Studies on phenolase enzyme in prawns. II. The inhibitory action on the enzyme by certain chemical agents

The effect of certain chemical agents on dopa oxidation by phenolases has been examined. Sulphur containing amino carboxylic acids are inhibitory agents for dopa oxidation. Tyrosine, a substrate for the enzyme also acts as an inhibitor for dopa oxidation by the enzyme. The possible mode of action has been discussed. The function of diethyl dithiocarbamate in suppressing the display of enzyme activity has been detailed and its behaviour has been compared to the other chemical agents studied.

杯芳烃羧酸萃取稀土、钍与含杯配合物结构研究

本文以大环化合物杯芳烃羧酸为萃取体系，系统考察稀土元素在该体系中的萃取分离性能，比较了钍与稀土元素的萃取性质差异，从而为杯芳烃羧酸在该分离领域中的应用提供一定的实验数据，此外，采用无机水热合成制备了含杯[8]芳烃的三元超分子配位聚合物并表征其结构，具体研究内容如下： 1、 合成杯芳烃并进行化学修饰得萃取剂杯芳烃羧酸，采用熔点测定、元素分析、TG-DTA、FT-IR和1H-NMR等分析方法表征，并利用两相滴定法测定了杯芳烃羧酸的基本常数。 2、 研究杯芳烃羧酸-CHCl3/RE-HCl萃取体系碱金属离子、离子强度、酸度、温度和萃取剂浓度对Eu(III)的萃取分配比影响，并分析其萃取机理。在此基础上，探索杯芳烃羧酸的协同萃取性能，发现杯[4]芳烃羧酸与伯胺N1923的ABC酸碱耦合协萃体系对轻、中、重稀土有不同的协萃能力，协萃系数与原子序数呈“双峰效应”。 3、 在萃取热力学基础上，利用层流恒界面池研究杯[4]芳烃羧酸萃取Nd(III)的动力学性质，确定了萃取反应控制模式随条件不同有所变化，化学反应在相界面上进行，并获得了萃取反应速率方程。 4、 以杯芳烃羧酸-CHCl3/Th-HCl体系研究钍的萃取性能，考察了碱金属离子、离子强度、酸度、温度和萃取剂浓度对Th(IV)的萃取影响，比较其与稀土萃取性能的差异，并在此基础上进一步研究与伯胺N1923协同萃取钍的性能，分析了协同萃取反应机制。 5、 水热合成并表征了含磺化杯[8]芳烃，2，2’-联吡啶与镍的三元超分子配合物。磺化杯[8]在该配合物中呈“双-反向锥式”构型，分子间由氢键和C-H…π相互作用将四核Ni簇连接成三维超分子结构。

Degradation products formed during UV-irradiation of humic waters

Natural humic lake water and aqueous solutions of humic substances were treated with ultraviolet (UV) radiation (λ = 254 nm). The effects on the dissolved organic carbon content (DOC) and the absorbance at 254 nm (Abs254) and 460 nm (Abs460) were monitored and the identity and concentrations of gas chromatographable organic degradation products were determined. The DOC content and the (Abs254) of the humic solutions decreased continuously with increasing UV-dose. Several aromatic and aliphatic degradation products were identified and roughly quantified The concentrations of aromatic hydroxy carboxylic acids and hydroxy aldehydes increased when relatively low UV-doses were used, but declined following further irradiation. The concentrations of aliphatic dibasic acids increased over the full range of UV-doses

Extraction and separation of rare earths from chloride medium with mixtures of 2-ethylhexylphosphonic acid mono-(2-ethylhexyl) ester and sec-nonylphenoxy acetic acid

BACKGROUND: 2-ethylhexylphosphonic acid mono-(2-ethylhexyl) ester (HEHEHP, H(2)A(2)) has been applied extensively to the extraction of rare earths. However, there are some limitations to its further utilization and the synergistic extraction of rare earths with mixtures of HEHEHP and another extractant has attracted much attention. Organic carboxylic acids are also a type of extractant employed for the extraction of rare earths, e.g. naphthenic acid has been widely used to separate yttrium from rare earths. Compared with naphthenic acid, sec-nonylphenoxy acetic acid (CA100, H2B2) has many advantages such as stable composition, low solubility, and strong acidity in the aqueous phase. In the present study, the extraction of rare earths with mixtures of HEHEHP and CA100 has been investigated. The separation of the rare earth elements is also studied.

