En route to coordination chemistry under confined conditions in a porous capsule: Pr3+ with different coordination shells

The highly charged nanocontainer capsule of the type [pentagon]12[linker]30 identical with [(Mo)Mo5O21(H2O)6]12[Mo2O4(SO4)]30 with 20 nanosized pores and channels allows the entrance of cations like Pr3+: the latter are positioned at two different sites and have two different coordination shells, corresponding to a coordination chemistry under confined conditions; a fascinating aspect is that capsule encapsulated water shells fixed by hydrogen bonds act formally as polydentate ligands.     

Synthesis,spectroscopy and crystal structure of a new heterodinuclear silver(I)—copper(I) cryptate

A new heterodinuclear cryptate [AgCuL](ClO₄ ^–)₂ was synthesized by transmetallation via its precursor [Ag₂L](ClO₄ ^–)₂ (L = ligand). The electrospray mass spectrum (ES-MS) showed that the heterodinuclear entity exists in the solution. The X-Ray structure analysis shows that the Ag^I ion has tetrahedral geometry while Cu^I lies in a three-coordinate environment.     

Furostanol saponins with inhibitory action against COX-2 production from Tupistra chinensis rhizomes

Two furostanol saponins were obtained from the n-butanol fraction of methanol extract from Tupistra chinensis rhizomes,a folk medicine of Shennongjia Forest District of Hubei Province.Their structures were determined as (25S)-26-O-(β-D-glucopyranosyl)- furost-1β,3β,22α,26-tetrol-3-O-β-D-glucopyranosyl-(1→4)-β-D-glucopyranosyl-(1→2)-β-D-glucopyranoside (1) and (25R)- 26-O-(β-D-glucopyranosyl)-furost-1β,3β22α,26-tetrol 3-O-β-D-glucopyranosyl-(1→4)-β-D-glucopyranosyl-(1→2)-β-D-glu- copyranoside (2),on basis of chemical and spectroscopic evidences.1 and 2 displayed marked inhibitory action towards COX-2 production in macrophages of the rat abdomen induced by LPS at 20μg/mL.     

羧酸铜与单螺旋吡啶胺配体自组装的两种新型超分子配合物

Two novel supramolecular complexes [Cu（bpapa）（dhbd）]·CHaOH （1） and [Cu（bpapa）（ma）]·ma （2） （bpapa= bis[6-（2-pyridylamino）pyrid-2-yl]amine, dhbd=2,3-dihydroxybutanedioate dianion, ma=a-methacrylate） were rationally designed, synthesized and characterized by single crystal X-ray diffraction, IR, electronic spectroscopy and thermogravimetric analyses. Complex 1 was the first oligo-a-pyfidylamino complex based on hydroxypolycarboxylate and self-assembled into a 3D honeycomb configuration network with open channels and tubes containing 1D ladder-shaped double chains formed by hydrogen bonds and aromatic π-π stacking interactions. Complex 2 constructed a 2D supramolecular network extended by 1D chains from dimeric supramolecular synthon through noncovalent supramolecular interactions. In the two complexes, the chelating monohelical ligand adopted all-anti configuration. Density functional theory calculations were applied to 1 and 2.     

Wismutmonojodid BiJ,eine Verbindung mit Bi(O) und Bi(II)

Bismuth Monoiodide, a Compound with Bi(O) and Bi(II) Bismuth monoiodide was synthesized in closed tubes from the elements as well as from Bi and HgI₂ as a black coloured crystalline compound. With increasing temperature BiI passes two transitions. α-BiI is stable below 370 K and changes to β-BiI by a martensitic transition. γ-BiI is the stable modification above 564 K and decomposes at 585 K peritectically to BiI₃ and a lower iodide. All three modification crystallize in the monoclinic space group C2/m. The structures (single crystal studies) of α-BiI and β-BiI are characterized by onedimensional infinite chains [Bi₄I₄] with covalent bonds but only weak interactions in between. The [Bi₄I₄]-chains are built up by two completely different Bi atoms. Bi(A) is only bonded to three Bi whereas Bi(B) has bonds to one Bi and four I. The average bond lengths are Bi? Bi = 304.5 pm and Bi? I = 313.7 pm respectively. The configuration of the Bi(A) atoms is typical for Bi^O and that one of the Bi(B) atoms is characteristic for Bi²⁺ with the electron configuration s²p¹. Therefore, α-BiI and β-BiI are mixed valence compounds [Bi^OBi²⁺I₄]. The structures are variants of the simple cubic polonium type of structure and differ in the stacking of connected units. The structures and their transitions, the possible configurations for monohalides BiX on principle as well as the energy balances of the disproportionation of Bi⁺ are discussed together in detail.     

