He(I) and He(II) photoelectron spectra of Hyprrole-2-CHN′t-Bu and the biscarbonyl Rh(I) and Ir(I) complexes of its anion

The He(I) and He(II) photoelectron spectra of a series of [(LL)M(CO)₂] (LL = pyrrole-2-CHN′ R; R = t-Bu; M = Rh, Ir) complexes are reported. Assignments are proposed based on He(I)/He(II) intensity differences, on molecular orbital calculations of related complexes and of free ligands, and by comparison with the spectra of the free ligands Hpyrrole-2-CHN′t-Bu, Hpyrrole-2-carbaldehyde and Hpyrrole.The electronic structure of the complexes is discussed and conclusions are drawn about the metal-ligand interaction.     

Structural, photolysis and biological studies of the bis(μ2-chloro)-tris(triphenylphosphine)-di-copper(I) and chloro-tris(triphenylphosphine)-copper(I) complexes. Study of copper(I)-copper(I) interactions

Direct reaction of copper(I) chloride with triphenylphosphine (tpp) in molar ratio 2:3 and 1:3, results in the formation of the [(tpp)Cu(μ₂-Cl)₂Cu(tpp)₂] (1) and {[CuCl(tpp)₃]·(CH₃CN)} (2) complexes. The complexes have been characterized by melting point, FT-IR, UV-Vis spectroscopic data and X-ray crystallography. Complex 1 is di-nuclear. Two μ₂-Cl atoms bridge two copper(I) ions with tetrahedral and trigonal geometry respectively. The short copper-copper bond distance of 2.9039(6) ? in case of 1 indicates d¹⁰-d¹⁰ interaction between metal centers. Thus, our studies were extended here in the determination of the quasi-aromaticity, which results in strong Cu-Cu interactions, using the computational method of nucleus-independent chemical shifts (NICS). The NICS calculated at the inner region of the Cu₂Cl₂P₃ core in complex 1 is shielded up to −6.05 ppm. Complex 2 is mono-nuclear where three phosphorus and one chloride atoms form a tetrahedron around the copper(I) ion. Photolysis of both complexes 1 and 2, results in the formation of triphenylphosphine oxide.The complexes 1 and 2, were tested for their in vitro cytotoxic activity against leiomyosarcoma cells (LMS) and human breast adenocarcinoma cells (MCF-7). The type of LMS cell death caused by the complexes was also evaluated by use of a flow cytometry assay. The results show that at concentration of 5 μΜ of complexes 1 and 2, 34.1% (1) and 19.6 (2)% of LMS cells undergo programmed cell death (apoptosis), while at 10 μΜ, 80.4% (1) and 65.2% (2) of LMS cells undergo apoptosis. The light sensitivity of the complex is discussed in relation with the biological activity.     

Carbonyl complexes of Rh(I), Ir(I) and Mo(0) containing substituted derivatives of 1,10-phenanthroline and 2,2′-bipyridine

The A₁ symmetry v_CO of the carbonyl complexes [Mo(chel)(CO)₄], [M(chel)(CO)₂] [PF₆] (M=Rh, Ir; chel=bipy, phen and substituted derivatives) are used for determining the electron donor-acceptor properties of the title ligands. The steric hindrance of the methyl groups in positions 2 and 9 of the phenanthroline favours the formation of Rh(I) and Ir(I) pentacoordinated derivatives.     

DFT study of (17)O, (1)H and (13)C NMR chemical shifts in two forms of native cellulose, I(α) and I(β)

This computational study is intended to shed light on the crystalline and molecular structure, together with the hydrogen bonding (H-bonding) differences between two forms of native cellulose. DFT calculations were carried out to characterize the ¹⁷O, ¹H and ¹³C nuclear magnetic resonance (NMR) parameters in cellulose I_α and I_β with the B3LYP functional employing the 6–311++G7 and 6–31+G1 basis sets. Geometry optimization revealed that the average HB length is shortened by 0.01–0.08 Å when the chains are aligned, whereas the average bond angle increases by about 4–8° exhibiting the enhancement of HB strength. For the isolated cellotetramer chains, the isotropic ¹⁷O–H chemical shifts were plotted as a function of HB length. Our results indicated that as the HB length in cellotetramer I_α increases, the ¹⁷O–H chemical shift isotropy increases, but this parameter changes in the opposite direction for the other structure. Moreover, B3LYP/6–311++G7 calculations reveal that there is an acceptable correlation between the calculated ¹³C chemical shifts of the two structures and their experimental values.     