Solvent extraction study of rare earth elements from chloride medium by mixtures of sec-nonylphenoxy acetic acid with Cyanex301 or Cyanex302

The extraction of rare earth elements from chloride medium by mixtures of sec-nonylphenoxy acetic acid (CA100) with bis(2,4,4-trimethylpentyl) dithiophosphinic acid (Cyanex301) or bis(2,4,4-trimethylpentyl) monothiophosphinic acid (Cyanex302) in n-heptane has been studied. The synergistic enhancement of the extraction of lanthanum (III) by mixtures of CA100 with Cyanex301 has been investigated using the methods of slope analysis and constant mole. The extracted complex of lanthanum (III) is determined. The logarithm of the equilibrium constant is calculated as - 1.41. The formation constants and the thermodynamic functions, Delta H, Delta G, and Delta S have also been determined.

Solvent extraction of rare earths from chloride medium with mixtures of 1-phenyl-3-methyl-4-benzoyl-pyrazalone-5 and sec-octylphenoxyacetic acid

The extraction of rare earth elements from chloride medium by mixtures of sec-nonylphenoxy acetic acid (CA100) with bis(2,4,4-trimethylpentyl) dithiophosphinic acid (Cyanex301) or bis(2,4,4-trimethylpentyl) monothiophosphinic acid (Cyanex302) in n-heptane has been studied. The synergistic enhancement of the extraction of lanthanum (III) by mixtures of CA100 with Cyanex301 has been investigated using the methods of slope analysis and constant mole. The extracted complex of lanthanum (III) is determined. The logarithm of the equilibrium constant is calculated as - 1.41. The formation constants and the thermodynamic functions, Delta H, Delta G, and Delta S have also been determined.

Extraction and separation of yttrium from the rare earths with sec-octylphenoxy acetic acid in chloride media

Extraction and separation of yttrium from the rare earths in chloride medium using sec-octylphenoxy acetic acid (CA-12), tri-n-butyl phosphate (TBP) as modifier, in kerosene has been investigated. The separation coefficients, beta, were obtained and the extraction selectivity has been enhanced when compared with that of naphthenic acid. The experimental results indicated that CA-12-TBP system could be employed to separate yttrium, from rare earths. Fractional extraction (15 stages for extraction and 10 stages for scrubbing) was studied, the raffinate of the first stage was abundant in purity yttrium of 99.5%, with a yield of > 95%, percentage of yttrium in the mixture rare earths was less than 5% in the loaded organic phase of the 25th stage and loaded capability was about 0.2 mol/L.

Solvent extraction of scandium(III), yttrium(III), lanthanides(III), and divalent metal ions with sec-nonylphenoxy acetic acid

Such physicochemical properties of sec-nonylphenoxy acetic acid (CA-100) as the solubility in water, acid dissociation constant in water, dimerization constant in heptane, and distribution constant in organic solvent-water were measured by two-phase titration. The extraction behaviors of scandium (III), yttrium (III), lanthanides (III), and divalent metal ions from hydrochloric acid solutions with CA-100 in heptane have been investigated, and the possibilities of separating scandium (yttrium) from lanthanides and divalent metal ions have been carefully discussed. The stoichiometries of the extracted metal complexes were investigated by the slope-analysis technique. The effect of the nature of diluent on the extraction of yttrium (III) with CA100 has been studied and correlated with the dielectric constant.

