Studies on the reactions of ruthenium(II) substrates with tridentate (N,N,O) azo ligands

Reactions of 1-{[2-(arylazo)phenyl]iminomethyl}-2-phenol, HL_sal, 1, [where H represents the dissociable protons upon complexation and aryl groups of HL_sal are phenyl for HL¹_sal, p-methylphenyl for HL²_sal, and p-chlorophenyl for HL³_sal], ligands with Ru(H)(CO)(Cl)(PPh₃)₃ afforded complexes of composition [(L_sal)Ru(CO)(Cl)(PPh₃)] and (L_sal)₂Ru where the N,N,O donor tridentate (L_sal)⁻ ligands coordinated the metal centre facially and meridionally, respectively. Stepwise formation of [(L_sal)₂Ru] has been ascertained. Reaction of 1-{[2-(arylazo)phenyl]iminomethyl}-2-napthol, HL_nap, 2, [where H represents the dissociable protons upon complexation and aryl groups of HL_nap are phenyl for HL¹_nap, p-methylphenyl for HL²_nap, and p-chlorophenyl for HL³_nap], ligands with Ru(H)(CO)(Cl)(PPh₃)₃ afforded exclusively the complexes of composition [(L_nap)Ru(CO)(Cl)(PPh₃)], where N,N,O donor tridentate (L_nap)⁻ was facially coordinated. The ligand 1-{[2-(phenylazo)phenyl]aminomethyl}-2-phenol, HL, 3, was prepared by reducing the aldimine function of HL¹_sal. Reaction of HL with Ru(PPh₃)₃Cl₂ afforded new azosalen complex of Ru(III) in concert with regiospecific oxygenation of phenyl ring of HL. All the new ligands were characterized by analytical and spectroscopic techniques. The complexes were characterized by analytical and spectroscopic techniques and subsequently confirmed by the determination of X-ray structures of selected complexes.     

水稻生长及其体内C、N、P组成对开放式空气CO2浓度增高和N、P施肥的响应

采用FACE（Free Air Carbon-dioxide Enrichment)技术,研究了不同N、P施肥水平下,水稻分蘖期、拔节期、抽穗期和成熟期根、茎、穗生长,C/N比、N、P含量及N、P吸收对大气CO2浓度升高的响应,结果表明,高CO2促进水稻茎、穗和根的生长,增加分蘖期叶干重,对拔节期、抽穗期的成熟期叶干重没有显著增加,降低茎、叶N含量;增加抽穗期穗N含量;降低成熟期穗N含量;对分蘖期根N含量影响不显著,而降低拔节期,抽穗期和成熟期根N含量,增加拔节期、抽穗期和成熟期叶P含量,对茎、穗、根P含量影响不显著,水稻各组织C含量变化不显著,C/N比增加,显著增加水稻地上部分P吸收;增加N吸收,但没有统计显著性,N、P施用对水稻各组织生物量没有显著影响,高N（HN）比低N（LN）增加组织中N含量,而不同P肥水平间未表现出明显差异,高N条件下高CO2增加水稻成熟期地下部分/地上部分比,文中还讨论了高CO2对N、P含量及地下部分/地上部分比的影响机制。     

蛋白质体积对其亚细胞定位的影响

为了探索N(2)-L-丙氨酰-L-谷氨酰胺的合成工艺,确定最佳工艺以符合工业化生产的需求,以L-谷氨酰胺为原料,通过氨解反应合成L-丙氨酰-L-谷氨酰胺,并对反应条件及精制工艺进行优化.实验结果显示,当设定氨解反应温度为60℃,反应压力为0.5 MPa,反应时间为5.5h,以及氨水体积与α-D-氯丙酰-L-谷氨酰胺质量之比(V∶m)为1.5∶1时,将所得粗品用75％乙醇溶液进行精制,合成得到的N(2)-L-丙氨酰-L-谷氨酰胺经检测含量为99.65％,总收率约为55.77％.结果表明,经优化后的工艺简便安全、条件温和易控、生产周期短,适合工业化大量生产,且产品纯度、收率较高.     