Rectangular tetranuclear silver(I) and μ8-selenide-centered octanuclear copper(I) complexes containing bis(diphenylphosphino)amide ligands

Interaction of Ag(CF₃CO₂) with bis(diphenylphosphino)amide (dppa) in THF gave a tetranuclear Ag₄-coplanar silver(I) complex [Ag₄(μ-dppa)₂(μ₄-O₂PPh₂)₂(μ-CF₃CO₂)₂] (1). The trinuclear trigonal-bipyramid copper(I) complex [Cu₃(μ₃-Cl)₂(μ-dppa)₃][CuCl₂] (2) was obtained from the reaction of [CuCl] powder with bis(diphenylphosphino)amide (dppa) in THF. Treatment of 2 with (Me₃Si)₂Se in THF afforded a μ₈-selenide-centered octanuclear copper(I) complex [Cu₈(μ₈-Se)(μ₄-Se)(μ₄-SeH)₃(μ-dppa)₄][(Ph₂PO)₂N] (3). The structures of 1-3 were determined by single-crystal X-ray diffraction analyses. Complex 1 comprises a rectangular Ag₄ array with each edge bridged with a pair of μ-dppa, μ₄-O₂PPh₂ and μ-CF₃CO₂ ligands that are approximately perpendicular to each other. Complex 2 contains a trigonal-bipyramid [Cu₃(μ₃-Cl)₂]⁺ core surrounded by three μ-dppa ligands. The cationic complex in 3 consists of four [Cu₂(μ-dppa)] fragments side-capped by one μ₄-Se and three μ₄-SeH ligands and center-connected by a μ₈-Se atom.     

Homobimetallic anthracene-bridged η-cyclopentadienyl derivatives of rhodium(I) and iridium(I): large molecules or supramolecular species?

The reaction of 9,10-bis[(cyclopentadienylmethyl)thallium(I)]anthracene (2), obtained from 9,10-bis(cyclopentadienylmethyl)anthracene (1), with the chloro derivatives of rhodium(I) of formula [RhClL₂]₂ (L=η²-C₈H₁₄ or L₂=η⁴-C₈H₁₂) leads to the corresponding bimetallic complexes [L₂Rh{C₅H₄CH₂(9,10-anthrylene)CH₂C₅H₄}RhL₂] 3 (L=η²-C₈H₁₄) and 4 (L₂=η⁴-C₈H₁₂), in 22.8% and 15.0% yields, respectively. Analogously, by reacting 2 with [IrClL₂]₂ (L=η²-C₈H₁₄ or L₂=η⁴-C₈H₁₂), the corresponding bimetallic iridium(I) complexes [L₂Ir{C₅H₄CH₂(9,10-anthrylene)CH₂C₅H₄}IrL₂] 5 (L=η²-C₈H₁₄) and 6 (L₂=η⁴-C₈H₁₂) were obtained, in 24.5% and 43.0% yields, respectively. All complexes have been characterised by elemental analysis, mass spectrometry, and ¹H NMR. The structure of 4 was elucidated also by single crystal X-ray diffraction: it crystallises in the P2₁/c space group with a=19.932(11), b=6.4417(4), c=12.377(2) Å; α=90°, β=100.90(4)°, γ=90°. V=1560.5(9) ų. Z=2, D_calc=1.606 g cm⁻¹, R₁=0.0449 [I>σ(I)], wR₂=0.1121. The UV-Vis spectra (280-530 nm) of 3-6 are indicative of the existence of strong electronic interactions among the 9,10-anthrylene chromophore and the two cyclopentadienylML₂ moieties. When excited at ca. 370 nm, 1 results to be an efficient light-emitting molecule, while the fluorescence emission of the 9,10-anthrylene chromophore is almost completely quenched in complexes 3-6. The study of the electrochemical behaviour of 3-6 in strictly aprotic conditions allows a satisfactory interpretation of the observed electrode processes and gives information about the location of the redox sites along with the thermodynamic characterisation of the corresponding redox processes. These data show that the occurrence of an intramolecular charge-transfer process between the photo-excited 9,10-anthrylene group and the cyclopentadienylML₂ moiety is a possible route for the observed quenching of emission in the compounds 3-6. The one-electron oxidation of compounds 3-6 by thallium(III) trifluoroacetate leads to the formation of the corresponding cation radicals. Three of them, i.e., 3⁺, 5⁺ and 6⁺, give rise to good X-band EPR spectra that were fully interpreted by computer simulation as well as by semi-empirical calculations (PM3 level) of the spin density distribution.     

