Manganese(III) complexes of N2O2 donor 5-bromosalicylideneimine ligands: Combined effects of electron withdrawing substituents and chelate ring size variations on electrochemical properties

A series of mononuclear manganese(III) complexes of formulae [Mn(L)(X)(H₂O)] (1-13) and [Mn(L)(X)] (14-17) (X = ClO₄, F, Cl, Br, I, NCS, N₃), derived from the Schiff bases of 5-bromosalicylaldehyde and different types of diamine (1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane and 1,4-diaminobutane), have been synthesized and characterized by the combination of IR, UV-Vis spectroscopies, cyclic voltammetry and by X-ray crystallography. The redox properties of all the manganese(III) complexes show grossly identical features consisting of a reversible or quasireversible Mn^III/Mn^II reduction. Besides Mn^III/Mn^II reduction, the complexes 4, 5, 10, 13 and 16 also show reversible or quasireversible Mn^III/Mn^IV oxidation. A linear correlation has been found for the complexes 5, 7, 11 and 13 [Mn(L²)(X)(H₂O)] (X = F, Cl, Br, I) when E_1/2 [Mn^III/Mn^II] is plotted against Mulliken electronegativities (χ_M). The effect of the flexibility of the ligand on redox potential has been studied. It has been observed that the manganese(II) state is stabilized with increasing flexibility of the ligand environment. The crystal structure of 6 shows an octahedral geometry.     

Stabilization of Mn(II) and Mn(III) in mononuclear complexes derived from tridentate ligands with N2O donors: Synthesis, crystal structure, superoxide dismutase activity and DNA interaction studies

A new family of tridentate ligands PhimpH (2-((2-phenyl-2-(pyridin-2-yl)hydazono)methyl)phenol), N-PhimpH (2-((2-phenyl-2-(pyridin-2-yl)hydrazono)methyl)napthalen-1-ol), Me-PhimpH (2-(1-(2-phenyl-2-(pyridine-2-yl)hydrazono)ethyl)phenol) have been synthesized and characterized. The ligands PhimpH and N-PhimpH after deprotonation react with manganese(II) and manganese(III) starting materials affording [Mn(Phimp)₂] (1), [Mn(Phimp)₂](ClO₄) (2), [Mn(N-Phimp)₂] (3), [Mn(N-Phimp)₂](ClO₄) (4). Complexes [Mn(Phimp)₂] (1) and [Mn(N-Phimp)₂] (3) convert to [Mn(Phimp)₂]⁺ (cation of 2) and [Mn(N-Phimp)₂]⁺ (cation of 4) respectively upon oxidation. Ligand Me-PhimpH stabilized only manganese(III) centre resulting [Mn(Me-Phimp)₂](ClO₄) (5). The molecular structures of [Mn(Phimp)₂], 1 and [Mn(Phimp)₂](ClO₄), 2 were determined by single crystal X-ray diffraction. X-ray crystal structures of 1 and 2 have revealed the presence of distorted octahedral MnN₄O₂ coordination sphere having meridionally spanning ligands. Electrochemical studies for the complexes showed Mn(II)/Mn(III), (E_1/2 = 0.14-0.40 V) and Mn(III)/Mn(IV), (E_1/2 = 0.80-1.06 V) couples vs. Ag/AgCl. The redox properties were exploited to examine superoxide dismutase (SOD) activity using Mn(II)/Mn(III) couple. The complexes 1, 2, 4 and 5 have been revealed to catalyze effectively the dismutation of superoxide () in xanthine-xanthine oxidase-nitro blue tetrazolium assay and IC₅₀ values were found to be 0.29, 0.39, 1.12 and 0.76 μM respectively. DNA interaction studies with complex 2 showed binding of DNA in a non-intercalative pathway. Complexes 1, 2 and 4 exhibited nuclease activity in presence of H₂O₂ and inhibition of activity was noted in presence of KI.     

