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1.
The reaction between nickel(II) nitrate and potassium phosphorus-1,1-dithiolates (di-sec-butyl and di-iso-butyl) in methanol yields 2:1 complexes which were characterized by FT-IR and NMR spectroscopy. 2:1 pyrazole adducts of both compounds were also obtained.The X-ray diffraction analysis of the compounds reveals square planar, four-coordination geometry for the homoleptic compounds and a six-coordinated distorted octahedral geometry for the adducts. In Ni[S2P(OBus)2]2 the molecules are associated through C-H?O hydrogen bonds (2.652 Å), and in Ni[S2P(OBui)2]2 the molecules are associated through C-H?S hydrogen bonds (2.948 Å). The pyrazole adducts are associated through N-H?O bonds and N-H?S bonds from the pyrazole nitrogen atoms, to form supramolecular assemblies. Thus, Ni[S2P(OBus)2(Pz)2]2 (Pz = pyrazole) forms bi-dimensional layers through N-H?O and N-H?S bonds (2.502 and 2.965 Å, respectively), whereas Ni[S2P(OBui)2(Pz)2]2 forms linear chains with N-H?S bonds 2.728 Å. The dithiophosphato groups behave as isobidentate chelating ligands.  相似文献   

2.
Lu Y  Guo J 《Carbohydrate research》2006,341(5):610-615
A single-crystal of SmCl3·C5H10O5·5H2O was obtained from methanol-water solution and its structure determined by X-ray. Two forms of the complex as a pair of anomers and related conformers were found in the single-crystal in a disordered state. One ligand is α-d-ribopyranose in the 4C1 conformation and the other one is β-d-ribopyranose. The anomeric ratio is 1:1. Both ligands provide three hydroxyl groups in ax-eq-ax orientation for coordination. The Sm3+ ion is nine-coordinated with five Sm-O bonds from water molecules, three Sm-O bonds from hydroxyl groups of the d-ribopyranose and one Sm-Cl bond. The hydroxyl groups, water molecules and chloride ions form an extensive hydrogen-bond network. The IR spectral C-C, O-H, C-O, and C-O-H vibrations were observed to be shifted in the complex and the IR results are in accord with those of X-ray diffraction.  相似文献   

3.
Dihydrohexacyanoferrates (II and III) of aromatic N-heterocyclic cations X+ (such as N-methylquinoxalinium, pyridinium, dipyridinium) and X2+ (such as pyridylpyridinium, dipyridinium) are synthesized and characterized. For the first time, the crystal structures of acidic dihydrohexacyanoferrates are described. The formation of the and X2+H2[Fe(CN)6] species which contain the [Fe(CN)6]4− and [Fe(CN)4(CNH)2]2− anions from acidic solutions occurs after the formation of the H[Fe(CN)6]3− species as can be established from the outer-sphere charge transfer (OSCT) bands in the absorption spectra. The crystal structures of these species contain extensive network of intermolecular N-H?N, N-H?O and O-H?N hydrogen bonds which link the hexacyanoferrate anions with solvent water (if present) and N-heterocyclic cations if the later can participate in the H-bond formation. In the crystals of dihydrohexacyanoferrates, the H-bond networks can be two-dimensional (species 1) and three-dimensional (species 2-7). The lack of acidic protons for the H-bond network formation can be compensated by solvent water molecules. The H-bond network plays an important role in stabilization of such strongly-acidic species such as the H2Bpy2+ and HPypy2+ cations and the [FeII(CN)4(CNH)2]2− anion.  相似文献   

4.
Xanthates, like thiolates, form a variety of complexes with metals in which coordinating sulfur can serve as a hydrogen bond acceptor. Nickel tris xanthate complexes [Ni(xan)3], (xan = o-ethylxanthate, N-(carbamoylmethyl)ethylxanthate) have been synthesized and compared by a combination of X-ray crystallographic and spectroscopic measurements. Recent results from our studies of N-H?S hydrogen bonding interactions in metal-xanthate complexes shows N-S distances to be longer than those in related thiolate complexes, indicative of weaker hydrogen bonds for the xanthates. The complex (Et4N)[N-(carbamoylmethyl)ethylxanthate)] adopts an extended conformation in both the solid state and solution and lacks either intraligand or intermolecular N-H?S hydrogen bonds. The complex (CTA)[Ni(exa)3] exhibits N-H?S hydrogen bonds between the amide group of the counterion and the ligand sulfur. The amide-sulfur N-H?S distance is 3.567 Å.  相似文献   