中国西南地区大气降水中低分子有机酸研究（以贵阳市和尚重镇为例）

近几年随全球变暖和大气污染的加剧，有机气溶胶对气候和环境的影响引起了广泛的关注。其中低分子有机酸由于易溶于水，易挥发等特性可以改变大气颗粒物吸湿性、粒径分布以及形成云凝结核活性，进而改变全球的水循环和辐射平衡，而日益成为大气化学研究的重要内容。低分子有机酸极强的水溶性使雨水成为研究大气有机酸的理想载体。有机酸进入降水后是降雨的酸度重要贡献者，尤其是边远地区有机酸对降水酸度贡献高达65%。传统的大气降水研究主要侧重无机离子，认为硫酸和硝酸是降水酸度的主要贡献者，而忽略对降水中有机组分的研究。以贵阳和重庆等为代表的西南地区是我国酸雨污染的重灾区，该地区是典型喀斯特地形地貌区，生态环境具有极端的脆弱性和破坏后难以恢复性，在该地区研究酸雨形成和影响因素具有特殊的重要意义。本研究选取典型酸雨区(贵阳市)和人为污染较少黔东南州黎平县尚重镇为研究对象，2006-4～2007-4期间，收集大气降水样品221个，测定了大气降水中7种有机酸和主要阴、阳离子。对有机酸对酸雨的贡献及大气降水中无机离子和有机酸的浓度分布、变化规律、主要来源和沉降通量进行研究。主要得到了以下几点认识： 1、建立了离子色谱同时测定雨水中有机酸和无机酸分析条件。以戴安AS11-HC为分离柱、AG11-HC为保护柱，RFC-30淋洗液发生器在线产生KOH淋洗液，主要梯度条件为1mmol ( 0～6min) 、1mmol～30mmol (6～31min)。淋洗液流速1.5ml/min，柱温39℃。此条件下主要有机酸线性相关系数0.9992~0.9999，RSD%≤5%，精密度RSD%≤5%(丙酮酸RSD%=13.8%)，样品的加标回收率在80~120%之间，满足分析测试要求。 2、 贵阳市降水样品pH值的分布范围为2.49～6.92，年均值为3.28。雨水酸化率为73.8%，其中pH值小于4.0雨水占样品总数42%。尚重镇降水样品pH值的分布范围为5.01～6.50，年均值为5.83，降水的酸雨率为18.4%。贵阳市酸雨污染仍十分严重，重酸雨尤为突出(pH<4.0)，尚重镇酸雨污染较轻。 贵阳市降水样品电导率在10～1028μS/cm之间，平均值为248μS/cm，降水电导率高反映了贵阳市大气污染显著。尚重镇降水样品电导率在2.2～52.8μS/cm之间，平均值为18.1μS/cm，降水电导率低反映大气污染较轻。 3、贵阳市大气降水主要无机离子是SO42-、NO3-、H+、Ca2+、NH4+，雨量加权平均浓度分别为154.1μmol/L、33.9μmol/L、520.7μmol/L、226.4μmol/L和158.3μmol/L。采样期间，贵阳市H+年沉降通量为496.9mmol/m2/yr，夏季H+沉降占全年沉降总量的78%，贵阳市SO42-年沉降通量达到151.5mmol/m2/yr，有195.3mmol/m2/yr的Ca2+沉降。NH4+、Mg2+、Na+、K+、NO3-、Cl-的沉降通量分别为138.7mmol/m2/yr、50.9mmol/m2/yr、26.8mmol/m2/yr、11.4mmol/m2/yr、32.3mmol/m2/yr和12.6mmol/m2/yr。 尚重镇贵阳市大气降水主要无机离子是SO42-、NO3-、Ca2+、NH4+，其雨量加权平均浓度分别为43.1μmol/L、19.3μmol/L、33.0μmol/L和49.5μmol/L。采样期间，尚重镇[H+]年沉降通量为0.5mmol/m2/yr。SO42-、Ca2+和NH4+是发生沉降主要离子，分别为13.9mmol/m2/yr、10.6mmol/m2/yr和15.9mmol/m2/yr。Mg2+、Na+、K+、NO3-、Cl-的沉降通量分别为2.1mmol/m2/yr、5.9mmol/m2/yr、3.0mmol/m2/yr、6.2mmol/m2/yr和3.2mmol/m2/yr。 