Mononuclear iron(III) complexes supported by tripodal N3O ligands: Synthesis, structure and reactivity towards DNA cleavage

A new synthetic route to the known tripodal tetradentate N₃O ligand L¹ (HL¹ = [N-(3,5-di-tert-butyl-2-hydroxybenzyl)-N,N-di-(2-pyridylmethyl)]amine) is reported. The related compounds HLⁿ (n = 2, 3) were prepared by a similar procedure. Treatment of HLⁿ (n = 1-3) with FeCl₃·6H₂O in hot methanol led to the mononuclear iron(III) complexes [Fe(Lⁿ)Cl₂] (1: n = 1, 2: n = 2, 3: n = 3). The solid-state structures of complexes 1 and 2 were determined by X-ray crystallography. [Fe(L¹)Cl₂] (1) showed effective nuclease activity in the presence of hydrogen peroxide, converting supercoiled plasmid DNA to its linear form.     

Iron(III) complexes of tridentate N3 ligands as models for catechol dioxygenases: Stereoelectronic effects of pyrazole coordination

The iron(III) complexes of the tridentate N₃ ligands pyrazol-1-ylmethyl(pyrid-2-ylmethyl)amine (L1), 3,5-dimethylpyrazol-1-ylmethyl(pyrid-2-ylmethyl)amine (L2), 3-iso-propylpyrazol-1-ylmethyl(pyrid-2-ylmethyl)amine (L3) and (1-methyl-1H-imidazol-2-ylmethyl)pyrid-2-ylmethylamine (L4) have been isolated and studied as functional models for catechol dioxygenases. They have been characterized by elemental analysis and spectral and electrochemical methods. The X-ray crystal structure of the complex [Fe(L1)Cl₃] 1 has been successfully determined. The complex possesses a distorted octahedral coordination geometry in which the tridentate ligand facially engages iron(III) and the Cl⁻ ions occupy the remaining coordination sites. The Fe-N_pz bond distance (2.126(5) Å) is shorter than the Fe-N_py bond (2.199(5) Å). The systematic variation in the ligand donor substituent significantly influences the Lewis acidity of the iron(III) center and hence the interaction of the present complexes with a series of catechols. The catecholate adducts [Fe(L)(DBC)Cl], where H₂DBC = 3,5-di-tert-butylcatechol, have been generated in situ and their spectral and redox properties and dioxygenase activities have been studied in N,N-dimethylformamide solution. The adducts [Fe(L)(DBC)Cl] undergo cleavage of DBC²⁻ in the presence of dioxygen to afford major amounts of intradiol and smaller amounts extradiol cleavage products. In dichloromethane solution the [Fe(L)(DBC)Cl] adducts afford higher amounts of extradiol products (64.1-22.2%; extradiol-to-intradiol product selectivity E/I, 2.6:1-4.5:1) than in DMF (2.5-6.6%; E/I, 0.1:1-0.4:1). The results are in line with the recent understanding of the function of intra- and extradiol-cleaving catechol dioxygenases.     

Mono- and dinuclear Fe(III) complexes with the N2O2 donor 5-chlorosalicylideneimine ligands; synthesis, X-ray structural characterization and magnetic properties

Two novel monomeric [C₁₈H₁₇Cl₃N₂O₂Fe] (1) and dimeric [C₃₈H₃₆N₄O₄Cl₆Fe₂] (2) Fe(III) tetradentate Schiff base complexes have been synthesized and their crystal structures have been determined by single crystal X-ray diffraction analysis. In complex (1) the Schiff base ligand coordinates toward one iron atom in a tetradentate mode and each iron atom is five coordinated with the coordination geometry around iron atom which can be described as a distorted square pyramid. The presence of a short (2.89 Å) non-bonding interatomic Fe···O distances between adjacent monomeric Fe(III) complexes results in the formation of a dimer. Structural analysis of compound (2) shows that the structure is a centrosymmetric dimer in which the six coordinated Fe(III) atoms are linked by μ-phenoxo bridges from one of the phenolic oxygen atoms of each Schiff base ligand to the opposite metal center. The variable-temperature (2-300 K) magnetic susceptibility (χ) data of these two compounds have been investigated. The results show that for both complexes Fe(III) centers are in the high spin configuration (S = 5/2) and indicate antiferromagnetic spin-exchange interaction between Fe(III) ions. The obtained results are briefly discussed using magnetostructural correlations developed for other class of iron(III) complexes.     