5.
We prepared two new analogues of ([CH3Co((DO)(DOH)pn)L]+) [(DO)(DOH)pn = N2,N2′-propane-1,3-diylbis(2,3-butanedione-2-imine-3-oxime)] B12 models but with an O-BF2-O unit replacing the O-H?O unit as follows: [CH3Co((DO)(DOBF2)pn)L]PF6 with L = pyridine (py) and 1,5,6-trimethylbenzimidazole (Me3Bzm). Our goal was to compare the properties of these new O-BF2-O complexes with the well-established O-H?O analogues. The Co-CH31H NMR shifts indicate that the BF2 group makes the Co(III) less electron rich. The X-ray crystal structures determined for the new compounds were compared to the one known structure with L = imidazole (Im). With increasing size of L, in the series Im < py < Me3Bzm, the plane of L orients so as to avoid the bulky BF2 group. This orientation effect becomes apparent in the L 1H NMR shifts, which are not sensitive to Co(III) electronic properties. Thus, in the O-BF2-O versus the O-H?O analogue, the Me3Bzm H4 signal shifts 0.41 ppm upfield from the anisotropic effect of the equatorial ligand double bonds. We advance the concept (applicable to a broad series of complexes) that steric interactions between L and the equatorial ligands are alleviated by a combination of Co-Nax bond elongation and opening of the Neq-Co-Nax angles.  相似文献   

6.
The C36 CHARMM lipid force field has been extended to include sphingolipids, via a combination of high-level quantum mechanical calculations on small molecule fragments, and validation by extensive molecular dynamics simulations on N-palmitoyl and N-stearoyl sphingomyelin. NMR data on these two molecules from several studies in bilayers and micelles played a strong role in the development and testing of the force field parameters. Most previous force fields for sphingomyelins were developed before the availability of the detailed NMR data and relied on x-ray diffraction of bilayers alone for the validation; these are shown to be too dense in the bilayer plane based on published chain order parameter data from simulations and experiments. The present simulations reveal O-H:::O-P intralipid hydrogen bonding occurs 99% of the time, and interlipid N-H:::O=C (26-29%, depending on the lipid) and N-H:::O-H (17–19%). The interlipid hydrogen bonds are long lived, showing decay times of 50 ns, and forming strings of lipids, and leading to reorientational correlation time of nearly 100 ns. The spontaneous radius of curvature for pure N-palmitoyl sphingomyelin bilayers is estimated to be 43–100 Å, depending on the assumptions made in assigning a bending constant; this unusual positive curvature for a two-tailed neutral lipid is likely associated with hydrogen bond networks involving the NH of the sphingosine group.  相似文献   

7.
Fourier transform infrared (FT-IR) spectroscopic studies (3500-600 cm−1) showed some different bands of chitosan. The absorption at 3439 cm−1 is stretching vibration of -OH and -NH2 bonds, indicating the association of the hydrogen-bond between them. The bands at 1659, 1599 and 1321 cm−1 are attributable to the peaks of stretching vibrations of amide I (ν(CO)), II (δ(N-H)), and the peak of stretching and bending vibrations of III (ν(C-N)) (δ(N-H)). The chitosan showed strong free radical scavenging activities. Pretreatment with chitosan significantly prevented the decrease of antioxidant enzymes activities and the increase of p-JNK at 3 h after renal ischemia and reduced renal tubular epithelial cell apoptosis.  相似文献   

