Synthesis, crystal structure and magnetic properties of a novel complex [Cu(NIT2Py)(PDA)(H2O)]·(CH3OH)(H2O)

A novel complex [Cu(NIT2Py)(PDA)(H₂O)]·(CH₃OH)(H₂O) has been synthesized and structurally characterized by X-ray diffraction methods. It crystallizes in the monoclinic space group P2(1)/c. The structure consists of [Cu(NIT2Py)(PDA)(H₂O)] moiety, one solvent methanol molecule and one water molecule. The copper(II) ion is in a distorted octahedral environment: one nitrogen atom and one oxygen atom from the NIT2Py, one nitrogen atom from the PDA (2,6-pyridine dicarboxylic acid) and one oxygen atom from the aqueous in the basal plane; two oxygen atoms from the PDA in the axial position. The units of [Cu(NIT2Py)(PDA)(H₂O)] were connected as one dimension chain by the intermolecular hydrogen bonds. The complex exhibits intramolecular antiferromagnetic interactions between the Cu(II) ion and the NIT2Py.     

Structure and Magnetic Properties of a Novel Two‐Dimensional Complex from 1, 3, 5‐Benzenetricarboxylate and Neodymium(III) — {[Nd(1, 3, 5‐benzenetricarboxylate)(H2O)4] · H2O}n

A unique neodymium(III) complex, {[Nd(BTC)(H₂O)₄] · H₂O}_n (BTC = 1, 3, 5‐benzenetricarboxylate), was obtained from the reaction between Nd(ClO₄)₃ · xH₂O and Na₃BTC. Coordination bonds, hydrogen bonds, and π‐π stacking form a supramolecular structure with a novel, two‐dimensional framework. The temperature‐dependent magnetic susceptibilities were analyzed by the Curie‐Weiss law; the following values were found C = 1.32, θ = —18.3 K, respectively.     

负载稀土型酸活化膨润土的酯化催化活性

负载稀土型酸活化膨润土的酯化催化活性李永绣，冯天泽，胡平贵，何小彬，辜子英，廖荣辉（南昌大学化学系南昌３３００４７）关键词稀土，膨润土，催化酯化可用稀土、膨润土单独作酯化催化剂，但活性不高［１～３］。本文将稀土用离子交换的方法负载到酸活化膨润土中，寻...     

Chemistry of O-Benzoquinones and Masked O-Benzoquinones I. Diels-Alder Reactions of O-Benzoquinones with Dimethyl Acetylenedicarboxylate and Phenylacetylene

Diels-Alder reactions of six o-benzoquinones with dimethyl acetylenedicarboxylate has been examined. The yields of adducts vary with the natures of the o-benzoquinones, 3,4-Di-n-propyl-(1c), 3,6-di-n-propyl (1d). 3. 4-diallyl-(1e) and 3, 6-diallyl-o-benzoquinone (1f) are found to give bicyclic a-diketones exclusively without the formation of 1,4-dioxine derivatives, the yields ranging from 20 to 70%. In the case of 4, 5-dimethoxy-o-benzoquinone, dimethyl 4, 5-dimethoxyphthalate is produced in 42% yield, presumably derived from the decomposition of the corresponding initially formed α-diketone. 3, 6-Di-n-propyl-4, 5-dimethoxy-o-benzoquinone deteriorates without addition to dimethyl acetylenedicarboxylate upon heating. The additions of o-benzoquinones 1c , 1d and 1f to phenylacetylene are also studied. The yields of adducts, α-diketones, range from 23% to 82%.     

Alkanethiolate self-assembled monolayers as functional spacers to resist protein adsorption upon Au-coated nerve microelectrode

Alkanethiolate self-assembled monolayers (SAMs) of varied chain lengths were adsorbed upon Au-coated nerve microelectrodes and employed as protein-resistant spacers. The microelectrode spiraled as a cuff type can be used for restoring motor function via electrical stimulation on the peripheral nerve system; however, an increase of electrode impedance might occur during implantation. In this work, a thin-film SAMs treatment upon Au/polyimide (PI) surface of the microelectrode provided a hydrophobic characteristic, which retarded protein adsorption at the initial stage and subsequent pileup (or thickening) process. The protein-resistant effect exhibited comparable SAMs of different chain lengths adsorbed upon Au/PI surfaces. The increase of electrode impedance as a function of protein deposition time was mainly correlated with the addition of reactance that was associated with the pileup thickness of the deposited protein. Particularly, the SAMs-modified surface was capable to detach a significant portion of the accumulated protein from the protein-deposited SAMs/Au/PI, whereas the protein-deposited layers exhibited firm adhesion upon Au/PI surface. It is therefore very promising to apply thin-film SAMs adsorbed upon Au-coated surface for bioinvasive devices that have the need of functional electrical stimulations or sensing nerve signals during chronic implantation.     