CO2浓度升高与硝化抑制剂对冬小麦田间N2O排放量的影响

以冬小麦中麦175为供试品种,利用农田开放式CO_2浓度增高(FACE)系统,研究未来大气高CO_2浓度对冬小麦田间N_2O排放的影响,以及施用硝化抑制剂(2-氯-6-三氯甲基吡啶)是否可以起到抑制冬小麦田间N_2O的排放量升高的潜能。试验结果表明:CO_2浓度升高显著提高冬小麦田间N2O的排放增幅达到67.6%,追肥灌溉后小麦田N_2O排放量较大,随着冬小麦生育进程的推进N_2O的排放量逐渐减少,硝化抑制剂对中麦175田间N_2O排放量的影响并不明显。因此,在未来高CO_2浓度环境条件下,可以通过采取相应的耕作制度和栽培技术措施等来降低冬小麦田N_2O的排放量。试验结果对冬小麦田间是否选择施用2-氯-6-三氯甲基吡啶来控制N_2O的排放起到一定的参考作用。     

施用生物炭和秸秆还田对华北农田CO2、N2O排放的影响

以华北农田冬小麦-夏玉米轮作体系连续6a施用生物炭和秸秆还田的土壤为研究对象,于2013年10月—2014年9月,采用静态暗箱-气相色谱法,对CO_2、N_2O通量进行了整个轮作周期的连续观测,探究施用生物炭与秸秆还田对其排放通量的影响。试验共设4个处理:CK(对照)、C1(低量生物炭4.5 t hm~(-2)a~(-1))、C2(高量生物炭9.0 t hm~(-2)a~(-1))和SR(秸秆还田straw return)。结果表明:在整个轮作周期内,各处理CO_2、N_2O通量随时间的变化趋势基本一致。随着生物炭施用量的增加,CO_2排放通量分别增加了0.3%—90.3%(C1)、1.0%—334.2%(C2)和0.4%—156.3%(SR)。其中,C2处理对CO_2累积排放量影响最大,增幅为42.9%。对N_2O而言,C2处理显著降低了N_2O累积排放量,但增加了CO_2和N_2O排放的综合增温潜势,C1和SR处理对N_2O累积排放量及综合增温潜势均没有显著影响。相关分析表明,土壤温度和土壤含水量是影响CO_2通量最主要的因素,两者之间呈极显著的正相关关系;N_2O通量与土壤温度、土壤含水量、NO_3~--N和NH_4~+-N均表现出极显著的正相关关系,而与土壤p H值表现出极显著的负相关关系。由此可见,添加生物炭对于减少氮素的气体损失具有较大的潜力。     

Cobalt(III) complexes with linear hexadentate N6 or N4S2 donor set atoms providing pyridyl-amide-amine/thioether coordination

Two new cobalt(III) complexes of symmetric hexadentate ligand with N₆ [1,10-bis(2-picolinamide)-4,7-diazadecane (pycdpnen)] and N₄S₂ [1,8-bis(2-picolinamide)-3,6-dithiaoctane (pycdadt)] donor set atoms have been synthesized as perchlorate salts and characterized by spectroscopic methods. All two ligands with strong-field pyridylcarboxamido N donor stabilize Co(III) as demonstrated by the facile oxidation of the cobalt center. The structures of [Co(pycdpnenH₋₂)](ClO₄) (1) and [Co(pycdadtH₋₂)](ClO₄) · H₂O (2) investigated by COSY, HMBC, HMQC and NOESY NMR studies show that compounds 1 and 2 have the same geometrical configuration. The X-ray analysis reveals that complex 2 crystallizes in a orthorhombic space group Pccn. The cation [Co(pycdadtH₋₂)]⁺ is distorted octahedral with the two pyridyl groups in cis position.     

