The effect of hydrogen bonding in two crystal modifications of aquabis(N,N-dimethylglycinato-κN,κO)copper(II): Experimental and theoretical study

From the crystals of trans aquabis(N,N-dimethylglycinato-κN,κO)copper(II) dihydrate (compound 1, space group P2₁2₁2₁) novel crystal structure of trans aquabis(N,N-dimethylglycinato-κN,κO)copper(II) (compound 2, space group Pbca) was obtained and analysed by X-ray diffraction. In the crystal structure 1, the O-H?O hydrogen bonds form three-dimensional network. In the crystal structure 2, two-dimensional layers stacking to each other are formed, with non-polar N,N-dimethyl groups placed on the opposite sides of the layers, and with the polar part in the middle forming CO?O-H and C-H?O hydrogen bonds. Different hydrogen bonding patterns in 1 and 2 do not pronouncedly affect molecular geometry of the title compound. Molecular mechanics force field suited for studying the properties of bis(amino acidato)copper(II) complexes in the solid state can follow the differences between the experimental molecular structures in the two diverse crystalline surroundings. To make possible direct comparison between crystal lattices, the force field was applied to predict unit cell packing of supposed anhydrous bis(N,N-dimethylglycinato)copper(II) in space group Pbca. Relative intermolecular energies of hypothetic anhydrous crystal and simulated 1 and 2 crystals are discussed. On the basis of experimental and theoretical results we conclude that the main effect of two water molecules of crystallisation in 1 is to stabilise the crystal packing via hydrogen bonding, whilst similar pyramidal copper(II) coordination geometry in 1 and 2 is due to axially coordinated water molecule and its intermolecular interactions.     

Synthesis, characterisation and crystal structure of hydroxylamido-κN,O(iodo)[tris(3,5-dimethylpyrazol-1-yl)borato]nitrosylmolybdenum(II)

The unusual 18e seven-coordinate Mo(II) complex [Mo(NO)(H₂NO-κ²N,O)(Tp^Me2)I] (1; [Tp^Me2]⁻ is hydrotris(3,5-dimethylpyrazol-1-yl)borate) has been synthesised and characterised by IR, ¹H NMR and ESI-MS spectroscopies and by a single crystal X-ray diffraction study. The complex has a distorted pentagonal bipyramid structure with equatorial κ²-NH₂O⁻ ligand (d_N-O = 1.387 Å, d_Mo-N and d_Mo-O equal 2.049 and 2.092 Å, respectively). In the solid state 1 exists as a dimer (the point group C_i) due to the formation of two NH?O hydrogen bonds (d_N-H?O = 2.064 Å) between the adjacent NH₂O⁻ ligands, whilst in solution at/or above RT it resolves itself giving a monomer, which readily isomerises to more thermodynamically stable diastereoisomer.     

E. coli sabotages the in vivo production of O-linked β-N-acetylglucosamine-modified proteins

The O-linked β-N-acetylglucosamine (O-GlcNAc) post-translational modification is an important, regulatory modification of cytosolic and nuclear enzymes. To date, no 3-dimensional structures of O-GlcNAc-modified proteins exist due to difficulties in producing sufficient quantities with either in vitro or in vivo techniques. Recombinant co-expression of substrate protein and O-GlcNAc transferase in Escherichia coli was used to produce O-GlcNAc-modified domains of human cAMP responsive element-binding protein (CREB1) and Abelson tyrosine-kinase 2 (ABL2). Recombinant expression in E. coli is an advantageous approach, but only small quantities of insoluble O-GlcNAc-modified protein were produced. Adding β-N-acetylglucosaminidase inhibitor, O-(2-acetamido-2-dexoy-d-glucopyranosylidene)amino-N-phenylcarbamate (PUGNAc), to the culture media provided the first evidence that an E. coli enzyme cleaves O-GlcNAc from proteins in vivo. With the inhibitor present, the yields of O-GlcNAc-modified protein increased. The E. coli β-N-acetylglucosaminidase was isolated and shown to cleave O-GlcNAc from a synthetic O-GlcNAc-peptide in vitro. The identity of the interfering β-N-acetylglucosaminidase was confirmed by testing a nagZ knockout strain. In E. coli, NagZ natively cleaves the GlcNAc-β1,4-N-acetylmuramic acid linkage to recycle peptidoglycan in the cytoplasm and cleaves the GlcNAc-β-O-linkage of foreign O-GlcNAc-modified proteins in vivo, sabotaging the recombinant co-expression system.     

