Practical syntheses of [1,3,5]‐triazine dendritic molecules on solid supports

A practical and divergent synthesis of supported [1,3,5]‐triazine dendritic molecules on Wang resin, PEGA resin, SynPhase? Lanterns, and silica gel is described. The alkylamine linkers used allow derivatization with functionality for both synthetic (e.g., supported reagent and scavenger activity) and chemical biology applications. The use of supported intermediates allows differentiation of symmetric linkers without the need for protecting group chemistry. The synthetic route uses inexpensive, readily available starting materials in a straightforward and scaleable strategy. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2248–2259, 2006     

Cholesteric liquid crystal displays as optical sensors of barbiturate binding

The influence on the optical properties of cholesteric liquid crystal displays (LCDs) was examined for neutral molecule binding by mesogen/receptors in the mesomorphic phase. The motivation was to prepare neutral molecule sensors that use a colour change to signal analyte binding. A receptor that binds barbiturate analytes was modified with two or one cholesteryl groups to yield compounds 2 and 3, respectively. LCDs were prepared by incorporating one of the receptor/mesogen compounds into a cholesteric LC blend along with a potential H‐bonding guest. The optical properties of the LCDs were then determined by measuring the absorbance of the displays. For various LCDs, the colour of the display depended upon several factors: the amount of guest molecule used, the number of cholesteryl side chains on the receptor and the mole concentration of receptor/mesogen in the blend. In particular, complementary host/guest binding of H‐bonding analytes by the bis(cholesteryl) receptor 2 in a cholesteric LCD caused a change of up to +70 nm, which was observed by the naked eye as a blue‐to‐orange colour change. Control experiments confirm that the colour of an LCD is a consequence of molecular recognition in the mesomorphic phase.     

Structural and Kinetic Aspects of Blood Plasma Protein Adsorption on the Surface of Hydrophobic Polymers

Abstract

Due to the wide use of polymers in medicine, researchers are required to solve a very important problem–to understand the interaction between materials of nonphysiological origin and the surrounding biological liquids, and tissues, particularly blood.     

The crystal and molecular structure of a dinuclear copper(II) complex of a Robson-type macrocycle, [Cu2(C26H30N4O2)(H2O)2](BF4)2

Summary The crystal structure of the dinuclear complex [Cu₂(C₂₆H₃₀-N₄O₂)(H₂O)₂](BF₄)₂ was determined by x-ray crystallography. The crystals are triclinic, P¯1, witha = 10.945(5),b = 8.703(5),c = 8.495(5) Å, = 103.86(3)°, = 105.73(3)°, = 85.77(3)°, V = 756 ų D_c = 1.65 g cm^–3 for Z = 1. The copper(II) atoms are 5-coordinate and square-pyramidal. Selected bond distances are: Cu-N, 1.91 Å (mean); Cu-O(base) = 1.90(1) and 1.91(1) Å; Cu-O(apical) = 2.47(1) Å; There are O(water)-H ... F interionic hydrogen bonds in the structure. The Cu .. Cu distance is 2.847 Å.     

A simple method for extracting both active oily and water soluble extract (WSE) from Nigella sativa (L.) seeds using a single solvent system

The current study provides a way of extraction for both active NSO and WSE from Nigella sativa seeds using 98% methanol. About 1?kg of ground seeds was macerated by 1:2.5 w/v (g/mL) for 72?hours. After rotary evaporation and 7 days of continuous drying and chilling at 50 and 4?°C, NSO and WSE were obtained at the same instant. Solubility tests of 24 solvents and 11 thin layer chromatographic analyses while 2, 2-diphenyl-1-picrylhydrazyl free radical scavenging assay of NSO (73.66) , WSE (33.32) and NSO?+?WSE (78.22) against ascorbic acid (IC50?=?4.28?mg/mL) was performed. WSE was found to be highly soluble in water and 5% NaOH exhibiting the same Rf value of 0.95 for EtOH:DMSO (9:1) against the honey. WSE has revealed more than twofold higher anti-oxidant activity than others. Formulation of WSE with Tualang honey may provide better targeted hydrophilic drug delivery systems.     

