Structure and hydrodynamics of polyamic acid chains in solutions. Effect of “pin-joint” oxygen atom

The hydrodynamic characteristics and weight-average molecular weights of some samples of poly-(4,4′-oxydiphenylene) pyromellitamic acid (I) and poly (4,4′-phenylene) pyromellitamic acid (II) in DMF have been obtained by sedimentation, viscometry and light scattering. For (I) the dependence of S₀ on M was obtained and it was found that the hydrodynamic parameters $\text{F}{}^{\mathrm{<mtext>1</mtext><mtext>3</mtext>}}\text{P}{}^{\mathrm{?1}}$ depend on M up to M = 10⁵. The experimental results were treated by using two models, viz. a Yamakawa-Fujii persistent chain and a rotational isomeric chain with free rotation about valence bonds. It was shown that the hydrodynamic behaviour of macromolecules of (I) with a pin-joint oxygen atom in the main chain is satisfactorily described by the rotational isomeric chain model with free rotation about valence bonds. The dependence of [η] on M was obtained and the constants K and a in an equation of the Mark-Kuhn-Houwink type were determined for (II). The flexibility of the chain was estimated and the Kuhn segment was found to be 200 Å using the Yamakawa-Fujii theory. The flexibilities of the chains of (I) and (II) are compared; it is shown that the rigidity of the chain of (II) without a pin-joint oxygen atom in the monomer unit is much higher than that of the chain of (I). The dependence of S₀ on M obtained for (II) suggests that its macromolecules show a more pronounced tendency for formation of aggregates than those of (I).     

激光光散射研究丙烯酰胺-二甲基二烯丙基氯化铵共聚物的溶液行为

用激光光散射技术表征了阳离子含量受控的丙烯酰胺 二甲基二烯丙基氯化铵共聚物 (简称P(AM DMDAAC) )在 0 1mol LNaCl溶液中的基本参数和溶液行为 .表观基本参数 : Mw ,app =5 0 4× 10 5g·mol- 1 、app =39 9nm和A2 ,APP =1 5× 10 - 4cm3·mol·g- 2 .动态光散射研究结果表明 ,扩散系数Dt 与角度、浓度皆呈非线性依赖关系 ,当C >C 或在较大的散射角域 ,Dt 偏离线性关系所预示的理论值而向减小的方向发展 ,表明存在缔合物 ;流体力学半径Rh 分布有大、小两个范围 ,并随温度升高向小尺寸方向发展 ,证明了体系中存在缔合行为以及升温的解缔合作用 .在一定条件下 ,“亚稳定性”的存在有力地旁证了体系的缔合行为     

Calix[4]crown in dual sensing functions with FRET

A new calix[4]crown chemosensor based on dual sensing probes reveals Pb²⁺ ion selectivity over other metal ions, which arises from a hypsochromic shift of azo units in UV spectrum as well as a fluorescence enhancement of pyrenyl parts in fluorescence spectrum via a suppressed FRET.     

κ-卡拉胶热可逆凝胶化行为研究

用固体小角激光散射方法研究κ 卡拉胶 (KC)的热可逆凝胶化行为 .以散色斑点的突停点温度为体系的凝胶化点Tgel,考察了溶液中加入Na+ ,K+ ,NH+4,Ca2 + ,Cu2 + ,Zn2 + 等抗衡离子对Tgel的影响 .结果是随抗衡离子浓度增大Tgel上升 ;Tgel与Na+ 的浓度呈线性关系 ,与K+ ,NH+4,Ca2 + ,Cu2 + ,Zn2 + 等离子浓度的平方根成线性关系 ;另外 ,还得到 30℃时KC在KCl盐溶液中的溶胶 凝胶相图 ,并对比了KC在NaCl溶液中透析前后Tgel的变化 .     

用同步荧光法研究细胞色素C在水溶液中的存在形态

用同步荧光光谱法研究细胞色素Ｃ在水溶液中的存在形态，发现细胞色素Ｃ中色氨酸残基的同步荧光光谱随浓度改变而发生变化，在较稀的溶液中，只观察到色氨酸残基的一个荧光峰，在较浓的溶液中也观察到一个荧光峰，而在这两个浓度之间时，这两个峰共存，可能反映了细胞色素Ｃ在不同浓度溶液中聚集状态的不同，当向存在两个荧光峰的溶液中加入不同浓度的脲，在一定脲浓度范围内，细胞色素Ｃ不发生变性，脲的作用使细胞色素Ｃ的单体浓度     

κ-卡拉胶热可逆凝胶的非遍历行为研究

采用散射斑纹(speckle)技术,即散射光强涨落法,研究了κ-卡拉胶(KC)热可逆凝胶的非遍历行为.证明了非遍历性的存在,并研究了浓度、温度等条件对该非遍历性的影响.结果表明:该物理凝胶存在非遍历性,并随KC浓度增加,凝胶非遍历性增大;随温度升高,凝胶非遍历性逐渐减小,直至消失.     

Photothermochemical process in ammonium perchlorate crystals: II

The influence of phase transition (PT) on the process of thermal development of a latent image arising after X-ray and uv irradiation of ammonium perchlorate (AP) crystals has been studied. Despite the production of a large number of new dislocations accompanying PT, it essentially does not influence the thermal development: The developed image does not smear at PT, remaining as clear as before it. By comparing mirror-symmetric surfaces of cleavage planes of AP crystals, it has been shown that at doses of X-ray and uv irradiation sufficient for obtaining an image, no production of new dislocations was observed in AP crystals. It is suggested that latent image arises due to formation during irradiation of chlorine oxidic products of radiolysis: ClO₃, ClO₂, and ClO as well as the corresponding ions ClO^?, ClO^?₂, and ClO^?₃, i.e., initiators of AP low-temperature decomposition.     

Construction of a 2,6-difunctionalized 2-methyl-2H-1-benzopyran library by using a solid-phase synthesis protocol

[reaction: see text] A library containing 1200 analogues of 2,6-difunctionalized 2-methyl-2H-1-benzopyran was constructed by using a solid-phase synthesis protocol. Polymer-bound 6-amido-, 6-sulfonamido-, and 6-uredo-functionalized 2-hydroxymethyl-2-methylbenzopyrans 10 were prepared as part of a first-generation diversification step by employing reactions of respective acid halides, sulfonyl chlorides, and isocyanates with the amine precursor 7. Transformations of the resin-bound intermediates 10 by reactions with alkyl and acid halides were then used to produce a diverse series of 2,6-difunctionalized 2-methyl-2H-1-benzopyran analogues 12 and 14.     

Study of Tea Digitized Chromatographic Fingerprint Spectra Using Micellar Electrokinetic Chromatography

IntroductionTeaisthemostwidelyconsumedbeverageinpeople’slife .Theheightenedpopularityofthisbeveragethroughouttheworldinrecentyearsmaybedueinparttotheevidenceofarelationshipbetweenteaconsumptionandpreventionofcertainformsofhumandisease .Themaincomponentsofteaarepolyphenoliccompounds ,commonlyknownascatechins ,whichrepresentagroupofcom poundsbelongingtotheflavonoidfamily .Thesecom poundsarewidelydistributedinthetealeavesandconsti tuteupto 30 %ofthedryleafweight.1Muchinteresthasbeenfocusedoncat…