The many faces (and phases) of ceramide and sphingomyelin I – single lipids

Ceramides, the simplest kind of two-chained sphingolipids, contain a single hydroxyl group in position 1 of the sphingoid base. Sphingomyelins further contain a phosphocholine group at the OH of position 1 of ceramide. Ceramides and sphingomyelins show a variety of species depending on the fatty acyl chain length, hydroxylation, and unsaturation. Because of the relatively high transition temperature of sphingomyelin compared to lecithin and, particularly, of ceramides with 16:0–18:0 saturated chains, a widespread idea on their functional importance refers to formation of rather solid domains enriched in sphingomyelin and ceramide. Frequently, and especially in the cell biology field, these are generally (and erroneously) assumed to occur irrespective on the type of N-acyl chain in these lipids. This is because most studies indicating such condensed ordered domains employed sphingolipids with acyl chains with 16 carbons while scarce attention has been focused on the influence of the N-acyl chain on their surface properties. However, abundant evidence has shown that variations of the N-acyl chain length in ceramides and sphingomyelins markedly affect their phase state, interfacial elasticity, surface topography, electrostatics and miscibility and that, even the usually conceived “condensed” sphingolipids and many of their mixtures, may exhibit liquid-like expanded states. This review is a summarized overview of our work and of related others on some facts regarding membranes composed of single molecular species of ceramide and sphingomyelin. A second part is dedicated to discuss the miscibility properties between species of sphingolipids that differ in N-acyl and oligosaccharide chains.     

Synthesis and characterization of alkynes β-diketonate copper(I) complexes

The reactions of 1,3,5-tris-(trimethylsilylethynyl)benzene (1) with Cu₂O and 1,1,1,5,5,5,-hexafluoroacetylacetone in alkyne to Cu ratios 1:0.5, 1:1 and 1:3 in CH₂Cl₂ at room temperature give copper complexes (η²-1,3,5-tris(trimethylsilylethynyl)benzene)(Cu(hfac)) (2), (η²:η²-1,3,5-tris(trimethylsilylethynyl)benzene)(Cu(hfac))₂ (3) and (η²:η²:η²-(1,3,5- tris(trimethylsilylethynyl)benzene))₂(Cu(hfac))₃(4), respectively. In the same conditions, 2,5-bis-(trimethylsilylethynyl)thiophene (5) reacts with 0.5 or 1 equiv. of Cu₂O to give (η²:η²-2,5-bis(trimethylsilylethynyl)thiophene)(Cu(hfac)) (6) and (η²:η²-2,5-bis(trimethylsilylethynyl)thiophene)(Cu(hfac))₂ (7), respectively, and 1,4-bis(trimethylsilyl)-1,3-butadiyne (8) with 0.5 equiv. of Cu₂O give (η²:η²-1,4-bis(trimethylsilyl)-1,3-butadiyne)(Cu(hfac))₂(9). All the new compounds have been characterized by analytical and spectroscopic methods and their thermal properties were examined by thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC).     