干湿交替频率对不同土壤CO2和N2O释放的影响

干旱、半干旱和地中海气候区,乃至一些湿润地区,由干湿交替引起的土壤碳、氮的短暂脉冲式释放很大程度上决定着长时间尺度温室气体释放的总量,是土壤碳、氮温室气体释放的关键过程.选择我国降雨梯度下的森林、农田、草地和荒漠生态系统,采集土样进行实验室统一控制条件下的多重干湿交替循环,对比探讨不同生态系统土壤干湿交替频率对CO2和N2O释放的影响模式.结果表明:(1)干湿交替能够显著的激发土壤中CO2和N2O的释放,森林、农田、草地和荒漠土壤CO2和N2O释放速率对干湿交替的响应模式基本一致,其响应强度与土壤本底中碳和氮的含量有关;(2)在一定培养时间内,随着干湿交替频率的增加,土壤再湿润阶段CO2释放速率降低,但是,气体释放的总量较之于恒湿对照组有所增加.(3)不同土壤N2O的释放总量对于湿交替频率的响应模式表现出很大的差异,其中农田和荒漠土壤响应模式类似.     

一株兼性氧化亚氮还原菌的还原N2O能力

【目的】从水稻土中分离筛选出一株兼性氧化亚氮还原菌,并探索其在不同条件下还原N_2O的能力,为减少温室气体N_2O的排放提供重要依据。【方法】通过微生物富集培养分离技术从水稻土中分离得到纯菌;利用nosZ基因和16S rRNA的测序分析鉴定菌株;通过测定菌株在不同条件下N_2O的还原量,分析该菌株还原N_2O的能力及调控因子。【结果】经鉴定,该菌株含有nos Z基因,属于假单胞菌属,在温度30°C、厌氧条件下还原N_2O速率高达0.0219μmol/min以上,改变不同温度和氧气浓度后其能力相对减弱,但仍具备较强的还原N_2O作用。【结论】从水稻土中分离筛选得到的兼性氧化亚氮还原菌为假单胞菌,它在不同环境条件下都具备较强的还原N_2O能力,该菌株可能为减少土壤N_2O排放提供新途径,对保障生态环境安全具有重要的应用价值。     

水肥一体化条件下设施菜地的N2O排放

在保证作物产量的前提下,研究减少农田土壤N_2O排放的水肥统筹管理措施对全球温室气体减排具有重要意义。以京郊典型设施菜地为例,设置了农民习惯(FP)、水肥一体化(FPD)、优化水肥一体化(OPTD)和对照(CK)4个处理,采用静态箱-气相色谱法,对果菜-叶菜(黄瓜-芹菜)轮作周期内土壤N_2O排放进行了观测,并分析了氮肥施用量、灌溉方式、土壤温度和湿度等因素对土壤N_2O排放的影响。结果表明:在黄瓜-芹菜种植模式中,各施氮处理除基肥施用后N_2O排放峰持续10—15d外,一般施肥、施肥+灌溉事件后土壤N_2O排放峰均呈现3—5d短而急促的情形。黄瓜生长季N_2O排放通量与土壤湿度(WFPS)之间呈现显著相关的关系;芹菜生长季N_2O排放通量与土壤温度之间呈现显著相关的关系。观测期内FP处理N_2O排放量为(31.00±2.15)kg N/hm~2,FPD处理与之相比N_2O排放量减少了4.2%,而OPTD处理在减少40%化肥氮量的情况下,N_2O累积排放量比FP处理减少了42.7%,且达到显著水平。说明在水肥一体化条件下,合理改变施肥体系是减少N_2O排放的前提,在此基础上进行水肥优化是设施菜地保持产量、减少N_2O排放的重要技术措施。     

Synthesis and characterization of tetraphenylporphyrin manganese(III) complexes of phenylcyanamide ligands