Substitution of trans ligands in μ-oxo-bis(μ-acetato)diruthenium(III) complexes: Synthesis and kinetic studies

[Ru₂O(L)₆(acetate)₂](PF₆)₂ {L = pyridine 1; 4-picoline 2} undergo aquation in acetone-water (60:40 v/v) mixed solvent to form diaquo complexes in solution as shown by proton NMR studies. Ligands trans to the μ-oxo group are substituted. These diaquo complexes react with substituted pyridines and imidazoles to form respective disubstituted complexes. Rate constants for aquation and complexation under pseudo first order conditions of ligand are reported. Rate constants increase with increase in the basicity of incoming ligand. Disubstituted complexes proposed to be formed in solution have been isolated and characterized by elemental analyses, visible spectra, proton NMR. Single crystal X-ray structures of 4-picoline and 4-methylimidazole disubstituted complexes are reported. All the isolated complexes exhibit a strong peak between 570 and 585 nm in their visible absorption spectra. λ_max varies linearly with ∑pk_a of terminal ligands. In disubstituted complexes of 1 with 2-methyl and 4-methyl imidazole deprotonation of N(1)H of methylimidazoles takes place in solution.     

Synthesis, crystal structure and pH dependent cytotoxicity of (SP-4-2)-bis(2-aminoethanolato-κN,O)platinum(II) - a representative of novel pH sensitive anticancer platinum complexes

Solid tumors are often hypoxic and consequently the pH in the tumoral tissue is decreasing with increasing tumor size (pH 5.5-7.4 in solid tumors versus pH 7.4 in normal tissues). This marked difference in pH value is a problem for weak base organic drugs and could advantageously be used for the introduction of pH sensitive anticancer platinum drugs. Synthesis and structure determination of (SP-4-2)-bis(2-aminoethanolato-κ²N,O)platinum(II), its binding behavior to 5^′-GMP and its cytotoxicity against cisplatin sensitive cell lines under standard pH screening conditions (pH 7.4) as well as in acidified cell culture medium (pH 6.0) mimicking the conditions in a number of solid tumors is presented. There is evidence that this concept in anticancer platinum therapy, namely administration of rather unreactive drugs and activation under acidic pH conditions, can be realized.     

Nucleotide diversity and minisatellite in chloroplast Asp(GUC)–Thr(GGU) region in Elymus trachycaulus complex, Elymus alaskanus and Elymus caninus

Nucleotide variation in chloroplast Asp(GUC)–Thr(GGU) intergenic region and genetic relationships among this group were examined among Elymus trachycaulus complex, Elymus alaskanus and Elymus caninus. The estimates of nucleotide diversity (π) ranged from 0.00111 for Elymus virescens to 0.03086 for E. caninus. Highest nucleotide diversity was found for E. caninus among the taxa analyzed here and followed by Elymus hyperarcticus. E. virescens accessions are genetically very uniform. Phylogenetic analysis suggested that E. caninus is paraphyletic. Elymus violaceus is genetically distinct from both E. alaskanus and E. trachycaulus. Our result indicates that Asp (GUC)–Thr (GGU) intergenic region has a high rate of evolutionary in Elymus species. Large indels detected in this region appear to have a highly rate of evolution and are thus more prone to homoplasy. We also first reported a minisatellite discovered in Asp (GUC)–Thr (GGU) region in Elymus species. The minisatellite identified here is an excellent candidate marker for studying population structures of Elymus species.     

Synthesis, crystal structure and magnetic properties of a polynuclear Cu(II) complex: catena-poly[aqua(di-2-pyridylamine)copper(II)(μ-formato-O,O′)nitrate]

The synthesis, X-ray structure, spectroscopic and magnetic properties of a zig-zag formato-bridged chain complex with the formula [Cu(dpyam)(μ-O₂CH)(OH₂)]_n(NO₃)_n (1) (in which dpyam = di-2-pyridylamine) is described.The geometry of the copper(II) ion is distorted square pyramidal with a basal plane consisting of two nitrogen atoms of the dpyam ligand (Cu-N distances 1.987(3) and 2.010(3) Å) and two oxygen atoms of two different formato ligands (Cu-O distances 1.974(2) and 1.975(2) Å). A coordinated water molecule occupies the axial position at a distance of 2.222(3) Å. The copper atoms are bridged unsymmetrically by a formato anion in a syn-anti arrangement, resulting in a polymeric zig-zag chain structure.The magnetic susceptibility measurements (5-280 K) agree with a very weak ferromagnetic chain interaction between the Cu centres with a J value of 0.75 cm⁻¹.     

R-(-)-β-O-methylsynephrine, a natural product, inhibits VEGF-induced angiogenesis in vitro and in vivo

R-(-)-β-O-methylsynephrine (OMe-Syn) is an active compound isolated from a plant of the Rutaceae family. We conducted cell proliferation assays on various cell lines and found that OMe-Syn more strongly inhibited the growth of human umbilical vein endothelial cells (HUVECs) than that of other normal and cancer cell lines tested. In angiogenesis assays, it inhibited vascular endothelial growth factor (VEGF)-induced invasion and tube formation of HUVECs with no toxicity. The anti-angiogenic activity of OMe-Syn was also validated in vivo using the chorioallantonic membrane (CAM) assay in growing chick embryos. Expression of the growth factors VEGF, hepatocyte growth factor, and basic fibroblast growth factor was suppressed by OMe-Syn in a dose-dependent manner. Taken together, our results indicate that this compound could be a novel basis for a small molecule targeting angiogenesis.     