Synthesis and binding affinities of Re(I) and Tc(I)-containing 16α-substituted estradiol complexes: Models for potential breast cancer imaging agents

To develop technetium and rhenium-labeled imaging agents for estrogen receptor (ER) positive breast tumors, we have synthesized tridentate metal tricarbonyl chelates substituted at the 16α-position of estradiol. Their structures were characterized by IR, ¹H NMR, ¹³C NMR, HRMS or elemental analysis. The rhenium complex 7b showed the highest ER binding affinity (RBA = 25.7) among these compounds, so ligand 6b was selected to be labeled by the precursor [^99mTc(H₂O)₃(CO)₃]⁺ to yield technetium(I)-99m complex 7b′ with good radiochemical yields. The lipophilicity of corresponding technetium(I)-99m complex 7b′ was appropriately reduced, which might be favorable to target tissue selectivity in vivo. The stability of complex 7b′ is excellent in 1 mM histidine, 1 mM cysteine, PBS and bovine serum within 6 h in vitro.     

Synthesis and reactivity of perchlorate bis(tetrahydrothiophen)gold(I). 197Au Mössbauer spectra of three-coordinate gold(I) complexes

The displacement of tetrahydrothiophen (tht) in [Au(tht)₂]ClO₄ by neutral ligands gives bi-, tri- or tetra-coordinated complexes of the type [Au- (py)₂]ClO₄, [(tht)AuPPh₂NHPPh₂Au(tht)] (ClO₄)₂, [LAu(LL)]ClO₄ (L=tht, PPh₃; LL=bipy, phen) or [AuL₄]ClO₄ (L=PPh₃, AsPh₃ or SbPh₃). The reaction between [Au(tht)₂]ClO₄ and (Bu₄N)[AuR₂] (R=C₆F₅, C₆Cl₅, C₆F₃H₂) yields RAu(tht). The ¹⁹⁷Au Mössbauer spectrum of [LAu(LL)]ClO₄ establishes it as a tri-coordinated species, albeit with an asymmetrically linked bidentate ligand.     

Dermatoglyphic and anthropometric relationships within the I?upiat (Eskimo) hand

On the basis of earlier findings with Easter Islanders suggesting a positive correlation between dermatoglyphic variables and hand anthropometric measurements, the present study was designed to determine if such a relationship could be generalized to another population, namely, I?upiat (Eskimo). Since some dermatoglyphic and anthropometric variables were available for both sides of the body, the extension of this study to explore the question of asymmetry was also possible. The I?upiat sample numbered 142 male and 176 female adult inhabitants of five Alaskan North Slope communities. The major findings of this study included, for males, significant negative correlations between left arm length and digital ridge counts and positive relationships between the palmar variable of axial index and hand length on both hands. For females, the hand breadth/length index was negatively related to most of the digital variables. Very little definitive information regarding the relationship of the asymmetry variables between the two types of measures was ascertained.     

Structural changes of cellobiohydrolase I (1,4-β-D-glucan-cellobiohydrolase I, CBHI) and PNPC (p-nitro-phenyl-β-D-cellobioside) during the binding process

Conformational changes to 1,4-β-D-glucan cellobiohydrolase I (CBHI) in response to its binding with p-nitrophenyl β-D-cellobioside (PNPC) were analyzed by second-derivative fluorescence spectrometry at the saturation binding point. Irreversible changes to the configuration of PNPC during the course of the binding process were characterized by UV spectral analysis. Isothermal titration calorimetry (ITC) was used to determine the stoichiometry of binding (i.e. the number of molar binding sites) of PNPC to CBHI. Two points on the surface of the CBHI molecule interact with PNPC, and irreversible changes to the configuration of PNPC occur during its conversion to p-nitrophenyl (PNP). The ITC studies demonstrated that the binding of PNPC to CBHI is an irreversible process, in which heat is released, but where there is no reversible equilibrium between PNPC-CBHI and CBHI and PNPC. On the other hand, PNP and cellobiose need to be released from the PNPC-CBHI complex to facilitate the repeated binding of new PNPC molecules to the renewable CBHI molecules. Therefore, we speculate that the energy, which powers the configurational change of PNPC as it is converted to PNP, is generated from cyclic changes in the conformation of CBHI during the binding/de-sorption process. These new insights may provide a basis for a better understanding of the binding mechanism in enzyme-substrate interactions.     