8.
Photometric titration measurements indicated in the reaction of diazacrown ether N,N-dibenzyl-1,4,10,13-tetraoxo-7,16-diazacyclooctadecane (DD18C6, 2) with iodine in chloroform that a complex was formed in the molar ratio DD18C6:I2=1:4. This complex was also prepared on a preparative scale as dark brown compound and characterized by microanalysis, UV-Vis, IR, and Raman spectroscopy. By X-ray diffraction analysis the solid-state structure of the complex was shown to be [(DD18C6)H2]I8 ([3]I8) consisting of a doubly protonated macrocycle and an octaiodide dianion (I8 2−) in the typical (nearly planar) Z-shaped geometry. The macrocycle is Ci symmetric and the protonated nitrogen atoms adopt an endo-endo orientation that is stabilized by the three-center hydrogen bonds N-H(?O)2, where the oxygen atoms of the macrocycle act as hydrogen acceptors. The orientation of the phenyl groups of the benzyl sidearms are turned above and below the macrocycle. Quantum chemical calculations on the DFT level of theory of the non-protonated and the doubly protonated macrocycle (DD18C6, 2c) and [(DD18C6)H2]2+ (3c), respectively, were performed and discussed for 3c in terms of conformational strain of the macrocycle, the strength of the intramolecular N-H?O hydrogen bonds and cation-π interactions.  相似文献   

9.
The syntheses of the tetraazamacrocyclic ligands 1,4,7,11-tetraazacyclotetradecane (isocyclam) and 1,5,9,13-tetraazacyclohexadecane ([16]aneN4) in two steps starting from the corresponding tetraamine and diethylmalonate is reported. The trans-dicyanochromium(III) complexes, trans-[Cr(isocyclam)(CN)2]PF6 and trans-[Cr([16]aneN4)(CN)2]PF6 have also been prepared. Both are 2Eg emitters with 0-0 band emission wavelengths at 721.2 and 704.8 nm, respectively. The isocyclam complex has a room temperature excited state lifetime of 147 μs in aqueous solution which increases to 215 μs upon macrocyclic N-H deuteration, whereas the corresponding lifetime of the [16]aneN4 complex is 25 μs and is unaffected by macrocyclic N-H deuteration. The implications of the temperature dependence of the excited state lifetimes are also presented.  相似文献   

10.
The self-assembled reaction of 2-hydroxynicotinic acid, KOH and tri-n-butyltin chloride in CH3OH and H2O (V/V = 5:1) under solvothermal condition (150 °C) affords a novel mixed tri- and dibutyltin macrocyclic complex 1. Characterization of the complex 1 was achieved using elemental analysis, IR, NMR (1H, 13C and 119Sn) spectroscopy, TGA and X-ray crystallography diffraction analysis. X-ray data revealed that it is an unusual 16-membered macrocycle containing eight tin atoms, and they can be divided into four sorts by the distinct environments, the endocyclic tin atoms are best described as five- and six-coordinate and the exocyclic tin atoms as five-coordinate. Furthermore, a 2D corrugated sheet is formed by intermolecular C-H?Cl, O-H?N and O-H?O weak interactions.  相似文献   

11.
Four new triorganotin complexes of 3-amino-5-mercapto-1,2,4-triazole with the type of R3Sn(SC2N3HNH2-3) (R = Me, 1; n-Bu, 2; Ph, 3; PhCH2, 4) have been synthesized. All the complexes have been characterized by elemental analysis, IR, 1H NMR and 13C NMR spectra. Complexes 1, 3 and 4 have been characterized by X-ray crystallography analyses too. The geometry about Sn of complex 1 is distorted trigonal bipyramidal and the supramolecular structures of complex 1 has been found consist of channels built up by intermolecular N-H?N hydrogen bonding. The geometry of tin atoms in complexes 3 and 4 are distorted tetrahedron and 1D polymers connected by intermolecular N-H?N hydrogen bonding or N-H?N and N-H?S hydrogen bonding. Additionally, 1D polymer of complex 3 aggregated in 2D layer by intermolecular N-H?S hydrogen bonding.  相似文献   