Révision systématiquedu genre Steginoporella smitt, 1873 (Bryozoa Cheilostomata)

Systematic revision of the genus Steginoporella: until now about eighty species were described. Only twenty recent species and thirty-four fossil ones are maintained. Several species and subspecies are new.The main interest of this revision is to establish a biostratigraphical scale: the settlement of this scale is based on the known stratigraphical distribution and on an attempt of phylogeny.The second advantage is ecological: all recent species live in marine tropical environment. The Steginoporella are good paleoecological indicators.At last, the establishment of a paleobiogeography, even incomplete and not definitive, allows to understand more easily recent distribution of Steginoporella connected with the great events of earth evolution.     

2(S),4(R)-4-(β-d-Galactopyranosyloxy)-4-isobutyl-glutamic acid: A new amino acid in Reseda odorata

2(S),4(R)-4-(β-d-Galactopyranosyloxy)-4-isobutylglutamic acid (I) has been isolated from the flowers of Reseda odorata, wherein it occurs in substantial quantity. Hydrolysis of I gives d-galactose, 2(S),4(R)-4-hydroxy-4-isobutylglutamic acid (II) and 3(R),5(S)-3-hydroxy-3-isobutyl-2-pyrrolidone-5-carboxylic acid (III) and its treatment with nitrous acid yields a galactoside of a non-nitrogenous hydroxy acid lactone (IV). The structures of I and its degradation products are supported by PMR, ¹³C-NMR and other spectroscopic methods. ¹³C-NMR spectroscopy of the model compound 2-(β-d-galactopyranosyloxy)isobutyric acid confirmed the structure of the natural product. The S- (or l-) configuration at C(2) in the amino acid moiety of I has been established by the use of the Clough—Lutz—Jirgenson rule and the R-configuration at C(4) of the same unit has been assigned tentatively. I represents the first example of a glycoside of a higher plant amino acid in which the carbohydrate residue is linked to an aliphatic hydroxy group.     

Modification de la fonction antibiotique de deux diatomées marines, Asterionella japonica (Cleve) et Chaetoceros lauderi (Ralfs), par le dinoflagelléProrocentrum micans (Ehrenberg)

Two diatoms, Asterionella japonica (Cleve) and Chaetoceros lauderi (Ralfs), produced a similar lipidic antibiotic, whose activity increased after irradiation by visible light.In mixed cultures with the dinoflagellate Prorocentrum micans Ehrenberg, their cells contained higher amounts of the photoactivated antibiotic and a lower quantity of carotenoid pigments.These observations suggest the action of a chemical mediator released into the medium by P. micans, which inhibits the synthesis of pigments, thus leading to an increase of the photoactivation of the lipidic antibiotics in vivo. A similar inverse relationship between the concentration of carotenoids and the antibiotic activity was observed in several clones of Asterionella japonica isolated from different sea-water samples, and in cultures of the same diatom in the presence of diphenylamine. The importance of such phenomenon in a natural environment is discussed.     

Rats’ (Rattus norvegicus) temporal discrimination of brief auditory stimuli: How does it compare with that of humans (Homo sapiens) and zebra finches (Taeniopygia guttata)?

The present study with rats replicated an experiment on the ability of zebra finches and humans to discriminate among brief auditory stimuli (see Weisman et al., 1999, Experiment 2). We trained rats with 27 3-kHz tones that varied in duration from 10 ms to 1420 ms. Reinforcement was contingent on responding (approaching the food well) to the nine medium-durations range tones (56-255 ms) but not to the nine short-durations range (10-46 ms) or long-durations range tones (309-1420 ms). Rats also received post-discrimination transfer tests with 2 kHz and 4 kHz tones that varied over the same durations as the 3 kHz tones. Rats acquired the temporal discrimination to a slightly lower level of accuracy than seen in finches or humans by Weisman et al. (1999). We tested for transfer of the temporal discrimination to find that rats, similar to humans (data from Weisman et al., 1999), transferred to untrained 2-kHz and 4-kHz tones at levels approaching accuracy to that achieved to the trained 3-kHz tone. By contrast, zebra finches (data from Weisman et al., 1999) failed to transfer their discrimination to the trained tone. We conclude that (a) rats discriminate among tone durations at least as well as they do among auditory frequencies and (b) rats like humans, but unlike finches, are insensitive to absolute pitch in their temporal discrimination.     