From D-glucose to biologically potent L-hexose derivatives: synthesis of alpha-L-iduronidase fluorogenic detector and the disaccharide moieties of bleomycin A2 and heparan sulfate

A novel and convenient route for the synthesis of biologically potent and rare L-hexose derivatives from D-glucose is described. Conversion of diacetone-alpha-D-glucose (14) into 1,2:3,5-di-O-isopropylidene-beta-L-idofuranose (19) was efficiently carried out in two steps. Orthogonal isopropylidene rearrangement of compound 19 led to 1,2:5,6-di-O-isopropylidene-beta-L-idofuranose (27), which underwent regioselective epimerization at the C3 position to give the L-talo- and 3-functionalized L-idofuranosyl derivatives. Hydrolysis of compound 19 under acidic conditions furnished 1,6-anhydro-beta-L-idopyranose (35) in excellent yield, which was successfully transformed into the corresponding L-allo, L-altro, L-gulo, and L-ido derivatives via regioselective benzylation, benzoylation, triflation and nucleophilic substitution as the key steps. Applications of these 1,6-anhydro-beta-L-hexopyranoses as valuable building blocks to the syntheses of 4-methylcoumarin-7-yl-alpha-L-iduronic acid and the disaccharide moieties of bleomycin A(2) as well as heparan sulfate are highlighted.     

Titrimetric determination of thiocyanate and thiosulphate ions by oxidation with iodine in alkaline solution

Thiocyanate (2.7-90 mug) and thiosulphate (4.5-90 mug) ions are oxidized by iodine in alkaline media to sulphate ions. After acidification, the excess of iodine is extracted into chloroform, and the iodide ions formed in the redox reaction subjected to an amplification reaction. Either a titrimetric or a spectrophotometric finish may be used. Each thiocyanate and thiosulphate ion results in the ultimate production of 19 and 24 iodine molecules, respectively.     

膦化聚2,6—二甲基1,4—苯醚负载钯催化剂的表征及其催化性能

报道了四种不同P/Pd摩尔比的膦化聚2,6-二甲基1,4-苯醚负载把催化剂的加氢和异构化性能;通过XPS、电镜和远红外对催化剂进行了表征;并考察了溶剂和温度对催化剂活性的影响.     

OSW saponins: facile synthesis toward a new type of structures with potent antitumor activities

[reaction: see text] OSW saponins, featuring a 16beta,17alpha-dihydroxycholest-22-one aglycon and an acylated beta-D-xylopyranosyl-(1-->3)-alpha-L-arabinopyranosyl residue attached to the 16-hydroxyl group, have recently been discovered from a group of lily plants, which show potent antitumor activities with a novel mechanism of action. This paper describes an aldol approach to the stereoselective construction of the 16alpha,17alpha-dihydroxycholest-22-one structure from 16alpha-hydroxy-5-androsten-17-ones and propionates. Elaboration of the aldol adducts toward OSW-1, involving installation of the isoamyl ketone side chain, inversion of the 16-hydroxyl configuration, and selective protection of the C22-oxy function, has been explored and accomplished. In particular, the present route was found convenient for the synthesis of OSW saponin analogues with a C22-ester side chain. Thus, the 23-oxa-analogue of OSW-1 (40) was prepared starting from the industrial dehydroisoandrosterone (1) in a linear eight-step sequence and in 26% overall yield. Analogues with a variety of modified side chains were prepared, via aldol condensation with propionates of varying length, thiopropionate, and acetate (for preparation of 68-75) or via aminolysis of the 22,16-lactone 26 (for preparation of the 23-N-analogues). Cross metathesis (CM) reaction was also found feasible for modification at the final stage from C22-allyl ester 70. Valuable structure-activity relationships (SAR), together with the practical synthetic approach, have thus been provided to set a new stage for further studies on this new type of antitumor structures.