12.
Synthesis and crystal structure of two coordination polymers of composition [MnII(H2bpbn)1.5][ClO4]2 · 2MeOH · 2H2O (1) and [CoII(H2bpbn)(H2O)2]Cl2 · H2O (2) [H2bpbn = N,N′-bis(2-pyridinecarboxamido)-1,4-butane], formed from the reaction between [Mn(H2O)6][ClO4]2/CoCl2 · 4H2O with H2bpbn in MeCN, are described. In 1 each MnII ion is surrounded by three pyridine amide units, providing three pyridine nitrogen and three amide oxygen donors. Each MnII center in 1 has distorted MnN3O3 coordination. In 2 each CoII ion is coordinated by two pyridine amide moieties in the equatorial plane and two water molecules provide coordination in the axial positions. Thus, the metal center in 2 has trans-octahedral geometry. In both 1 and 2, the existence of 1D zigzag network structure has been revealed. Owing to π-π stacking of pyridine rings from adjacent layers 1 forms 2D network; 2 forms 2D and 3D network assemblies via N-H?Cl and O-H?Cl secondary interactions. Both the metal centers are high-spin.  相似文献   

13.
Microsensors, including a recently developed NO3 biosensor, were applied to measure O2 and NO3 profiles in marine sediments from the upwelling area off central Chile and to investigate the influence of Thioploca spp. on the sedimentary nitrogen metabolism. The studies were performed in undisturbed sediment cores incubated in a small laboratory flume to simulate the environmental conditions of low O2, high NO3, and bottom water current. On addition of NO3 and NO2, Thioploca spp. exhibited positive chemotaxis and stretched out of the sediment into the flume water. In a core densely populated with Thioploca, the penetration depth of NO3 was only 0.5 mm and a sharp maximum of NO3 uptake was observed 0.5 mm above the sediment surface. In sediments with only few Thioploca spp., NO3 was detectable down to a depth of 2 mm and the maximum consumption rates were observed within the sediment. No chemotaxis toward nitrous oxide (N2O) was observed, which is consistent with the observation that Thioploca does not denitrify but reduces intracellular NO3 to NH4+. Measurements of the intracellular NO3 and S0 pools in Thioploca filaments from various depths in the sediment gave insights into possible differences in the migration behavior between the different species. Living filaments containing significant amounts of intracellular NO3 were found to a depth of at least 13 cm, providing final proof for the vertical shuttling of Thioploca spp. and nitrate transport into the sediment.  相似文献   

14.
Some experimental data are given on the infrared spectra between 3300 and 3500 cm?1 of dilute solutions in carbon tetrachloride of three types of model compounds: CH3?CONH-CH(R1)-CONH(R2), (I); CH3-CON(CH3)-CH(R1)-CONH(R2), (II) and CH3-CONH-CH(R1)-CON(R2)2, (III). In studying the N-H stretching bands, it was found that there are two types of intramolecular hydrogen bonds in these molecules; these result in two different cyclized conformations, C5 and C7, which contain respectively, five and seven atoms in the ring. By using model substances I, II, and III, in which the nitrogen atoms are unequally substituted, it is possible to identify the N-H stretching bands which are to be ascribed to the N-H oscillators included in the two different chelated conformations. It is found also that the stretching frequency of a free N-H oscillator depends upon the substituent on the nitrogen atom. Thus, it is possible to observe, with some of the model compounds I, four different absorption bands located at 3340, 3420, 3440, and 3460 cm?1. The first two are ascribed to the N-H oscillators included in the H? bonds which lock the C7 and C5 conformations; the last two correspond to free N-H which differ with the substituent on the nitrogen atom.  相似文献   