One-pot efficient synthesis of 13(R),14(R)-epoxy-17β-methyl-20(S)-hydroxyl-18-nor-pregna-4-en-3-one via a tandem epoxidation-rearrangement-epoxidation reaction sequence

One-pot synthesis of an 18-norsteroid compound, 13(R),14(R)-epoxy-17β-methyl-20(S)-hydroxyl-18-nor-pregna-4-en-3-one has been achieved with peracetic acid/acetic acid under a mild condition, via a proved tandem epoxidation-rearrangement-epoxidation sequence. Its structure was designated on the basis of NMR and X-ray crystallography data.     

白顶鹀(Emberiza stewarti)——中国鸟类新纪录

白顶鹀(Emberiza stewarti)为中亚特有物种,比较罕见。2013年5月12日,喀什地区观鸟爱好者与户外摄影人在新疆乌恰县境内膘尔托阔依乡(39°20'N和75°05'E,海拔2 100 m)帕米尔东麓拍摄到一只雄性白顶鹀照片,经过查阅文献,确认是中国鸟类新纪录。     

广东封开县发现白眉棕啄木鸟(Sasia ochracea)

正2013年6月1日,我们在广东省肇庆市封开县黑石顶省级自然保护区(23°27'N,111°53'E)调查时发现2只白眉棕啄木鸟(Sasia ochracea)。发现地点生境是常绿阔叶林区(海拔约350 m),2只个体均栖立于钩藤属(Uncaria)植物上,其中1只为幼鸟,另一只雌性成鸟正在取食藤条上的蚁巢(见封4图a),并有饲喂幼鸟的行为,表明其可能在本地繁殖。同年10月初,再次在保护区内记录到1只。白眉棕啄木鸟体型较小,体长不到10 cm,上体橄榄绿色。眼后有一白色眉纹,一直延伸至颈     

Biosynthesis of α-spinasterol from (2- 14C (4R)-4-3H1) mevalonic acid by Spinacea oleracea and Medicago sativa

Leaves of Spinacea oleracea and Medicago sativa were incubated with (2-¹⁴C, (4R)-4³H₁ mevalonic acid and the sterols isolated. Cycloartenol had a ³H: ¹⁴C atomic ratio of 6:6 whilst oxidation to cycloartenone resulted in a ratio of 5:6 showing that tritium was present in the 3α-position and that the cycloartenol was symmetrically labelled. Separation of the 4-demethyl sterols gave α-spinasterol and a mixture of stigmast-7-enol and 24-methylcholest-7-enol, which had ³H: ¹⁴C atomic ratios of 3:5. Ozonolysis of α-spinastery] acetate gave the terminal side chain fragment as 2-ethyl-3-methyl butanoic acid. The acid contained ¹⁴C but no tritium thus showing that the C-24 hydrogen of cycloartenol is lost during the alkylation reactions leading to the C-24 ethyl group of α-spinasterol.     

越南植物Michelia tonkinensis(木兰科)的模式考订

Michelia tonkinensis A. Chev.这个名称在发表时未指定模式,曾被处理为M. balansae (Aug. DC.) Dandy的异名。在查阅了其原白和原始材料后,确认采自越南北部Tuyen Quang省的标本——Fleury 37.667 (P)是该种唯一的原始材料,应该作为模式看待,同时确认Michelia tonkinensis是一独立的种,不应该处理为M. balansae的异名。此外,还提供了M. tonkinensis的异名、俗名、描述、分布及查阅的标本等综合信息。     

Heteroleptic κ(N,C)-2-phenylpyridine platinum complexes: The use of bis(pyrazolyl)borates as ancillary ligands

Luminescent platinum(II) bis(pyrazolyl)borate complexes bearing orthometalated phenylpyridines (based on 2-phenylpyridine, 3-hexyloxy-2-phenylpyridine and (4-(pyridine-2-yl)-phenyl)methanol) and bis(pyrazolyl)borate ligands (employed as potassium dihydridobis(pyrazolyl)borate and potassium dihydridobis(3,5-dimethylpyrazolyl)borate) have been synthesized and characterized. By reaction of K₂PtCl₄ with phenylpyridine ligands a precursor has been obtained which was further converted to the corresponding heteroleptic complexes. All platinum(II) bis(pyrazolyl)borate complexes have been investigated by nuclear magnetic resonance, Fourier transform infrared spectroscopy, thermal analysis and UV-Vis absorption spectroscopy. Luminescence as well as lifetime measurements in solution and in the solid state have been performed to establish a qualitative relationship between structure and luminescence properties. The absorption and emission properties of these complexes are governed by the nature of the orthometalating ligand with emission maxima ranging from 488 to 551 nm. Emission spectra at room temperature show well-resolved vibronic fine structures and a strong spin-orbit coupling. For the compounds under investigation the mixing of the excited states leads to apparent lifetimes in the microsecond regime (5.7-8.6 μs), rendering these materials phosphorescent.