4、在贵阳市、尚重镇大气降水中共检测出7种低分子有机酸，分别是甲酸、乙酸、草酸、丙酮酸、丙酸、甲烷磺酸和乳酸。其中甲酸、乙酸和草酸是三种主要的有机酸。贵阳市甲酸、乙酸和草酸年平均浓度分别为14.24μmol/L、9.35μmol/L和2.79μmol/L，而在尚重镇它们浓度分别为4.95μmol/L、1.35μmol/L和2.31μmol/L。根据酸平衡常数计算法，贵阳市有机酸对自由酸贡献分别为：甲酸-7.9%，乙酸-4.7%，草酸-6.1%，三种主要有机酸贡献了18.7%的自由酸；尚重镇有机酸对自由酸贡献分别为：甲酸-25.1%，乙酸-7.5%，草酸-25.5%，有机酸对自由酸贡献率为58.1%。贵阳市有机酸占阴离子比值1.7～19.2%，平均值为6.6%。尚重镇有机酸对阴离子的贡献为0.5～92.2%，平均值为13.2%。有机酸对酸雨形成和大气降水化学起不可忽视的重要作用。 采样期间，贵阳市甲酸、乙酸和草酸的湿沉降通量分别为13.5mmol/m2/year 、8.9mmol/m2/year和2.6mmol/m2/year，甲酸和乙酸干沉降通量分别为26.7mmol/m2/year 和14.5mmol/m2/year，干沉降和湿沉降是贵阳市有机酸的主要沉降形式。尚重镇甲酸、乙酸和草酸的湿沉降通量分别为1.59mmol/m2/year 、0.43mmol/m2/year和0.04mmol/m2/year，甲酸和乙酸干沉降通量分别为0.1mmol/m2/year 和0.17mmol/m2/year，湿沉降是尚重镇有机酸的主要沉降形式。 5、尚重镇大气降水有机酸生长季节浓度高于非生长季节浓度，说明生长植物或土壤的释放可能是尚重镇大气有机酸的主要来源。贵阳市大气降水中有机酸非生长季节浓度高于生长季节浓度，主要原因是贵阳市降雨主要发生在夏季，降雨量的增加加大了对大气中微量气体的淋滤作用，降低了大气中有机酸浓度，同时夏季降雨pH值较低也不利于雨水对大气有机酸的溶解吸收。气象条件是影响有机酸浓度的重要因素。贵阳市大气有机酸主要在降雨初期进入降水并被清除的，降雨初期(1～2h)对大气有机酸清除占总清除的50～80%。随降雨的进行雨水中有机酸浓度逐渐降低，降雨后期略有升高，大降雨量对雨水中有机酸浓度起稀释的作用。尚重镇降雨量对有机酸浓度影响作用不明显，说明有机酸浓度不受雨量稀释作用控制，在降雨过程可能存在有机酸的液相来源。不同来源气团对贵阳市雨水中有机酸浓度影响不同，其中以北面方向气团降水中有机酸最高，与我国内陆大气污染较重有关。而源于海洋方向的东南气团雨水中有机酸浓度最低。 6、利用统计分析方法(相关性分析、主成分分析和聚类分析)和有机酸来源判别方法结合不同的来源释放有机酸通量得出：尚重镇大气中有机酸主要来源植物或者土壤直接或间接释放，而贵阳市有机酸来源相对复杂，其中植物的直接释放和机动车辆尾气排放不是大气有机酸的主要来源，生物质燃烧直接释放以及植物和人类活动向大气排放大量的不饱和有机物大气氧化可能是大气有机酸的重要来源。 7、从大气降水的电导率和pH值对比来看，贵阳市大气污染严重，雨水酸化率高，尚重镇大气污染较轻，雨水酸化率低。贵阳市大气降水中水溶性离子浓度是尚重镇的2～5倍左右，尚重镇地区酸沉降只有贵阳市0.1%，酸沉降对尚重镇不会造成太大影响。有机酸占贵阳市大气降水自由酸的19%，而尚重镇有超过1/2的自由酸是来源于低分子有机酸，是边远地区大气降水酸度的主要贡献者。来源分析表明尚重镇有机酸主要为生物源，贵阳市有机酸为人为源和生物源并重。 8、 传统的大气降水化学研究主要侧重于无机离子的研究，而忽略了对大气降水中有机组分的研究。本文第一次较全面、系统的研究了西南典型酸雨污染区大气降水化学组成以及降水酸度的来源，指出有机酸组分是西南地区大气降水化学的重要组成部分，对酸雨形成有不可忽视的影响。