Several complexes of TPPMn-L, where TPP is the dianion of tetraphenylporphyrin and L is monoanion of 4-methylphenylcyanamide (4-Mepcyd) (1), 2,4-dimethylphenylcyanamide (2,4-Me₂pcyd) (2), 3,5-dimethylphenylcyanamide (3,5-Me₂pcyd) (3), 4-methoxyphenylcyanamide (4-MeOpcyd) (4), phenylcyanamide (pcyd) (5), 2-chlorophenylcyanamide (2-Clpcyd) (6), 2,5-dichlorophenylcyanamide (2,5-Cl₂pcyd) (7), 2,6-dichlorophenylcyanamide (2,6-Cl₂pcyd) (8), 4-bromophenylcyanamide (4-Brpcyd) (9), and 2,3,4,5-tetrachlorophenylcyanamide (2,3,4,5-Cl₄pcyd) (10), have been prepared from the reaction of TPPMnCl and thallium salt of related phenylcyanamide. Each of the complexes has been characterized by IR, UV-Vis and ¹H NMR spectroscopies.4-Methylphenylcyanamidotetraphenylporphyrin manganese(III) crystallized with one molecule of solvent CHCl₃ in the triclinic crystal system and space group with the following unit cell parameters of: a = 11.596(6) Å; b = 11.768(9) Å; c = 17.81(2) Å; and α, β, γ are 88.91(9)°, 88.16(7)°, 67.90(5)°, respectively; V = 2251(3) Å³; Z = 2. A total of 4234 reflections with I > 2σ(I) were used to refine the structure to R = 0.0680 and R_w = 0.2297. The Mn(III) shows slightly distorted square pyramidal coordination with the 4-methylphenylcyanamide in the axial position, coordinated from nitrile nitrogen. The reduction of each of the TPPMn-L complexes was also examined in dichloromethane and spectroelectrochemical behavior of (1) was investigated and compared to TPPMnCl.     

城市化地区典型水体的N2O排放通量特征——以南京市为例

内陆淡水水体是大气中N₂O的重要排放源,然而目前对于内陆典型城市水体N₂O排放通量的监测数据依然匮乏,典型城市水体的N₂O排放特征及驱动因素尚不清楚。本研究选取了南京市江北新区的典型水体,包括湖库、河流、养殖池塘和景观池塘,在2020年5月-2021年4月利用漂浮箱法连续监测了不同水体类型的水-气界面N₂O排放特征,并通过测定水环境特征,探究驱动水体N₂O排放通量的关键因素。研究结果表明,典型城市水体整体均表现为N₂O排放源,河流和养殖池塘的日平均排放通量最大,分别为（503±1236）μg m^-2 d^-1和（508±797）μg m^-2 d^-1,其次为景观池塘（（179±989）μg m^-2 d^-1）,而湖库的N₂O排放通量最小,仅表现为微弱的N₂O排放源（（54±212）μg m^-2 d^-1）。水体的N₂O排放呈现季节性差异,河流和养殖池塘夏季的N₂O排放通量显著高于其他季节（P<0.01）。水体全年N₂O排放数据与水体温度和溶解氧含量（DO）呈显著相关。而在温度较高的5月份-9月份（>20℃）,氮输入成为影响N₂O排放通量的关键因素（P<0.01）,因此控制城市水体的氮输入尤其是在水温较高的夏季是减少N₂O排放的有利措施。此外,由于水文化学条件差异等因素,小型封闭水体包括养殖池塘和景观池塘的N₂O排放通量差异较大,未来应加强监测不同水体的水文化学特征和N₂O的时空排放特征,探讨影响小型封闭水体水-气界面N₂O排放通量的具体驱动因素。此研究为城市区域N₂O排放的精准核算提供了数据支撑,为N₂O排放模型的修正提供了科学依据。     

Kinetic studies of the reduction of hexaaquacobalt(III) perchlorate by a cobaloxime, [Co(dmgBF2)2(H2O)2]

The reaction of with Co(dmgBF₂)₂(H₂O)₂ in 1.0 M HClO₄/LiClO₄ was found to be first-order in both reactants and the [H⁺] dependence of the second-order rate constant is given by k_2obs = b/[H⁺], b at 25 °C is 9.23 ± 0.14 × 10² s⁻¹. The [H⁺] dependence at lower temperatures shows some saturation effect that allowed an estimate of the hydrolysis constant for as K_a = 9.5 × 10⁻³ M at 10 and 15 °C. Marcus theory and the known self-exchange rate constant for Co(OH₂)₅OH^2+/+ were used to estimate an electron self-exchange rate constant of k₂₂ = 1.7 × 10⁻⁴ M⁻¹ s⁻¹ for .     