P effects on N uptake and remobilization during regrowth of Italian ryegrass (Lolium multiflorum)

The influence of P deficiency on the utilization of two sources of N, mineral N (exogenous N) and reserved N (endogenous N), for regrowth of Italian ryegrass (Lolium multiflorum) was studied. P-sufficient (+P) or P-free (−P) nutrition solution was applied from 7 days before defoliation to 24 days of regrowth and the N flows derived from two different N sources within the plant were quantified by ¹⁵N pulse-chase labeling. Shoot regrowth significantly reduced by 12 days of regrowth, while root growth was more in −P plants. Inorganic P (P_i) concentration was highly reduced by P deprivation more in the stubble and regrowing shoots and less in the roots. At defoliation, P deprivation had induced a higher accumulation for all N compounds in the stubble and for amino acids in the roots. The previously incorporated ¹⁵N in stubble and roots as nitrate and amino acids was much decreased in −P plants especially for the first 6 days of regrowth. Total N content in the regrowing leaves was not significantly different between +P and −P plants, but percentage contribution of remobilized N for total leaf N formation was significantly higher in −P plants (78%) than in +P plants (69%) at 6 days of regrowth. From day 12, the utilization of both endogenous and exogenous N was apparently inhibited in −P plants.     

Delocalization of polar plasm components caused by grandchildless mutations, gs(1)N26 and gs(1)N441, in Drosophila melanogaster

Two maternal-effect grandchildless (gs) mutations of Drosophila melanogaster, gs(1)N26 and gs(1)N441, cause delay in nuclear arrival at the polar plasm. In mutant embryos, polar plasm loses its ability to induce pole cells during retarded nuclear migration to the posterior pole of embryos. In the present study, it was shown that in N26 and N441 embryos, mitochondrial large rRNA (mtlrRNA), an essential factor for pole cell formation, is delocalized during the delay in nuclear arrival. This suggests that the loss of mtlrRNA causes failure of the mutants to form pole cells. Furthermore, it was shown that all of the other polar plasm components examined, namely Vasa protein, Germ cell-less protein, nanos mRNA and Polar granule component RNA start to be delocalized during the delay in nuclear arrival. This suggests that polar plasm integrity is not maintained in mutant embryos. It was finally shown that Vas is also delocalized in embryos that are inhibited to form pole cells by reducing the amount of mtlrRNA. This indicates that the segregation of polar plasm into pole cells is required to maintain polar plasm integrity. The mechanism regulating polar plasm integrity in embryos is discussed.     

Solid-state and proton NMR characterization of an iron(II) complex of a tridentate, facially coordinating N,N,O donor ligand

Despite the many enzymes that use 2-His-1-carboxylate facial triads to bind iron(II), there are few crystallographically characterized synthetic iron(II) complexes of tridentate ligands that bind through two imidazoles and one carboxylate. We report ¹H NMR characterization of the equilibrium between one such ligand and aqueous Fe²⁺. The formation of 1:1 and 2:1 complexes is evident, but the 1:1 complex is never the exclusive compound in solution. This behavior has not been reported previously for N,N,O ligand-iron(II) complexes. The 2:1 ligand/iron complex crystallizes from solution, and it has been completely characterized including an X-ray crystal structure.     

Influence of initial organic N reserves and residual leaf area on growth, N uptake, N partitioning and N storage in alfalfa (Medicago sativa) during post-cutting regrowth

BACKGROUND AND AIMS: The influence of initial residual leaf area and initial N reserves on N uptake, final N distribution, and yield in alfalfa regrowing after cutting, were studied. METHODS: The effects of two levels of initial residual leaf area (plants cut to 15 cm, with (L+) or without (L-) their leaves) and two initial levels of N status [high N (HN) or low N (LN)] on growth, N uptake and N partitioning, allocation and storage after 29 d of post-cutting regrowth were analysed. KEY RESULTS: During most of the regrowth period (8-29 d after the initial harvest), HN and L+ plants had higher net N uptake rates than LN and L- plants, respectively, resulting in a greater final mineral N uptake for these treatments. However, the final partitioning of exogenous N to the regrowing shoots was the same for all treatments (67 % of total exogenous N on average). Final shoot growth, total plant N content, and N allocation to the different taproot N pools were significantly lower in plants with reduced initial leaf area and initial N reserve status. CONCLUSIONS: Although both initial residual leaf area and initial N reserves influenced alfalfa regrowth, the residual leaf area had a greater effect on final forage production and N composition in the taproot, whereas the N uptake rate and final total N content in plant were more affected by the initial N reserve status than by the residual leaf area. Moreover, N storage as proteins (especially as vegetative storage proteins, rather than nitrate or amino acids) in the taproot allowed nitrate uptake to occur at significant rates. This suggests that protein storage is not only a means of sequestering N in a tissue for further mobilization, utilization for growth or tissue maintenance, but may also indirectly influence both N acquisition and reduction capacities.     