Simulation chamber studies of the atmospheric degradation of naphthalene, 1-nitronaphthalene and phthaldialdehyde

A detailed series of simulation chamber experiments has been performed on the atmospheric degradation pathways of the primary air pollutant naphthalene and two of its photooxidation products, phthaldialdehyde and 1-nitronaphthalene. The measured yields of secondary organic aerosol (SOA) arising from the photooxidation of naphthalene varied from 6-20%, depending on the concentrations of naphthalene and nitrogen oxides as well as relative humidity. A range of carbonyls, nitro-compounds, phenols and carboxylic acids were identified among the gas- and particle-phase products. On-line analysis of the chemical composition of naphthalene SOA was performed using aerosol time-of-flight mass spectrometry (ATOFMS) for the first time. The results indicate that enhanced formation of carboxylic acids may contribute to the observed increase in SOA yields at higher relative humidity. The photolysis of phthaldialdehyde and 1-nitronaphthalene was investigated using natural light at the European Photoreactor (EUPHORE) in Valencia, Spain. The photolysis rate coefficients were measured directly and used to confirm that photolysis is the major atmospheric loss process for these compounds. For phthaldialdehyde, the main gas-phase products were phthalide and phthalic anhydride. SOA yields in the range 2-11% were observed, with phthalic acid and dihydroxyphthalic acid identified among the particle phase products. The photolysis of 1-nitronaphthalene yielded nitric oxide and a naphthoxy radical which reacted to form several products. SOA yields in the range 57-71% were observed, with 1,4-naphthoquinone, 1-naphthol and 1,4-naphthalenediol identified in the particle phase. On-line analysis of the SOA generated in an indoor chamber using ATOFMS provided evidence for the formation of high-molecular-weight products. Further investigations revealed that these products are oxygenated polycyclic compounds most likely produced from the dimerization of naphthoxy radicals. These results of this work indicate that naphthalene is a potentially large source of SOA in urban areas and should be included in atmospheric models. The kinetic and mechanistic information could be combined with existing literature data to produce an overall degradation mechanism for naphthalene suitable for inclusion in photochemical models that are used to predict the effect of emissions on air quality.

Synthetic and stereochemical aspects of intramolecular reactions of α-diazoketones catalysed by rhodium(II) carboxylates

