长江三角洲地区雨水中NH4+-N/NO3--N和δ15NH4+值的变化

2003年6月至2005年7月,利用自行设计的雨水收集器对位于长江三角洲地区的常熟、南京和杭州3个观测点进行了全年性雨水观测,分析了雨水中NH₄⁺-N/NO₃^--N和铵态氮自然丰度(δ¹⁵NH₄⁺)值的变化.结果表明：研究区3个观测点雨水中NH₄⁺-N/NO₃^--N和δ¹⁵NH₄⁺值均呈相似的季节性变化规律,两者的规律性变化在以田间农事耕作为主的常熟观测点尤其明显,而位于市区的南京观测点和位于城乡结合部的杭州观测点的规律性次之;雨水中NH₄⁺-N/NO₃^--N的峰值出现在6月下旬到8月上旬,然后逐渐下降,冬季降到最低;雨水中δ¹⁵NH₄⁺值在6月下旬到8月中旬为负值,在8月下旬到11月中下旬为正值,12月至翌年3月又变为负值,5至6月中旬又转变为正值.雨水中NH₄⁺-N/NO₃^--N和δ¹⁵NH₄⁺值的季节变化与不同作物生育期间氮肥的施用、当地气候的季节性变化以及其他NH3释放源的NH3挥发有关（人和动物排泄物、氮污染水体及有机氮源中的氨挥发）,其对大气湿沉降中NH₄⁺的来源、形态组成及陆地不同NH₃排放源的强度具有明显的指示意义.     

A versatile entry into aqueous niobium chemistry: isolation and structure of the intermediate Nb4(μ2-O)2(μ2-OC2H5)4Cl4(OC2H5)4(HOC2H5)4

The reduction of ethanolic solutions of niobium pentachloride with zinc, followed by treatment with aqueous acids serves as a versatile entry into the aqueous solution chemistry of niobium. From the zinc-reduced solution, the major intermediate, Nb₄(μ₂-O)₂(μ₂-OC₂H₅)₄Cl₄(OC₂H₅)₄(HOC₂H₅)₄, was isolated and the crystal structure determined by X-ray crystallography. The complex crystallizes in the orthorhombic space group Pccn, with Z=4, a=21.0105(9), b=11.0387(5), c=19.1389(8), V=4438.9(3) ų, M_r=1090.19,R₁=0.0327 and wR₂=0.0876. The structure revealed a centrosymmetric tetrameric Nb(IV) complex, consisting of a pair of edge-sharing bi-octahedral Nb₂(μ₂-OC₂H₅)₄Cl₂(OC₂H₅)₂(HOC₂H₅)₂ units that are joined by two axial oxo ligands. The Nb-Nb distance of 2.7458(3) Å is consistent with a single metal-metal bond.     

Oxidation of [Ir(η-C5Me5)(C8H4S8)] and crystal structures of [IrI(η-C5Me5)(C8H4S8)](I3) and [IrI(η-C5Me5)(C8H4S8)](I3)1/2(I7)1/2

[Ir(η⁵-C₅Me₅)(C₈H₄S₈)] (1) [ = 2-{(4,5-ethylenedithio)-1,3-dithiole-2-ylidene}-1,3-dithiole-4,5-dithionate(2−)] was reacted with iodine in dichloromethane to afford one-electron- and two-electron-oxidized species [IrI(η⁵-C₅Me₅)(C₈H₄S₈)] (2), [IrI(η⁵-C₅Me₅)(C₈H₄S₈)](I₃) (3) and [IrI(η⁵-C₅Me₅)(C₈H₄S₈)](I₅) (4). The oxidized species exhibit electrical conductivities of (1.1-5.0) × 10⁻⁶ S cm⁻¹ measured for compacted pellets at room temperature. The X-ray crystal structures of the two-electron-oxidized complexes 3 and 4 revealed the Ir-I bonds for both of them and the presence of for 3 and ions for 4 as the counter anions. They have many S-S and S-I non-bonding contacts to form two-dimensional molecular interaction sheets in the solid state.     

Redox reactions of the hydrogenase-cytochrome C3 system from Desulfovibrio gigas with the synthetic analogue of ferredoxin active sites [Fe4S4 (SCH2CH2OH)4]2−

The synthetic cluster [Fe₄S₄ (SCH₂CH₂OH)₄]^2? and ferredoxin I from $\text{Desulfovibrio}\text{gigas}$ have been comparatively reacted in the presence of hydrogen with two enzyme components isolated from the $\text{D.}\text{gigas}$ electron carrier system: hydrogenase and cytochrome c₃. The reactions have been followed by spectrophotometric and manometric methods. No reduction is detected unless both enzymes are simultaneously present. The easy reduction in the presence of hydrogenase-cytochrome c₃ combination takes place in two stages corresponding each to one equivalent of reduction. The first stage is reversible while the second is not and yields a super reduced species deriving from the cluster complex.     

