化聚丙烯的成核与生长方式发生了变化;5.采用DMA研究了官能化聚丙烯的动态热机械行为,官能化后聚丙烯的耐热性提高了,而且随着接枝率的升高,耐热性又有进一步的提高。以官能化聚丙烯作为反应型增容剂,采用反应共棍的方法,制备了耐油型全 硫化CNBR/PP热塑性弹性体,并研究了热塑性弹性体的形态、结构与性能。主要 结果如下:1.采用红外光谱法表征了梭基丁睛粉末橡胶和PP-g-GMA间的反应。 2.透射电子显微镜和原子力显微镜结果表明,当一部分聚丙烯被官能化聚丙烯替代后,体系中橡胶粒子的尺寸明显变小了,分布也更加均一了。在CNBR/PP-g-GMIA 体系中,原位增容反应形成的共聚物位于cNBR和PP-g-GMA两相的界面处。3.加入少量接枝聚丙烯后共混物的力学性能,如拉伸强度、100%定伸强度和断裂伸长 率均有明显的提高,而且,对于CNBR/PPPP-g-GMA共混物,只需少量的界面增 容剂便可以使两相界面达到饱和并达到较好的增容效果。4.动力学和热力学因素 均影响共混物中聚丙烯的结晶行为,在CNBR/PP体系中,动力学因素占主导地位,而CNBR/PP-g-GMA体系中热力学因素占主导作用。另外,采用Avromi方程描述了CNBR/PP和CNBR/PP-g-GMA体系的等温结晶动力学。5.接枝聚丙烯的加入阻碍了接枝聚丙烯与梭基丁睛橡胶两相间的界面层滑移,因此提高了体系的粘度。以官能化聚丙烯作为反应型增容剂,采用反应共混的方法,制备了耐油型全硫化NBR/PP热塑性弹性体,并研究了热塑性弹性体的形态、结构与性能。主要结果如下:1.采用红外光谱法表征了官能化聚丙烯与端氨基液体丁睛橡胶间的反应,但仅从红外光谱的结果很难断定产物的分子结构;2.采用透射电子显微镜观察了NBR/PP共混物的微观形态,结果表明,NBR/PP共混物体系中除了含有直径为几十纳米的小橡胶粒子外,还有直径为几微米甚至几十微米的大橡胶粒子存在,且随着橡胶含量的增加,体系中大橡胶粒子的数量增多了,小橡胶粒子的分布也变得密集了;3.采用差示扫描量热法表征了NB侧PP共混物的受限结晶行为,结果表明,(1)在220℃的高温下,部分丁睛橡胶分子产生了一定的运动,从而限制了聚丙烯分子的运动,使聚丙烯分子产生了受限结晶行为;(2)随着橡胶含量的增加,橡胶粒子间的距离逐渐变小,这使得位于橡胶粒子间隙的聚丙烯分子的运动受到限制,因此聚丙烯表现出受限结晶的行为;(3)受限的聚丙烯分子更倾向于Y型结晶。
Resumo:
A NADH and glucose biosensor based on thionine cross-linked multiwalled carbon nanotubes (MWNTs) and Au nanoparticles (Au NPs) multilayer functionalized indium-doped tin oxide (ITO) electrode were presented in this paper. The effect of light irradiation on the enhancement of bioelectrocatalytic processes of the biocatalytic systems by the photovoltaic effect was investigated.
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Two highly connected cobalt(II) and zinc(II) coordination polymers with tetranuclear metal clusters as the nodes of network have been prepared, being the first example of an 8-connected self-penetrating net based on a cross-linked alpha-Po subnet.
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This paper presented a new approach for preparing a new type of slow-release membrane-encapsulated urea fertilizer with starch-g-PLLA as biodegradable carrier materials. By solution-casting and washing rapidly with water the urea was individually encapsulated within the starch matrix modified by L-lactide through in situ graft-copolymerization.
Resumo:
Chitosan(chitin)/cellulose composites as biodegradable biosorbents were prepared under an environment-friendly preparation processes using ionic liquids. Infrared and X-ray photoelectron spectra indicated the stronger intermolecular hydrogen bond between chitosan and cellulose, and the hydroxyl and amine groups were believed to be the metal ion binding sites. Among the prepared biosorbents, freeze-dried composite had higher adsorption capacity and better stability. The capacity of adsorption was found to be Cu(II) (0.417 mmol/g) > Zn(II) (0.303 mmol/g) > Cr(VI) (0.251 mmol/g) > Ni(II) (0.225 mmol/g) > Ph(II) (0.127 mmol/g) at the same initial concentration 5 mmol L-1. In contrast to some other chitosan-type biosorbents, preparation and component of the biosorbent were obviously more environment friendly. Moreover, adsorption capacity of chitosan in the blending biosorbent could be fully shown.