15.
How soil fungi function in soil carbon and nutrient cycling is not well understood by using fungal enzymatic differences and their interactions with soil colloids. Eight extracellular enzymes, EEAs (chitinase, carboxymethyl cellulase, β-glucosidase, protease, acid phosphatase, polyphenol oxidase, laccase, and guaiacol oxidase) secreted by ten fungi were compared, and then the fungi that showed low and high enzymatic activity were co-cultured with soil colloids for the purpose of finding fungi-soil interactions. Some fungi (Gomphidius rutilus, Russula integra, Pholiota adiposa, and Geastrum mammosum) secreted 3–4 enzymes with weak activities, while others (Cyathus striatus, Suillus granulate, Phallus impudicus, Collybia dryophila, Agaricus sylvicola, and Lactarius deliciosus) could secret over 5 enzymes with high activities. The differences in these fungi contributed to the alterations of functional groups (stretching bands of O-H, N-H, C-H, C = O, COO- decreased by 11–60%, while P = O, C-O stretching, O-H bending and Si-O-Si stretching increased 9–22%), surface appearance (disappearance of adhesive organic materials), and elemental compositions (11–49% decreases in C1s) in soil colloids. Moreover, more evident changes were generally in high enzymatic fungi (C. striatus) compared with low enzymatic fungi (G. rutilus). Our findings indicate that inter-fungi differences in EEA types and activities might be responsible for physical and chemical changes in soil colloids (the most active component of soil matrix), highlighting the important roles of soil fungi in soil nutrient cycling and functional maintenance.  相似文献   

16.
DEAE-cellulose-purified Trypanosoma lewisi from 4-day (dividing trypanosomes) and 7-day (non-dividing trypanosomes) infections in rats were compared for initial uptake of glucose, leucine, and potassium. Glucose entered the parasitic cells by mediated (saturable) processes, whereas leucine and K+ entered by mediated processes and diffusion. Glucose entry was significantly elevated in 4-day cells (Vmax 4.00 ± 1.02 nmoles/ 1 × 108 cells/min) with respect to 7-day cells (Vmax 1.83 ± 0.62 nmoles 1 × 108 cells/min). Likewise, the affinity of the glucose carrier was significantly greater in 4-day cells (Km = 0.30 ± 0.02 mM) than in 7-day cells (Km = 0.59 ± 0.11 mM). When leucine and K+ transport were compared in 4- and 7-day populations, significant elevations in the rate of entry (Vmax) of both substrates were observed for 4-day cells; Km values for leucine and K+ were not altered by the stage of infection. For leucine, the Vmax and Km for 4-day cells were 2.40 ± 0.50 nmoles/1 × 108 cells/30 sec and 78 ± 7 μM, respectively; corresponding values in 7-day cells were 1.06 ± 0.02 nmoles/1 × 108 cells/30 sec and 66 ± 11 μM. For K+, the Vmax and Km for 4-day cells were 15.97 ± 0.38 nmoles/1 × 108 cells/min and 1.2 mM, respectively; corresponding values in 7-day cells were 4.76 ± 1.82 nmoles/1 × 108 cells/min and 1.05 mM. The observed increase in the rate of K+ entry into 4-day cells was attributable to enhanced influx; no significant difference in the rate of K+ efflux was noted when 4- and 7-day cells were compared (t12 of K+ leak for 4- and 7-day cells were 68.1 ± 9.3 and 67.9 ± 15.2 min, respectively). Potassium influx was ouabain insensitive. Membrane function in 7-day cells was not uniformly inhibited. No significant difference in the activity of the membrane-bound enzyme, 5′-nucleotidase, was observed when 4- and 7-day cells were compared.  相似文献   

17.
The dehalogenation reactions of pure zinc bromoacetate and its mixtures with hexamethylenetetramine, 2,2′-bipyridine, 1,10-phenanthroline were studied in water solutions. Due to the decomposition of hexamethylenetetramine during reaction, the cadmium bromoacetate-hexamethylenetetramine system was also studied. The four new coordination compounds, catena-[bis(μ2-α-hydroxyacetato-κ3O1,O2:O1′)-zinc], catena[μ2-1-(8-carboxylateethyl)-1,3,5,7-tetra-aza-adamantan-1-ium-N,O′]-dibromo-cadmium, dibromo-(2,2′-bipyridine-N,N′)-zinc, dibromo-(1,10-phenanthroline-N,N′)-zinc were synthesised and characterised by elemental and thermal analysis, IR and UV-vis spectroscopy, and X-ray crystallography. All compounds are air stable and well soluble in water. The zinc hydroxyacetate creates two-dimensional 4-c uninodal net. The zinc atoms are four and six coordinated and the cadmium atom is five coordinated. The coordination polyhedra of central atoms can be described as octahedron and trapezoidal pyramid for Zn and Cd polymers, respectively, and as trigonal pyramid for ZnBr2 complexes. The bond valences considerations show that the chelating amines are bonded almost two times stronger to the central atoms than the chelating carboxylate groups. In the structures of polymeric compounds exist O-H?O, C-H?O, C-H?N and C-H?Br hydrogen bonds. The IR spectra show typical vibrations for chelating amine molecules. The thermal decomposition of studied compounds proceeds via multiple steps with gradual evolution of ligands.  相似文献   