苦瓜籽蛋白的PEG/（NH4）2SO4双水相分离及抑菌作用的研究

优化试验条件影响因素,建立PEG/(NH4)2SO4双水相系统,确定出分离苦瓜籽蛋白的最适PEG6000和(NH4)2SO4质量分数分别是22%、25%,分配系数为0.089,回收率为96%。双水相分离的苦瓜籽蛋白经SDS-PAGE凝胶电泳显示,主要蛋白质是50 KD4、3 KD和10 KD亚基结合形成的多聚体12S(327 KD)球蛋白,还原条件下出现诸多小于35 kD的蛋白组分,表明蛋白质亚基是通过二硫键结合。抑菌试验显示苦瓜籽蛋白对受试细菌菌和真菌产生明显的抑菌活性,其MIC远低于苯甲酸钠,而且在不同盐离子浓度、温度、pH及紫外线等因素处理时,均具有一定的稳定性。此外试验还表明苦瓜籽蛋白也具有较强的清除羟自由基能力和总抗氧化能力。     

C3与C4植物的环境调控

环境条件决定着不同光合类型植物的地理分布范围和区域 ,一般来说 ,C4 植物分布于高温、强光的环境而 C3植物分布于阴凉、湿润的环境 ,且 C4 比 C3植物光合速率高。但环境条件影响着不同光合类型植物的光合潜能的发挥 ,C4 植物在高温、强光、干旱条件下所表现出来的优势在其它环境条件下未必就显现出来。环境条件甚至可以引起 C3、C4 光合途径间的相互转化 ,这使得目前几种鉴别植物光合类型的方法出现不一致的结果。因此 ,在判断植物的光合类型时 ,要注意多种手段的综合利用 ,同时注意植物所处环境条件的影响。     

NH4+对L-色氨酸发酵的影响

目的:探究NH₄⁺浓度对大肠杆菌E.coli TRTH发酵生产L-色氨酸的影响。方法:通过外源添加试验,利用30 L发酵罐进行分批补料发酵试验,考察E. coli TRTH发酵生产L-色氨酸过程中生物量、L-色氨酸产量、有机酸含量、耗糖速率、发酵液中NH₄⁺浓度及质粒稳定性变化。建立了大肠杆菌合成L-色氨酸的代谢流平衡模型,应用 MATLAB 软件计算出E. coli TRTH发酵中后期代谢网络的代谢流分布。结果:发酵结果显示,利用NaOH和氨水混合补料,控制NH₄⁺浓度在120 mmol/L以下,菌体能够以较长时间和较高比生长速率保持对数生长,最终菌体生物量和L-色氨酸产量分别提高了12.16%和19.80%。随着NH₄⁺浓度的增加,发酵液中丙酮酸、乳酸及乙酸浓度均略有增加,细胞质粒稳定性下降。控制NH₄⁺浓度在120 mmol/L以下,E. coli TRTH发酵生产L-色氨酸的代谢流量分析结果表明,EMP途径的代谢流量降低7.31%,PP途径的代谢流量增加7.14%,TCA循环的代谢流量降低22.04%。结论:高浓度的NH₄⁺导致菌体生长提前结束,耗糖速率降低,产酸受阻,控制NH₄⁺浓度在120 mmol/L以下,解除了NH₄⁺对菌体生长和产物生成的抑制,使得菌体生物量和L-色氨酸产量大幅提高,实现了高密度发酵培养的目的。     

Potassium(I)thallium(I) heterometallic 3D polymeric mixed-anions compound, succinate-nitrate [K2Tl(μ-C4H4O4)(μ-NO3)]n

A three-dimensional polymeric K^ITl^I heterometallic compound [K₂Tl(μ-C₄H₄O₄)(μ-NO₃)]_n, with mixes succinate and nitrate ligands, has been synthesized and characterized. Its single-crystal X-ray structure shows two types of K⁺-ions with coordination numbers of seven and eight and one Tl⁺-ion with a coordination number of five. However, the arrangement of O-atoms for Tl^I suggests a gap or hole in the coordination geometry around this atom. This ‘hole’ is possibly occupied by a stereochemically ‘active’ electron lone pair of thallium atoms. Two hydrogen atoms of succinate situated 3.26 Å above the proposed site on the lone pair of Tl^I is oriented in such a way that it might be thought to be forming weak Tl-Lp?H-C hydrogen bond or agostic interactions, thus attaining of environment TlO₅H₂.     