New liquid‐crystal alignment agents based on fluorinated polyimides with trifluoromethyl‐substituted benzene or diphenylether in the side chain

Fluorinated copolyimides derived from 4,4′‐oxydiphthalic anhydride (ODPA) with 4,4′‐oxydianline (ODA) and trifluoromethyl‐containing aromatic diamines have been synthesized and characterized. The trifluoromethyl‐containing diamines include 2,4‐diamino‐3′‐trifluoromethylazobenzene, 2,4‐diamino‐1‐[(4′‐trifluoromethylphenoxy) phenyl] aniline, 3,5‐diamino‐1‐[(4′‐trifluoromethylphenoxy) phenyl] benzamide, 3,5‐diamino‐1‐[(3′‐trifluoromethyl) phenyl] benzamide, 1,4‐bis(4′‐aminophenoxy)‐2‐(3′‐trifluoromethylphenyl) benzene, 3,5‐diaminobenzenetrifluoride, 4,4′‐diamino‐4″‐(p‐trifluoromethyl phenoxy) triphenylamine, and 4‐[(4′‐trifluoromethylphenoxy) phenyl]‐2,6‐bis(4″‐aminophenyl)pyridine. Strong and flexible copolyimide films, produced by casting the polyamic acid solution followed by thermal imidization, exhibited great thermal stability and high mechanical properties. The polyimides had an ultraviolet–visible absorption cutoff at 330–340 nm and pretilt angles as high as 20° for nematic liquid crystals, making them great potential candidates for advanced liquid‐crystal display applications. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1583–1593, 2002     

The inclusion behavior of benzo-15-crown-5 with hydrated transition metal picrates

Six kinds of benzo-15-crown-5 (L) adducts having the stoichiometric formula M(Pic)₂ · L · xH₂O (M=Mn, Cu, x=2; M=Co, Ni, Zn, Cd, x=4; Pic means picrate anion) have been synthesized and characterized by EA, IR, UV and molar conductance. The X-ray crystal structural analysis of the benzo-15-crown-5 adduct with hydrated copper(II) picrate revealed that the benzo-15-crown-5 molecule virtually acts as a second-sphere ligand, which associates with the copper(II) ion by hydrogen bonding of the coordinating water molecule. By the comparison of the IR, UV spectra and molar conductance of the new adducts prepared, it can be deduced that the other adducts exhibit the similar coordination environment to that of the copper adduct.     

四-α-(2，2，4-三甲基-3-戊氧基)酞菁金属配合物(M=Co，Ni，Cu，Zn)的合成与光谱性质(英)

A series of [tetra-α-(2,2,4-tirmethyl-3-pentoxy) phthalocyaninato] metal complexes(M=Co, Ni, Cu, Zn)were prepared by cyclotetramerization of 3-(2,2,4-tirmethyl-3-pentoxy)phthalonitrile with corresponding anhydrous metal salts， using 1.8-diazabicyclo[5.4.0] undec-7-ene (DBU) as the catalyst. HPLC analysis shows that one isomer predominates in the product of nickel complex, while at least two main constitutional isomers exist in the product of other metal complexes. The complexes (in the form of mixture of constitutional isomers) were characterized by elemental analyses, MS, IR and UV-Vis spectroscopy.     

Palladium-catalyzed cascade reactions of benzyl halides with N-allyl-N-(2-butenyl)-p-toluenesulfonamide

Reaction of benzyl halides with N-allyl-N-(2-butenyl)-p-toluenesulfonamide 1 in the presence of a palladium catalyst afforded dihydropyrroles 3 in moderate to excellent yields. It is proposed that the cyclic products were formed via a palladium-catalyzed cascade cyclization-coupling process.     

High accuracy mass measurement of peptides with internal calibration using a dual electrospray ionization sprayer system for protein identification

A dual-ESI-sprayer system was constructed and applied to achieve high accuracy of peptide mass measurement for protein identification by means of peptide mapping. Sample was introduced in one sprayer, and reference in the other, thus making internal calibration possible greatly enhancing the mass accuracy. Several samples were utilized to evaluate the reliability of this dual-ESI-sprayer system. The range of mass errors was 0.16-5.37 ppm. The peptide masses of tryptic digests of myoglobin (horse) were measured by the HPLC/dual-ESI-MS system, with mass deviations ranging from 0.01-7.67 ppm, and about 75% mass deviations below 5 ppm with 40% below 1[?]ppm. These peptide masses were utilized to perform database searching for protein identification, and compared to results obtained by external calibration. This comparison showed that the internal calibration provides a more reliable method of protein identification, with a much smaller number of required peptides for matching, and with less CPU time consumed for database searching.