18.
Pullulan-sodium alginate blend films were prepared and characterized as a function of water activity (aw). At low aw, the incorporation of alginate into pullulan film increased the tensile strength and elastic modulus, but decreased the elongation at break of the composite films; the opposite trends were observed at elevated aw. Above 0.43 aw, water exerted a typical plasticization effect upon the biopolymer blends. As aw increased from 0.23 to 0.43, an anti-plasticization effect was observed as tensile strength and elastic modulus increased. The glass transition temperature of all samples decreased substantially as aw increased from 0.23 to 0.84 due to the plasticization effect of water. Within this aw range, one transition temperature was observed for all film specimens. The stretching vibration band of O-H was investigated using attenuated total reflection Fourier transform infrared spectroscopy to identify the various species of water interacting with the polysaccharide films.  相似文献   

19.
Some zinc (II) complexes having formula [Zn(PziPr2H)(μ-PziPr2)(RCOO)]2 [(PziPr2H = 3,5-diisopropylpyrazole, RCOO = carboxylate ligands with R is CH3 for 1, CF3 for 2, CH3(CH2)2 for 3, CH3(CH2)4 for 4 and CH3(CH2)5 for 5] were prepared and structurally characterized by different techniques including single crystal X-ray. The X-ray studies suggested that all these complexes are centrosymmetric dinuclear with tetrahedral geometry around each zinc center. The pyrazole ligand is coordinated in both terminal as well as a bridging fashion whereas the carboxylates behave as monodentate ligand. All the complexes show hydrogen bonding between hydrogen atom of pyrazole (N-H of terminal pyrazole) and nonbonded oxygen atom of carboxylate. Out of these complexes only 5 [Zn(PziPr2H)(μ-PziPr2)(CH3(CH2)5COO)]2 exhibited emission at room temperature.  相似文献   

20.
Organic and water extracts of Isochrysis galbana T-ISO (=Tisochrysis lutea), Tetraselmis sp. and Scenedesmus sp. were evaluated for their antioxidant activity, acetylcholinesterase (AChE) inhibition, cytotoxicity against tumour cell lines, and fatty acids and total phenolic content (TPC). I. galbana T-ISO had the highest TPC (3.18 mg GAE g?1) and radical scavenging activity, with an IC50 value of 1.9 mg mL?1 on the acetone extract. The extracts exhibited a higher ability to chelate Fe2+ than Cu2+, and the maximum Fe2+ chelating capacity was observed in the hexane extract of Scenedesmus sp. (IC50=0.73 mg mL?1) and Scenedesmus sp. (IC50?=?0.73 mg mL?1). The highest ability to inhibit AChE was observed in the water and ether extracts of Scenedesmus sp., with IC50 values of 0.11 and 0.15 mg mL?1, respectively, and in the water extract of I. galbana (IC50?=?0.16 mg mL?1). The acetone extract of I. galbana T-ISO significantly reduced the viability of human hepatic carcinoma HepG2 cells (IC50?=?81.3 μg mL?1) as compared to the non-tumour murine stromal S17 cell line, and displayed a selectivity index of 3.1 at the highest concentration tested (125 μg mL?1). All species presented a highly unsaturated fatty acids profile. Results suggest that these microalgae, particularly I. galbana T-ISO, could be a source of biomolecules for the pharmaceutical industry and the production of functional food ingredients and can be considered as an advantageous alternative to several currently produced microalgae.  相似文献   

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