Influence of CH3 group of μ-N-C-S ligand on the properties of [Fe2(C4H5N2S)2(NO)4] complex

Bi-nuclear neutral sulfur-nitrosyl iron complex [Fe₂(SR)₂(NO)₄] (I) has been obtained by replacement of thiosulfate ligands in dianion [Fe₂(S₂O₃)₂(NO)₄]²⁻ by 1-methyl-imidazole-2-yl. From X-ray analysis data, the complex has centrosymmetrical dimeric structure, with the iron atoms being linked via μ-N-C-S bridge. From Mossbauer spectroscopy, isomeric shift δ_Fe is 0.180(1) mm/s and quadrupole splitting ΔE_Q is 0.928(2) mm/s at T = 290 K. By comparative studying the mass-spectra in the gaseous phase of solid samples decomposition and kinetics of NO release in 1% aqueous solutions of dimethylsulfoxide, using of the ligand with CH₃ substituent in position 1 of imidazole-2-thiol was shown to yield a more stable donor of nitrogen monoxide than earlier obtained analog with imidazole-2-thiol, [Fe₂(C₃H₃N₂S)₂(NO)₄].     

(NH4)2SO4对瓜尔豆幼苗在不同光照下耐冷性的影响

通过温室穴盘育苗试验,研究叶面喷施(NH₄)₂SO₄对低温胁迫12 h后不同光通量密度（PFD）条件下,瓜尔豆幼苗在常温培养过程中幼苗生存及叶片SOD活性、POD活性和MDA含量的影响。结果表明：低温处理一夜后,在温室自然光照（强光）下进行常温恢复时,瓜尔豆叶片中SOD和POD活性始终显著低于对照,MDA含量显著高于对照,幼苗死亡率显著高于对照;在90 μmol·m^-2·s^-1弱光下恢复2～4 d后,叶片中保护酶活性显著高于对照,MDA含量保持较低水平,幼苗均正常生长。叶面喷施(NH₄)₂SO₄能显著提高低温处理后的植株叶片抗氧化酶类活性,减少叶片中MDA的产生,降低幼苗死亡率,0.2% (NH₄)₂SO₄处理效果最好,其次为0.4%(NH₄)₂SO₄。短期低温后,使植物处在弱光环境下能减少活性氧的发生,为植物抗氧化系统达到新的平衡提供有利条件,从而减轻甚至消除低温伤害。     

New palladacyclopentadiene complexes containing an N,P-donor setting. Crystal structure of [Pd{C4(COOMe)4}(o-Ph2PC6H4CHNPr)]

The synthesis of palladacyclopentadiene derivatives with the mixed-donor bidentate ligands o-Ph₂PC₆H₄CHNR (N^∧P) has been achieved. The new complexes of general formula [Pd{C₄(COOMe)₄}(o-Ph₂PC₆H₄CHNR)] [R=Me (1), Et (2), ⁱPr (3), ^tBu (4), NHMe (5)] have been prepared by reaction between the precursor [Pd{C₄(COOMe)₄}]_n and the corresponding iminophosphine. The polymer complex [Pd{C₄(COOMe)₄}]_n also reacts with pyridazine (C₄H₄N₂) to give the insoluble dinuclear complex [Pd{C₄(COOMe)₄}(μ-C₄H₄N₂)]₂ (6), which has been successfully employed as precursor in the synthesis of pyridazine-based palladacyclopentadiene complexes. The reaction of 6 with tertiary phosphines yielded complexes containing an N,P-donor setting of formula [Pd{C₄(COOMe)₄}(C₄H₄N₂)(L)] (L=PPh₃ (7), PPh₂Me (8), P(p-MeOC₆H₄)₃ (9), P(p-FC₆H₄)₃ (10)). The new complexes were characterized by partial elemental analyses and spectroscopic methods (IR, ¹H, ¹⁹F and ³¹P NMR). The molecular structure of complex 3 has been determined by a single-crystal diffraction study, showing that the iminophosphine acts as chelating ligand with coordination around the palladium atom slightly distorted from the square-planar geometry.     