施肥对板栗林地土壤N2O通量动态变化的影响

2011年6月—2012年6月期间,在浙江省临安市典型板栗林地进行施肥对土壤N2O通量变化影响的试验研究。目的在于探明不同施肥处理下板栗林地土壤N2O通量的动态变化规律,并探讨土壤N2O通量和土壤环境因子之间的关系。试验设置4个处理:对照(不施肥)、无机肥、有机肥、有机无机混合肥。采用静态箱-气相色谱法测定了板栗林地土壤N2O通量,并测定了土壤温度、水分、水溶性有机碳(WSOC)和微生物量碳(MBC)含量。结果表明:板栗林土壤N2O通量呈显著季节性变化,最大值出现在夏季,最小值出现在冬季;而且,施肥处理显著提高土壤N2O年均通量和年累积量;在整个试验期间,无机肥、有机肥和有机无机混合肥处理下土壤N2O的排放系数分别达到0.96%、1.45%和1.29%。此外,施肥也显著增加了土壤WSOC和MBC的含量(P<0.05)。不同施肥处理条件下,土壤N2O通量与土壤5 cm处温度、WSOC含量间均呈极显著正相关(P<0.01),但与MBC含量之间的相关性不显著。土壤N2O排放与土壤含水量间除对照处理外均没有显著相关性。综上所述,施肥引起土壤WSOC含量的增加可能是施肥增加板栗林地土壤N2O排放速率的主要原因之一。     

浅表层水稻土N2O消耗能力及其与N2O还原微生物的耦合关系

土壤不仅能够产生、排放温室气体N_2O,还具有截留、吸收、转化N_2O的能力。土壤消耗N_2O已经成为很重要的一种降低大气N_2O浓度的途径,但目前关于土壤N_2O消耗过程及其微生物调控机制的系统研究较为缺乏。试验以浅表层水稻土柱(0—5 cm)为研究对象,通过外源添加N_2O气体研究N_2O迁移通过淹水土柱的动态过程,以及N_2O消耗能力与氧化亚氮还原酶基因丰度变化和其他土壤养分含量变化的联系,揭示浅表层水稻土N_2O消纳量与N_2O还原微生物之间的耦合关系。结果显示,淹水厌氧条件下5 cm土壤深度外源添加的N_2O迁移通过浅表层土柱后,仅有7.17—9.80%部分逸散出土表,表明0—5 cm淹水水稻土层具有极强的N_2O截留能力(90%以上)而减少N_2O净排放量。排放出土表的N_2O也可被淹水土柱继续吸收消耗,且吸收转化速率随N_2O浓度增加而大幅提高,最高可达到3896.75μg N m~(-2) h~(-1)。与此同时,土壤DOC含量大量消耗,含nosZⅠ基因的反硝化微生物数量显著增长(P0.01),而nosZⅡ基因丰度的无显著变化。说明高浓度N_2O添加能够促进淹水土壤N_2O吸收消耗能力,此刺激作用可能主要由含nosZⅠ基因的N_2O还原微生物进行调控。浅表层土壤强大的N_2O吸收消耗功能可进一步深入系统研究,为实践温室气体减排提供理论基础。     

二氧化钛纳米颗粒对沼泽土壤反硝化和N2O排放的影响

近年来,二氧化钛纳米颗粒（TiO₂NPs）环境释放量不断增加,并通过多种途径进入湿地生态系统,不可避免地影响到湿地生态系统环境和功能。然而,关于TiO₂NPs对沼泽土壤反硝化作用和氧化亚氮（N₂O）排放的影响机及制尚不明确。选择典型沼泽土壤,通过室内培养实验研究土壤理化性质、反硝化酶活性、反硝化速率（DNR）和N₂O排放对不同剂量TiO₂NPs 0 mg/kg （CK）、10 mg/kg （A10）、100 mg/kg （A100）、1000 mg/kg （A1000）输入的响应,探讨TiO₂NPs输入对沼泽土壤反硝化作用和N₂O排放影响的内在机制。结果表明：不同剂量TiO₂NPs处理显著降低了土壤pH （P<0.05）,A10处理显著降低土壤总有机碳（TOC）含量（P<0.01）,A1000处理显著降低硝态氮（NO₃^--N）和亚硝态氮（NO₂^--N）含量（P<0.05）。TiO₂NPs处理抑制硝酸盐还原酶（NAR）活性,促进一氧化氮还原酶（NOR）和氧化亚氮还原酶（NOS）活性（P<0.01）,A1000处理先促进后抑制了亚硝酸盐还原酶（NIR）活性（P<0.05）。不同剂量TiO₂NPs处理抑制了土壤DNR,促进了N₂O排放,TiO₂NPs处理通过抑制NIR活性,降低土壤DNR,同时通过促进NOR活性,提高N₂O排放。综上,TiO₂NPs输入通过影响反硝化还原酶活性改变沼泽土壤反硝化过程,导致沼泽土壤N₂O排放增加,改变湿地氮的源、汇功能,影响全球气候变化。为TiO₂NPs输入的湿地环境风险评估研究提供理论基础。     