In search of a new class of stable nitroxide: synthesis and reactivity of a peri-substituted N,N-bissulfonylhydroxylamine

Acyclic bissulfonylnitroxides have never been isolated, and degrade through fragmentation. In an approach to stabilising a bissulfonylnitroxide radical, the cyclic, peri-substituted N,N-bissulfonylhydroxylamine, 2-hydroxynaphtho[1,8-de][1,3,2]dithiazine 1,1,3,3-tetraoxide (1), has been prepared by formal nitrogen insertion into the sulfur-sulfur bond of a sulfinylsulfone, naphtho[1,8-cd][1,2]dithiole 1,1,2-trioxide. The heterocyclic ring of 1 is shown to adopt a sofa conformation by X-ray crystallography, with a pseudo-axial hydroxyl group. N,N-Bissulfonylhydroxylamine 1 displays high thermal, photochemical and hydrolytic stability compared to acyclic systems. EPR analysis reveals formation of the corresponding bissulfonylnitroxide 2 upon oxidation of 1 with the Ce(IV) salts CAN and CTAN. Although 2 does not undergo fragmentation, it cannot be isolated, since hydrogen atom abstraction to reform 1 occurs in situ. The stability and reactivity of 1 and 2 are compared with the known cyclic benzo-fused N,N-bissulfonylhydroxylamine, N-hydroxy-O-benzenedisulfonimide (6), for which the X-ray data, and EPR of the corresponding nitroxide 10, are also reported for the first time.     

Surface functionalization of ultrananocrystalline diamond films by electrochemical reduction of aryldiazonium salts

The surface functionalization of ultrananocrystalline diamond (UNCD) thin films via the electrochemical reduction of aryl diazonium cations is described. The one-electron-transfer reaction leads to the formation of solution-based aryl radicals, which in turn react with the UNCD surface forming stable covalent C-C bonds. Cyclic voltammetry (CV), X-ray photoelectron spectroscopy (XPS), ac impedance spectroscopy, and contact angle measurements have been employed to characterize the organic overlayer and estimate the surface coverage. The grafting of 3,5-dichlorophenyl groups renders the UNCD surface hydrophobic, whereas the attachment of 4-aminophenyl groups makes the surface relatively hydrophilic. The surface coverage, estimated from the electrochemical and XPS measurements, is as high as 70% of a compact monolayer. The aminophenyl terminated surface was obtained by electrochemical reduction of the tethered nitrophenyl groups. This two-step approach yields a UNCD surface with functional moieties available for the potential covalent coupling of a wide variety of biomolecules (e.g., DNA and proteins).     

Experimental and Computational Study of the Thermal Decomposition of 3‐Methyl‐3‐buten‐1‐ol in m‐Xylene Solution

An experimental study of the thermal decomposition of a β‐hydroxy alkene, 3‐methyl‐3‐buten‐1‐ol, in m‐xylene solution, has been carried out at five different temperatures in the range of 513.15–563.15 K. The temperature dependence of the rate constants for the decomposition of this compound in the corresponding Arrhenius equation is given by ln k (s^?1) = (25.65 ± 1.52) ? (17,944 ± 814) (kJ·mol^?1)·T^?1. A computational study has been carried out at the M05–2X/6–31+G(d,p) level of theory to calculate the rate constants and the activation parameters by the classical transition state theory. There is a good agreement between the experimental and calculated rate constants and activation Gibbs energies. The bonding characteristics of reactant, transition state, and products have been investigated by the natural bond orbital analysis, which provides the natural atomic charges and the Wiberg bond indices. Based on the results obtained, the mechanism proposed is a one‐step process proceeding through a six‐membered cyclic transition state, being a concerted and slightly asynchronous process. The results have been compared with those obtained previously by us (Struct Chem 2013, 24, 1811–1816) for the thermal decomposition of 3‐buten‐1‐ol, in m‐xylene solution. We can conclude that in the compound studied in this work, 3‐methyl‐3‐buten‐1‐ol, the effect of substitution at position 3 by a weakly activating CH₃ group is the stabilization of the transition state formed in the reaction and therefore a small increase in the rate of thermal decomposition.     

高聚合度Ⅱ-型聚磷酸铵的合成

用聚合反应-热处理两段工艺合成了高聚合度的聚磷酸铵（APP）阻燃材料,其结构经XRD,粒度及平均聚合度表征。优化反应条件为：磷酸氢二铵1mol,n（磷酸氢二铵）：n（五氧化二磷）：n（脲）：1．0：1．0：0．3．干燥氨气氛下于290℃反应30min,再经250℃-280℃后处理100min-110min。APP的平均聚合度大于150,粒度小于50μm。