Overproduction and one-step purification of the N 5,N 10-methenyltetrahydro-methanopterin cyclohydrolase (Mch) from the hyperthermophilic Methanopyrus kandleri

N ⁵,N ¹⁰-Methenyltetrahydromethanopterin cyclohydrolase (Mch) is an enzyme involved in methanogenesis from CO₂ and H₂ which represents the energy metabolism of Methanopyrus kandleri, a methanogenic Archaeon growing at a temperature optimum of 98°C. The gene mch from M. kandleri was cloned, sequenced, and expressed in Escherichia coli. The overproduced enzyme could be purified in yields above 90% in one step by chromatography on phenyl Sepharose in 80% ammonium sulfate. From 3.5 g cells (250 mg protein), approximately 18 mg cyclohydrolase was obtained. The purified enzyme showed essentially the same catalytic properties as the enzyme purified from M. kandleri cells. The primary structure and properties of the cyclohydrolase are compared with those of the enzyme from Methanococcus jannaschii (growth temperature optimum 85°C), from Methanobacterium thermoautotrophicum (65°C), and from Methanosarcina barkeri (37°C). Of the four enzymes, that from M. kandleri has the lowest isoelectric point (3.8) and the lowest hydrophobicity of amino acid composition. Besides, it has the highest relative content of glutamate, leucine, and valine and the lowest relative content of isoleucine, serine, and lysine. Some of these properties are unusual for enzymes from hyperthermophilic organisms. They may reflect the observation that the cyclohydrolase from M. kandleri is not only adapted to hyperthermophilic conditions but also to the high intracellular concentrations of lyotrophic salts prevailing in this organism. Received: July 14, 1997 / Accepted: August 28, 1997     

Recent Progress in First Principles O(N) Methods

Abstract

We describe recent progress in developing practical first principles methods for which the computer effort is proportional to the number of atoms: linear scaling or O(N) methods. It is shown that the locality property of the density matrix gives a general framework for constructing such methods. We then outline some of the main technical problems which must be solved in order to develop a practical O(N) method based on density functional theory and the pseudopotential method. Recent progress in solving these problems is presented, and we show that the spatial cut-off distances needed to achieve good accuracy are small enough to make the calculations feasible. Parallel implementation of the O(N) methods in the CONQUEST code is outlined, and it is shown that the code exhibits excellent linear-scaling behaviour on test systems of several thousand atoms. It is pointed out that the most important remaining problem concerns the optimal strategy for seeking the ground state. It is argued that there are three different mechanisms of ill-conditioning which cause present search methods to be inefficient, and some partial solutions are suggested.     

不同氮肥喷涂吡啶对夏玉米田氮素利用及土壤N2O排放的影响

为减少土壤N₂O排放,提高作物氮素利用,采用田间试验法研究了不同氮肥用量喷涂一定比例的吡啶(0、180、270、360 kg N·hm^-2)对夏玉米生育期内土壤N₂O排放和氮素表观损失、籽粒产量及氮素利用的影响.结果表明:不同氮肥用量下喷涂吡啶的土壤N₂O排放主要集中在播种-苗期和拔节-抽雄期,基肥和追肥后均会出现显著的土壤N₂O排放通量高峰.随氮肥用量增加,玉米产量不断增加,但270和360 kg N·hm^-2间无显著差异,2种施氮量下的玉米分别净增收5209和5426元·hm^-2.与不施氮肥比,各施氮处理下的玉米籽粒吸氮量提高幅度为109.6%～134.1%.各处理间的氮肥农学效率和氮肥利用率均以氮肥喷涂吡啶270 kg N·hm^-2较大,而土壤氮素表观损失较小.氮肥喷涂吡啶在270 kg N·hm^-2时玉米增产增收,氮肥利用效率较高,土壤N₂O排放和氮素表观损失较少,是一种较为合理的氮肥调控施用技术.     