小流域内植被类型对土壤NO3-/NH4+空间变化的影响

流域内植被类型、地形地貌特征对土壤氮循环过程有重要的作用,是影响下游水体无机氮素来源以及富营养化的关键因子。通过比较小流域内4种植被类型(落叶松人工林、油松人工林、天然阔叶次生林和农田(玉米))对土壤NO3--N和NH4+-N含量空间变化的影响,揭示流域内不同立地条件下水源涵养林与土壤无机氮变化特征之间的关系。结果表明:4种植被类型土壤NO3--N和NH4+-N含量差异显著(P<0.05);由坡上到坡下土壤NO3--N和NH4+-N含量显著降低;在土壤表层NO3--N和NH4+-N含量最高,随着土层深度增加无机氮含量减少;与水源涵养林天然植被和人工林植被相比,农田土壤NO3--N含量最高(11.86mg·kg-1),有较高的氮流失风险。     

原始森林土壤NH4+/NO3-生境特征与某些针叶树种的适应性

在陆地生态系统中,生存地段的土壤养分环境构成了植物的“营养生境”。植物在长期进化过程中往往产生对原生营养生境的生态适应,其中对NH4 和NO3-两种无机氮源的吸收、利用特性便可能是这种适应的一个重要方面。由于硝化抑制(限制)或微生物对NO3-的强烈吸收、固持作用,酸性、弱酸性的原始森林土壤中NH4 含量大都远高于NO3-,从而形成了以NH4 占绝对优势的“氮营养生境”。很多针叶树种(尤其是演替晚期阶段占优势者)对其长期所处的NH4 优势生境产生了充分适应,以致对非还原态氮(NO3-)的吸收、利用能力严重下降。这些针叶树往往表现出典型的“喜铵性”,而在NO3-优势环境中则会引起氮代谢失调和生长下降。从氮同化酶、高耐铵性、根对NH4 和NO3-的相对吸收能力及NO3-吸收的反馈控制、养分关系与养分平衡、根部碳流失、光合作用及耐荫性等多方面阐述了喜铵针叶树适应的生理生化机制。这种生态适应可能是顶极森林群落维持长期稳定的重要机制之一,而采伐干扰后NO3-明显增加的立地条件则可能会导致喜铵的“原优势针叶树种”更新困难。在温带退化森林生态系统恢复与重建过程中,顶极针叶树种对NH4 营养生境的固有适应性是必须充分考虑的问题。     

用于可视化光治疗的Mn3O4@CuS纳米粒的制备研究

摘要 目的：本研究旨在制备用于肿瘤可视化光治疗的多功能Mn₃O₄@CuS核壳型纳米粒,在磁共振成像的引导下,使用近红外光定点辐照,实现局部光热消融治疗。方法：（1）采用高温热解法制备油胺稳定的Mn₃O₄纳米粒,在其表面构建CuS壳层,并进行聚乙二醇修饰,得到分散于水相中的Mn₃O₄@CuS核壳型纳米粒。（2）通过透射电镜、紫外可见近红外吸收光谱等方法对该纳米粒进行理化性质表征,并研究其体外磁共振成像、光热升温等性能。结果：制备的水相分散的Mn₃O₄@CuS纳米粒,粒径均一且分散性较好,形态为近圆形,粒径为9.30±2.29 nm;紫外可见近红外吸收光谱图表明Mn₃O₄@CuS纳米粒在近红外区有较强吸收,最大吸收峰位于1100~1200 nm范围;磁共振成像分析结果可计算出Mn₃O₄@CuS纳米粒的纵向弛豫率r1为1.662 mM^-1s^-1,表明其具有较好的磁共振增强造影效果;光热升温曲线显示Mn₃O₄@CuS纳米粒可在785 nm近红外激光下升温至73.5 ℃,具备较好的光热治疗潜力。结论：本文成功制备出水相分散的Mn₃O₄@CuS核壳型纳米粒,具有良好的磁共振造影成像性能和光热升温效应,有望应用于磁共振成像引导下的肿瘤可视化光治疗。     