微生物提高石油采收率(I)

原油深藏于地下,并不呈油河的状态,而是分散于含油岩层岩石的毛细孔隙中。当钻井至油层时,分散的原油在地层原始压力的躯动下汇集起来,从采油井中喷至地表。依靠地层天然能量（自喷）采油称为一次采油。随着能量的消耗,自喷的原油逐渐减少,乃至停止。为维持地层压力,广泛采用了注水驱油和抽吸并用的技术,称为二次采油。即使如此,也只能采出油层原始储油量的１／３左右,大部分原油仍滞留在荷油岩中,或位于水驱的扫油面积之外,有待于研究开发新的采油技术去索取。微生物提高石油采收率（ＭＥＯＲ）就是其中引起注意的高新技术之一…     

中国禾本科植物新资料(I)

报道了2种禾本科植物,曲序黄花茅[Anthoxanthum flexuosum（Hook.f.）Veldkamp]在西藏的新分布,外来物种弗吉尼亚须芒草（Andropogon virginicus L.）在江西的归化,并提供了它们详细的形态学描述、图版、分布及生境等信息。此外,还讨论了弗吉尼亚须芒草的潜在入侵危险。     

秦岭的锈菌(续I)

全文分3次连载,共报告了采自秦岭林区的锈菌34属228种.其中有6个新种槭锈孢锈(Aecidium aceris)、糙苏鞘锈( Coleosporium phlomidis)、秦岭栅锈(Melampsoratsinlingensis) 、荩草生柄锈(Puccinia arthraxonicola)、冠毛草柄锈( Puccinia stephanachnes)和头状杜鹃夏孢锈( Uredo rhododendri-capiati) ;中国新记录锈菌13种米诺锈孢锈(Aecidiumminoense)、北极栅锈(Melampsora arctica)、紫藤赭痂锈(Ochropsora kraunhiae)、青篱竹柄锈Puccinia arundinariae)、高大柄锈(Puccinia exelsa)、哈氏柄锈(Puccinia kawakamiensisKakishima)、大泽柄锈(Puccinia ohsawaensis)、极细柄锈(Puccinia praegracilis)、美丽柄锈(Puccinia pulchella)、毡毛柄锈(Puccinia velutina)和帚菊夏孢锈( Uredo pertyae).文中列出了所有这些锈菌的寄主植物学名、分布及标本号,对新种作了拉丁文描述和图解,并对这些新种和部分已知种作了讨论. 本研究标本系作者及其同事们于1973～1998年采自秦岭林区的太白山、太白黄柏塬、宁陕火地塘及宁西、石泉、佛坪龙草坪、周至楼观台、南五台山、宝鸡天台山、辛家山、凤县等地.所有标本保存于西北林学院真菌标本室(NWFC).     

Substitution of glycine-661 by serine in the α1(I) and α2(1) chains of type I collagen results in different clinical and biochemical phenotypes

We have characterised a point mutation causing the substitution of serine for glycine at position 661 of the 1(I) chain of type I collagen in a child with a severe form of osteogenesis imperfecta. An identical glycine substitution in the 2(I) chain was previously detected in a woman with post-menopausal osteoporosis. Two of her sons were heterozygous for the mutation and the third son was homozygous as a result of uniparental isodisomy. Biochemical profiles of the type I collagen heterotrimers were studied in each of the patients and compared with a control. Medium and cell-layer collagens were overmodified in all patients. Overmodification was obvious in the patient with the 1(I) mutation but mild in the patients with the 2(I) mutation, being slightly less evident in the heterozygote than in the homozygote. Investigation of the melting curves of the mutant collagen trimers in all three patients showed the same slight decrease in thermal stability and, hence, a lack of correlation with phenotypic severity. In contrast, the degree of overmodification of the collagen alpha chains was correlated with the phenotypic severity. The clinical observations in these patients illustrate the possibly predominant role of mutations in the collagen 1(I) chains over the same mutations in the 2(I) chains in determining the clinical outcome.