Effects of metallic silver island films on resonance energy transfer between N,N'-(dipropyl)-tetramethyl- indocarbocyanine (Cy3)- and N,N'-(dipropyl)-tetramethyl- indodicarbocyanine (Cy5)-labeled DNA

Resonance energy transfer (RET) is typically limited to distances below 60 A, which can be too short for some biomedical assays. We examined a new method for increasing the RET distances by placing donor- and acceptor-labeled DNA oligomers between two slides coated with metallic silver particles. A N,N'-(dipropyl)-tetramethylindocarbocyanine donor and a N,N'-(dipropyl)-tetramethylindodicarbocyanine acceptor were covalently bound to opposite 5' ends of complementary 23 base pair DNA oligomers. The transfer efficiency was 25% in the absence of silver particles or if only one slide was silvered, and it increased to an average value near 64% between two silvered slides. The average value of the Forster distance increased from 58 to 77 A. The energy transfer data were analyzed with a model assuming two populations of donor-acceptor pairs: unaffected and affected by silver island films. In an affected fraction of about 28%, the apparent energy transfer efficiency is near 87% and the Forster distance increases to 119 A. These results suggest the use of metallic silver particles to increase the distances over which RET occurs in biomedical and biotechnology assays.     

A novel protocol based on HN(C)N for rapid resonance assignment in ((15)N, (13)C) labeled proteins: implications to structural genomics

A novel protocol, based on the HN(C)N experiment, has been developed for rapid assignment of backbone H(N) and (15)N resonances in ((15)N, (13)C) labeled proteins. The protocol exploits the directly observable (15)N and H(N) sequential correlations and the distinctive peak patterns in the different planes of the HN(C)N spectrum, depending upon the nature of the residues displaying the correlations. Glycines and prolines, which are responsible for the distinctive features, provide many check/start points for the sequential walks. These features enhance the speed of data analysis and render side chain assignments less crucial for the success of the assignments. The application of the protocol has been demonstrated with FK506 binding protein (FKBP, molecular mass 12 kDa).     

新的猪源性甲型H1N1流感病毒

2009年3月在美国和墨西哥流感样患者的呼吸道标本中鉴定出新的猪源性甲型H1N1流感病毒。该病毒可人一人传播,已蔓延到172个国家和地区。现就猪源性甲型H1N1流感病毒的鉴定、基因组结构特征做一综述。     

Enkephalin Metabolism by Microglia Aminopeptidase N (CD13)

Abstract: Rat microglia in culture showed a high capacity to degrade neuropeptides compared with other glial cells. Leu-enkephalin was readily hydrolyzed to free tyrosine and Gly-Gly-Phe-Leu. Inhibition experiments and immunostaining revealed that aminopeptidase N (CD13) on the surface of microglia was responsible for enkephalin cleavage. Endopeptidase-24.11 ("enkephalinase"), angiotensin-converting enzyme, or carboxypeptidases could not be detected on microglia. Aminopeptidase N activity in microglia was considerably higher than in rat peripheral monocytes and macrophages, which both also exhibited low endopeptidase 24.11 activities. Activity of aminopeptidase N was upregulated by culture of microglia on astrocytes and downregulated by exposure of microglia to lipopolysaccharide. The occurrence of aminopeptidase N on microglia is in line with the view that they originate from the monocytic lineage.     

Epidemiological update on swine influenza (H1N1) in pigs

The 2009 H1N1 pandemic has slowed down its spread after initial speed of transmission. The conventional swine influenza H1N1 virus (SIV) in pig populations worldwide needs to be differentiated from pandemic H1N1 influenza virus, however it is also essential to know about the exact role of pigs in the spread and mutations taking place in pig-to-pig transmission. The present paper reviews epidemiological features of classical SIV and its differentiation with pandemic influenza.     

棉铃虫幼虫中肠非糖基磷酯酰肌醇锚着氨肽酶N基因的克隆和测序

通过对棉铃虫Helicoverpa armigera (Hübner)幼虫中肠氨肽酶N的克隆和测序,鉴定了1个氨肽酶N基因APN1,其cDNA序列具有3 220个核苷酸,具有3 042 bp的开放阅读框,编码产生1 014个氨基酸的蛋白质。其推定的氨基酸序列具有氨肽酶N所共有的锌结合模体HEXXHX₁₈E和N末端20个氨基酸的疏水性信号序列,但C末端没有糖基磷酯酰肌醇（glycosylphosphatidylinositol,GPI）锚添加信号序列。该氨肽酶N的cDNA序列已提交GenBank,登录号为AY358034。