Chapter 1 of this thesis is a brief introduction to the preparation and reactions of α-diazocarbonyl compounds, with particular emphasis on the areas relating to the research undertaken: C-H insertion, addition to aromatics, and oxonium ylide generation and rearrangement. A short summary of catalyst development illustrates the importance of rhodium(II)carboxylates for α-diazocarbonyl decomposition. Chapter 2 describes intramolecular C-H insertion reactions of α-diazo-β-keto sulphones to form substituted cyclopentanones. Rhodium(II) carboxylates derived from homochiral carboxylic acids were used as catalysts in these reactions and enantioselection achieved through their use is discussed. Chapter 3 describes intramolecular Buchner cyclisation of aryl diazoketones with emphasis on the stereochemical aspects of the cyclisation and subsequent reaction of the bicyclo[5.3.0]decatrienones produced. The partial asymmetric synthesis achieved through use of chiral rhodium(II) carboxylates as catalysts is discussed. The application of the intramolecular Buchner reaction to the synthesis of hydroazulene lactones is illustrated. Chapter 4 demonstrates oxonium ylide formation and rearrangement in the decomposition of an α-diazoketone. The consequences of the use of chiral rhodium(II) carboxylates as catalysts are described. Particularly significant was the discovery that rhodium(II) (S)-mandelate acts as a very efficient catalyst for α-diazoketone decompositions, in general. Moderate asymmetric induction was possible in the decomposition of α-diazoketones with chiral rhodium(II) carboxylates, with rhodium(II) (S)-mandelate being one of the more enantioselective catalysts investigated. However, the asymmetric induction obtained was very dependent on the exact structure of the α-diazoketone, the catalyst, and the nature of the reaction. Chapter 5 contains the experimental details, and the spectral and analytical data for all new compounds reported.

Isolation and characterisation of antifungal compounds from lactic acid bacteria and their application in wheat and gluten-free bread

As part of the “free-from” trend, biopreservation for bread products has increasingly become important to prevent spoilage since artificial preservatives are more and more rejected by consumers. A literature review conducted as part of this thesis revealed that the evaluation of more suitable antifungal strains of lactic acid bacteria (LAB) is important. Moreover, increasing the knowledge about the origin of the antifungal effect is fundamental for further enhancement of biopreservation. This thesis addresses the investigation of Lactobacillus amylovorus DSM19280, Lb. brevis R2: and Lb. reuteri R29 for biopreservation using in vitro trials and in situ sourdough fermentations of quinoa, rice and wheat flours as biopreservatives in breads. Their contribution to quality and shelf life extension on bread was compared and related to their metabolic activity and substrate features. Moreover, the quantity of antifungal carboxylic acids produced during sourdough fermentation was analysed. Overall a specific profile of antifungal compounds was found in the sourdough samples which were strain and substrate dependently different. The best preservative effect in quinoa sourdough and wheat sourdough bread was achieved when Lb. amylovorus DSM19280 fermented sourdough was used. However, the concentration of the antifungal compounds found in these biopreservatives were much lower when compared with Lb. reuteri R29 as the highest producer. Nevertheless, the artificial application of the highest concentration of these antifungal compounds in chemically acidified wheat sourdough bread succeeded in a longer shelf life than achieved only by acidifying the dough. This evidences their partial contribution to the antifungal activity and their synergy. Additionally, a HRGC/MS method for the identification and quantification of the antifungal active compounds cyclo(Leu-Pro), cyclo(Pro-Pro), cyclo(Met-Pro) and cyclo(Phe-Pro) was successfully developed by using stable isotope dilutions assays with the deuterated counterparts. It was observed that the concentrations of cyclo(Leu-Pro), cyclo(Pro-Pro), and cyclo(Phe-Pro) increased only moderately in MRS-broth and wort fermentation by the activity of the selected microorganism, whereas the concentration of cyclo(Met-Pro) stayed unchanged.

