One-step preparation of highly concentrated well-stable gold colloids by direct mix of polyelectrolyte and HAuCl4 aqueous solutions at room temperature

Highly concentrated, well-stable gold colloids can be prepared directly from an amine-bearing polyelectrolyte-HAuCl4 aqueous solution at room temperature. It is found that increasing molar ratio of polyelectrolyte to gold leads to increasing particle size. UV-vis spectra, transmission electron microscopy (TEM), and X-ray photoelectron spectra (XPS) were used to characterize the products thus formed.     

Highly regioselective rearrangement of 2-substituted vinylepoxides catalyzed by gallium(III) triflate

Gallium(III) triflate catalyzed the rearrangement of 2-substituted vinylepoxides into beta,gamma-unsaturated carbonyl compounds with high regio- and chemoselectivity (>97/3) in low catalyst loading (1-5 mol %). The alkyl-substituted trimethylsilylvinyl epoxides gave beta,gamma-unsaturated ketone, but aryl-substituted vinylepoxides gave the aldehydes instead.     

NMR determination of absolute site-specific natural isotope ratios of hydrogen in organic molecules. Analytical and mechanistic applications

It has been shown that the “internal” isotope distribution within a given molecular species at the natural abundance level is accessible by a new method, SNIF-NMR, which is based on deuterium NMR. Relative internal factors, R_i/j,have been defined which enable the isotope content of a given site, i, to be compared to that of another molecular site, j, taken as the reference. Several referencing methods intended to provide direct access to relative $\text{externals}$, T_i , and $\text{absolute}$, (D/H)_i , site-specific parameters, are now discussed from both the theoretical and the experimental points of view. In the $\text{intramolecular referencing method}$, which involves a time-consuming chemical transformation of the sample, the risk exists of more or leas systematic errors resulting from discriminating fractionation effects. However this technique offers, conversely, an interesting way of investigating kinetic isotope effects without the need for specific labelling. In spite of its lower spectral precision the $\text{external referencing method}$ has the advantage of being fast and less sensitive to systematic errois and may be used for direct rough routine determinations of the site-specific isotope contents. More precise results can be obtained, at the price of contaminating the sample, when an $\text{intermolecular reference}$ is added and signal heights are used, remembering however that the intensity parameters then have no strict physical meaning in terms of absolute isotope contents. The site-specific parameters, T_i and (D/H)_i thus accessible, provide new information on the mechanisms of the fractionation effects occurring in natural conditions and examples are considered.     

Novel one-dimensional tubelike and two-dimensional polycatenated metal-organic frameworks

Two novel metal-organic frameworks (MOFs) [Zn(TITMB)(OAc)](OH).8.5H(2)O (1) and [Ag(TITMB)N(3)].H(2)O (2) [TITMB = 1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene, OAc = acetate anion] were synthesized and their structures were determined by X-ray crystallography. Complex 1 crystallizes in tetragonal space group P(-)4 with a = 23.2664(7) and c = 11.9890(3) A and Z = 8. 1 has a one-dimensional tubelike structure with large inner pore size of approximately 17 A. Complex 2 crystallizes in monoclinic space group C2 with a = 20.7193(10), b = 11.5677(8), and c = 12.2944(6) A, beta = 125.5770(10) degrees, and Z = 4. 2 consists of two-dimensional honeycomb networks that interpenetrate each other to generate a polycatenated structure. In these two complexes, both zinc(II) and silver(I) atoms are four-coordinated with the same tetrahedral coordination geometry. The topologies of 1 and 2 are predominated by the conformations of TITMB, which are cis, trans, trans in 1 and cis, cis, cis in 2, respectively.     

Use of p-dimethylaminobenzalhyde as a colored reagent for determination of procaine hydrochloride by spectrophotometry

Spectrophotometric determination of procaine hydrochloride is described. The procaine hydrochloride reacts with p-dimethylaminobenzalhyde in glacial acetic acid to form an Schiff base which is a yellow compound, and its maximum absorption wavelength is at 455nm, ₄₅₅=3.46×10⁴. The absorbance for procaine hydrochloride from 0.2 to 15 μg ml⁻¹ obeys Beer's law. The linear regression equation of the calibration graph is C=5.866A−0.02, with a linear regression correlative coefficient is 0.9994 and relative standard deviation (RSD) of 1.7%; the detection limit is 0.1 μg ml⁻¹; recovery is from 92.0 to 110.0%. Effects of reaction medium, temperature, gentamycin, beneylpenicillin, kanamycin, streptomycin, foreign ions, and stand for time on the determination of procaine hydrochloride have been examined. The results obtained by this method agreed with those by the official method (dead-stop titration). This method is rapid and simple, and can be used for the determination of procaine hydrochloride in injection solution of procaine hydrochloride.     