Na2SO4和Na2CO3胁迫下苦楝幼苗的形态及光合生理特性

为探索苦楝应对盐胁迫的响应机制,该文以1年生苦楝(Melia azedarach)实生苗为材料,在盆栽条件下设置中性盐Na_2SO_4和碱性盐Na_2CO_33个盐浓度(200、400、600 mmol·L~(-1))处理40 d,研究苦楝的抗盐碱水平及在不同程度盐碱胁迫条件下的生长及光合生理变化。结果表明:随着盐浓度的提高,苦楝的苗高、地径和生物量的增长量均呈现下降趋势,且碱性盐胁迫条件下降程度更大,盐胁迫提高苦楝的根冠比。处理10 d时,苦楝幼苗的所有光合指标随中性盐和碱性盐浓度的提高呈相似的下降特征,碱性盐胁迫条件下的降低幅度显著大于中性盐胁迫,且随处理时间的增加,中性盐和碱性盐处理下苦楝幼苗的净光合速率和蒸腾速率显著降低。随着盐浓度的提高,苦楝的叶绿素含量呈现下降趋势,200 mmol·L~(-1)盐胁迫对叶绿素含量影响较小,400、600 mmol·L~(-1)盐胁迫均对叶绿素含量有显著影响。600 mmol·L~(-1)碱性盐胁迫条件下,苦楝叶片相对电导率和饱和水分亏缺最高,显著高于其余处理。同等浓度下,碱性盐胁迫的苦楝叶片相对电导率和饱和水分亏缺显著高于中性盐胁迫处理。综上结果认为,苦楝具有一定的耐盐碱能力,碱性盐比中性盐对苦楝幼苗的影响更大。     

Preparation of cobalt sandwich diphosphine ligand [(η-C5H4Pr)Co(η-C4(PPh2)2Ph2)] and its chelated palladium complex: Application of diphosphine ligand in the preparation of mono-substituted ferrocenylarenes

The reaction of (η⁵-C₅H₄ⁱPr)Co(PPh₃)₂ with PhCCPPh₂ furnished two isomeric cyclobutadiene-substituted Cp′CoCb diphosphines, [(η⁵-C₅H₄ⁱPr)Co(η⁴-1,2-(PPh₂)₂C₄Ph₂)] (5-cis) and [(η⁵-C₅H₄ⁱPr)Co(η⁴-1,3-(PPh₂)₂C₄Ph₂)] (5-trans). Further reaction of 5-cis with one molar equivalent of Pd(COD)Cl₂ gave palladium complex [(η⁵-C₅H₄ⁱPr)Co(η⁴-1,2-(PPh₂)₂C₄Ph₂)-PdCl₂] (6) in good yield. Both of the molecular structures of 5-cis and 6 were determined by single-crystal X-ray diffraction methods. Unexpectedly, the palladium complex 6 was found to be more efficient than the combination of the commonly used Buchwald’s ligand, biphenyl-2-yl-di-tert-butyl-phosphane, with Pd(OAc)₂ as the catalytic precursor in the Suzuki-Miyaura reaction between ferroceneboronic acid and 4-bromoaldehyde. The X-ray structural analysis and DFT study of several palladium complexes containing sandwich-type diphosphine chelating ligands revealed that the variations in bite angles are much larger than those in bite distances. The more energetically favorable conformation in the Pd(II) complexes is the one with bite angle close to 90°.     

Binding of HIV-1 virions to α4β7 expressing cells and impact of antagonizing α4β7 on HIV-1 infection of primary CD4+ T cells

HIV-1 envelope glycoprotein is reported to interact with α4β7, an integrin mediating the homing of lymphocytes to gut-associated lymphoid tissue, but the significance of α4β7 in HIV-1 infection remains controversial. Here, using HIV-1 strain Ba L, the gp120 of which was previously shown to be capable of interacting with α4β7, we demonstrated that α4β7 can mediate the binding of whole HIV-1 virions to α4β7-expressing transfectants. We further constructed a cell line stably expressing α4β7 and confirmed the α4β7-mediated HIV-1 binding. In primary lymphocytes with activated α4β7 expression, we also observed significant virus binding which can be inhibited by an anti-α4β7 antibody. Moreover, we investigated the impact of antagonizing α4β7 on HIV-1 infection of primary CD4+ T cells. In α4β7-activated CD4+ T cells, both anti-α4β7 antibodies and introduction of shorthairpin RNAs specifically targeting α4β7 resulted in a decreased HIV-1 infection. Our findings indicate that α4β7 may serve as an attachment factor at least for some HIV-1 strains. The established approach provides a promising means for the investigation of other viral strains to understand the potential roles of α4β7 in HIV-1 infection.     

C3、C4和CAM途径的生态学意义

本文通过C_3,C_4和CAM植物在不同环境中的分布,从3个方面阐述了这3种碳同化途径在利用环境资源时的生态学意义——资源分隔: 1.光合途径的空间分异:(1)不同光合类型植物的气候带(水平和垂直带)和地理区域分布;(2)不同光合类型植物在微环境中的分布。 2.光合途径的时间分异。 3.光合途径在资源分隔中的重叠。