Chemistry and Release of Gases from the Surface Ocean

The sea-surface layer is the very upper part of the sea surface where reduced mixing leads to strong gradients in physical, chemical and biological properties1. This surface layer is naturally reactive, containing a complex chemistry of inorganic components and dissolved organic matter (DOM), the latter including amino acids, proteins, fatty acids, carbohydrates, and humic-type components,2 with a high proportion of functional groups such as carbonyls, carboxylic acids and aromatic moieties.3 The different physical and chemical properties of the surface of the ocean compared with bulk seawater, and its function as a gateway for molecules to enter the atmosphere or ocean phase, make this an interesting and important region for study. A number of chemical reactions are believed to occur on and in the surface ocean; these may be important or even dominant sources or sinks of climatically-active marine trace gases. However the sea surface, especially the top 1um to 1mm known as the sea surface microlayer (ssm), is critically under-sampled, so to date much of the evidence for such chemistry comes from laboratory and/or modeling studies. This review discusses the chemical and physical structure of the sea surface, mechanisms for gas transfer across it, and explains the current understanding of trace gas formation at this critical interface between the ocean and atmosphere.

An array-based study of reactivity under solvent-free mechanochemical conditions-insights and trends

An array-based approach is put forward to obtain insight into reactivity under mechanochemical solvent-free conditions. We describe a survey of sixty potential reactions between twelve metal salts MX2 {(M = Cu, X-2 = (OAc)(2), (HCO2)(2), (F3CCO2)(2), (acac)(2), (F(6)acac)(2), (NO3)(2), SO4; M = Ni, X-2 = (OAc)(2), (NO3)(2), SO4; M = Zn, X-2 (OAc)(2), (NO3)(2)} and five bridging organic ligands {isonicotinic acid (HINA), 1,4-benzenedicarboxylic acid (H2BDC), acetylenedicarboxylic acid (H(2)ADC), 1,3,5-benzenetricarboxylic acid (H3BTC), 4,4'-bipyridyl (BIPY). Reaction conditions involved a ball mill, applied for 15 min at 30 Hz, without external heating. When examined by XRPD, forty of the combinations gave detectable reactions, thirty-eight with crystalline products. Of these, twenty-nine reactions were quantitative (consuming all of at least one reactant). Comparison of XRPD patterns with patterns simulated from single crystal X-ray diffraction data in the Cambridge Structural Database allowed structural identification of six products. Of particular interest are the microporous framework materials [Cu(INA)(2)] and [Cu-3(BTC)(2)] (HKUST-1) obtained by reaction of the corresponding carboxylic acids with copper acetate. Other non-porous polymers with 3-dimensional connectivity, [Ni(ADC)(H2O)(4)], or 1-dimensional connectivity, [Cu(acac)(2)(BIPY)] and [Cu(F6acac)(BIPY)] were also obtained. Reaction between zinc acetate and H2ADC gave a new product which had not previously been characterised by single-crystal X-ray crystallography, but whose XRPD pattern suggests that it is isostructural with the known nickel polymer [Ni(ADC)(H2O)(4)]. Two further isostructural nickel and zinc products were obtained in reactions between HINA and nickel nitrate and zinc nitrate. Trends observed within the array are discussed. Copper acetate and copper formate were the most effective starting materials for reaction with carboxylic acids, potentially related to the basicity of their anions and the solvating effects of the formic and acetic acid byproducts. Amongst the ligands there was a general negative corelation between melting point and reactivity. The issue of pore templating in microporous phases and the generation of new structures is also discussed in relation to the Cu(INA)(2), Cu-3(BTC)(2) and nickel nitrate-BIPY systems. Overall, the study suggests that mechanochemical reactivity between metal salts and organic ligands under solvent free conditions is remarkably general. Use of array-based approaches as demonstrated here is advocated a useful way to reveal underlying trends in reactivity under solvent free mechanochemical conditions and to highlight particular cases for more detailed study.

Evaluation of Pt and Re oxidation state in a pressurized reactor: difference in reduction between gas and liquid phase

Determination of metal oxidation state under relevant working conditions is crucial to understand catalytic behaviour. The reduction behaviour of Pt and Re was evaluated simultaneously as a function of support and solvent in a pressurized reactor (autoclave). The bimetallic catalysts are used in selective hydrogenation of carboxylic acids and amides. Gas phase reduction reduced the metals more efficiently, in particular Pt.