Synthesis of four diastereomeric 3,5-dialkoxy-2,4-dimethylalkanals by a simple extension of the non-aldol aldol process to bis(propionates)

[formula: see text] The synthesis of all four diastereomers of bis(propionates), 3,5-dialkoxy-2,4-dimethylalkanals, by non-aldol aldol chemistry is described. The epoxy alcohols (3, 4) were converted into the mesylates (9, 11) which were cleanly rearranged to the desired 3,5-bis(oxygenated)-2,4-dimethylalkanals (10, 12) in high yield. The epoxy mesylates (13, 16) gave the desired products (14, 17) in good yield on treatment with TMSOTf and a hindered base.     

Equilibrium interaction of solid surfaces across a polymer melt

Forces across polymer melts are poorly understood despite their importance for adhesion and fabricating composite materials. Using an atomic force microscope (AFM), this interaction was measured for poly(dimethyl siloxane) (PDMS). The structure of the polymer at the surface changed during the first approximately 10 h. Afterward, short-range attractive forces were observed with short-chain PDMS (M(w) = 4200 g/mol). Using PDMS with a molecular weight (M(w) = 18 000 g/mol) above the entanglement limit, we measured a monotonically decaying repulsive force, which indicates that a quasi-immobilized layer had formed at the solid surface. Due to the small radius of curvature of the tip, forces could be measured in equilibrium.     

Aggregate manganese Schiff base moieties by terephthalate or acetate: dinuclear manganese and trinuclear mixed metal Mn2/Na complexes

A reaction system consisting of terephthalic acid, NaOH, inorganic Mn(II) or Mn(III) salt, and salicylidene alkylimine resulted in dinuclear manganese complexes (salpn)(2)Mn(2)(mu-phth)(CH(3)OH)(2) (1, salpn = N,N'-1,3-propylene-bis(salicylideneiminato); phth = terephthalate dianion), (salen)(2)Mn(2)(mu-phth)(CH(3)OH)(2) (2, salen = N,N'-ethylene-bis(salicylideneiminato)), (salen)(2)Mn(2)(mu-phth)(CH(3)OH)(H(2)O) (3), and (salen)(2)Mn(2)(mu-phth) (4), while the absence of NaOH in the reaction led to a mononuclear Mn complex (salph)Mn(CH(3)OH)(NO(3)) (5, salph = N,N'-1,2-phenylene-bis(salicylideneiminato)). In addition, a trinuclear mixed metal complex H[Mn(2)Na(salpn)(2)(mu-OAc)(2)(H(2)O)(2)](OAc)(2) (6) was obtained from the reaction system by using maleic acid instead of terephthalic acid. Five-coordinate Mn ions were found in 4 giving rise to an intermolecular interaction and constructing a one-dimensional linear structure. Antiferromagnetic exchange interactions were observed for 1-3, and a total ferromagnetic exchange of 4 was considered to stem from intermolecular magnetic coupling. (1)H NMR signals of phenolate ring and alkylene (or phenylene) backbone of the diamine are similar to those reported in the literature, and the phth protons are at -2.3 to -10.1 ppm. Studies on structure, bond valence sum analysis, and magnetic properties indicate the oxidation states of the Mn ions in 6 to be +3, which are also indicated by ESR spectra in dual mode. Ferromagnetic exchange interaction between the Mn(III) sites was observed with J = 1.74 cm(-1). A quasireversible redox pair at -0.29V/-0.12V has been assigned to the redox of Mn(2)(III)/Mn(III)Mn(II), implying the intactness of the complex backbone in solution.     

A Spectrophotometric Study OE Zirconium Complexes of 4,5-Dihydroxyfluorescein

Zirconium (IV) ions form violet red complex with 4,5-dihydroxyfluorescein in fairly strong mineral acid medium. The reagent has been successfully applied as a metal indicator in the direct EDTA titration of zirconium. The complex formed by 4,5-dihydroxyfluorescein and zirconium ions has been studied spectrophotometrically in 0.1M HCl solution. It is found that when an excess of metal ion is present, a violet red colored complex with metal-ligand ratio of 1:1, (MR) is formed and when an excess of 4,5-dihydroxyfluorescein is present a 1:2 complex (MR₂) may be predominant. The 1:1 complex has maximum absorption at 510 mμ and the 1:2 complex has very low solubility and tends to precipitate out from the solution. Job's method, log-ratio method and gravimetric method were used to establish the composition of complexes. The apparent stability constant of the 1:1 complex is found to be log K_h = 4.46 or K_h = 2.9×10¹ at pH 1.2.