Synthesis, molecular structure, and properties of six-coordinate iron(III) porphyrin, [OEPFe(Pz)2]ClO4

The effect of pyrazine as axial ligand on the formation and coordination of heme analogue has been studied. A new six coordinate and stable iron(III) heme analogue, [OEPFe^III(Pz)₂]ClO₄, where OEP is octaethylporphyrin and Pz is pyrazine, has been isolated. The compound has been characterized by different spectroscopic methods ¹H NMR, UV-Vis, IR as well as elemental analysis. ¹H NMR spectroscopy and magnetic moment measurements show that [OEPFe^III(Pz)₂]ClO₄ is paramagnetic and iron is six coordinate. The structure of [OEPFe^III(Pz)₂]ClO₄ has been determined by X-ray diffraction analysis. The four Fe-N_p, bond distances have average values of 1.985 Å.     

双季稻田种植不同冬季作物对甲烷和氧化亚氮排放的影响

研究双季稻收获后填闲种植不同冬季作物在其生长季节内CH₄和N₂O的排放特征,对合理利用冬闲稻田,发展冬季作物生产及合理评价不同种植模式具有重要意义。采用静态箱-气相色谱法对冬季免耕直播黑麦草、紫云英、油菜以及翻耕移栽油菜和冬闲的双季稻田中甲烷(CH₄)和氧化亚氮(N₂O)排放进行了分析。结果表明:在冬季作物生长期,CH₄、N₂O平均排放通量和总排放量均表现为翻耕移栽油菜＞免耕直播黑麦草＞免耕直播油菜＞免耕直播紫云英＞冬闲。不同冬季作物稻田CH₄和N₂O总排放量与对照(冬闲)的差异均达到极显著水平(P<0.01);翻耕移栽油菜的双季稻田中CH₄和N₂O排放量最高,分别达2.989 g/m²和0.719 g/m²。翻耕移栽油菜稻田的CH₄和N₂O温室效应总和也最大,为2893.92 kg CO₂/hm²;免耕直播黑麦草和免耕直播油菜处理次之,而免耕直播紫云英处理最低。种植不同冬季作物促进了稻田生态系统CH₄和N₂O的排放。     

New metal complexes of N2S2 tetradentate ligands: Synthesis and spectral studies

New tetradentate ligands 2-(2-mercaptoethylthio)-N-(pyridin-2-ylmethyl)acetamide H₂L¹ and 2-chloro-2-(2-mercaptoethylthio)-N-(pyridin-2-ylmethyl)acetamide H₂L² were synthesised from the reaction of 2-aminomethanepyridine with 1,4-dithian-2-one and 3-chloro-1,4-dithian-2-one, respectively. Monomeric complexes of these ligands, of general formulae K[Cr^III(Lⁿ)Cl₂], K₂[Mn^II(Lⁿ)Cl₂] and [M(Lⁿ)] (M = Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) or Hg(II); n = 1, 2) are reported. The mode of bonding and overall geometry of the complexes were determined through IR, UV-Vis, NMR and mass spectral studies, magnetic moment measurements, elemental analysis, metal content and conductance. These studies revealed octahedral geometries for the Cr(III), Mn(II) complexes, square planar for Ni(II) and Cu(II) complexes and tetrahedral for the Fe(II), Co(II), Zn(II), Cd(II) and Hg(II) complexes. The study of complex formation via molar ratio in DMF solution has been investigated and results were consistent to those found in the solid complexes with a ratio of (M:L) as (1:1).