Solid Phase Synthesis of 4(1H)Quinolones from Resin-Bound Cyclic Malonic Ester

The solid phase synthesis of 4 (1H) quinolones has been reported.

Solvent- and Catalyst-Free Microwave-Assisted Decarboxylation of Malonic Acid Derivatives

It has been found that microwave assisted decarboxylation of malonic acid derivatives can be achieved under solvent-free and catalyst free conditions. This new method produces the corresponding carboxylic acid in a pure manner and with a high yield in a very short reaction time: 3 - 10 min. In general terms, the condition under which this reaction is carried out accelerates the decarboxylation significantly of a series of disubstituted malonic acid derivatives, and makes this new process efficient, easy and environmentally friendly.

Application and Mechanism of Malonic Acid as a Green Alternative for Protein-Crosslinking

Formaldehyde fixation is the main method for crosslinking cellular proteins prior to their usage in immunocytochemistry. In order to create these links, formaldehyde undergoes a Mannich reaction in which the formaldehyde forms a methylene bridge between the aminogroup of two amino acids. Crosslinking increases protein stability allowing for more accurate preservation of in vivo conformations which in turn increases binding affinity of fluorochrome conjugated antibodies for fluorescent imaging. Formaldehyde is also a known carcinogen as classified by the National Cancer Institute. Malonic acid, a green, plant-based, water-soluble, and relatively inexpensive polycarboxylic acid has been shown to undergo crosslinking of proteins through an unknown mechanism. To test whether malonic acid can crosslink proteins within cells we fixed SH-5YSY cells with either malonic acid or formaldehyde and then stained with a fluorochrome conjugated antibody for the cytoskeletal protein α-tubulin. The cells were then imaged 72 hours after fixation. We observed a non-significant difference in the fluorescence of immunostained SH-5YSY cells fixed with malonic acid as compared to paraformaldehyde (p-value = 0.2469, ANOVA). In addition, we have created a theoretical mechanism showing malonic acid forming a propyl bridge for crosslinking proteins in a similar mechanism to that of formaldehyde. Here, we show that malonic acid is able to fix cells and retain fluorescence just as well as paraformaldehyde up to 72 hours after fixation and present several possible mechanisms for this chemical process.

Maleic acid and malonic acid reduced the pathogenicity of Sclerotinia sclerotiorum by inhibiting mycelial growth,sclerotia formation and virulence factors

Sclerotinia sclerotiorum is a necrotrophic plant pathogenic fungus with broad distribution and host range.Bioactive compounds derived from plant extracts have been proven to be effective in controlling S.sclerotiorum.In this study,the mycelial growth of S.sclerotiorum was effectively inhibited by maleic acid,malonic acid,and their combination at a concentration of 2 mg/mL,with respective inhibition rates of 32.5%,9.98%,and 67.6%.The treatment of detached leaves with the two acids resulted in a decrease in lesion diameters.Interestingly,maleic acid and malonic acid decreased the number of sclerotia while simultaneously increasing their weight.The two acids also disrupted the cell structure of sclerotia,leading to sheet-like electron-thin regions.On a molecular level,maleic acid reduced oxalic acid secretion,upregulated the expression of Ss-Odc2 and downregulated CWDE10,Ss-Bi1 and Ss-Ggt1.Differently,malonic acid downregulated CWDE2 and Ss-Odc1.These findings verified that maleic acid and malonic acid could effectively inhibit S.sclerotiorum,providing promising evidence for the development of an environmentally friendly biocontrol agent.

Probing and understanding interaction of Eu(Ⅲ)withγ-alumina in presenceof malonic acid

Radionuclide migration in aquatic environment is influenced by its sorption onto colloids/mineral oxides and the presence of organic complexing anions.With a view to understand the sorption of trivalent actinides by mineral oxides in presence of organic acid,in the present study,Eu(Ⅲ),malonic acid(MA)andγ-alumina are considered as representatives of trivalent actinides,low molecular weight natural occurring organic acid and aluminol sites,respectively.The influence of MA on sorption of Eu(Ⅲ)byγ-alumina was elucidated by batch sorption,spectroscopic techniques and surface complexation modeling,for the first time.Attenuated Total Reflection-Fourier Transform Infrared spectroscopic studies of MA sorbed onγ-alumina revealed the presence of two inner-sphere surface complexes.Batch sorption for binary(alumina-Eu(Ⅲ))and ternary(alumina-Eu(Ⅲ)-MA)systems were investigated as a function of p H,Eu(Ⅲ)concentration and sequential addition of Eu(Ⅲ)/MA.The p H edge for Eu(Ⅲ)sorption shifts to higher p H with increasing Eu(Ⅲ)concentration.In ternary systems,Eu(Ⅲ)sorption is significantly enhanced at p H<4.5.Eu(Ⅲ)speciation onγ-alumina is independent of addition sequence of Eu(Ⅲ)/MA.Time resolved fluorescence spectroscopy of Eu(Ⅲ)sorbed onγ-alumina exhibited two surface species,≡XOEu^2+and(≡YO)2 Eu^(+).The enhancement in I 616/I 592 and lifetime for ternary systems,as compared to binary system,at low p H,indicates the participation of Eu-MA complexes in the formation of surface species in ternary systems.The diffuse layer model has been employed to successfully model the experimental sorption profiles of binary and ternary systems,using code FITEQL 4.0,by considering the surface species identified by spectroscopic techniques.

Highly active Cu/SiO_2 catalysts for hydrogenation of diethyl malonate to 1,3-propanediol

Cu/SiO2 catalysts prepared by the ammonia evaporation method were applied to hydrogenation of diethyl malonate to 1,3‐propanediol. The calcination temperature played an important role in the structural evolution and catalytic performance of the Cu/SiO2 catalysts, which were systematically characterized by N2 adsorption‐desorption, inductively coupled plasma‐atomic emission spectros‐copy, N2O chemisorption, X‐ray diffraction, Fourier transform infrared spectroscopy, H2 tempera‐ture‐programmed reduction, transmission electron microscopy, and X‐ray photoelectron spectros‐copy. When the Cu/SiO2 catalyst was calcined at 723 K, 90.7%conversion of diethyl malonate and 32.3%selectivity of 1,3‐propanediol were achieved. Compared with Cu/SiO2 catalysts calcined at other temperatures, the enhanced catalytic performance of the Cu/SiO2 catalyst calcined at 723 K can be attributed to better dispersion of copper species, larger cupreous surface area and greater amount of copper phyllosilicate, which results in a higher ratio of Cu＋/Cu0. The synergetic effect of Cu0 and Cu＋is suggested to be responsible for the optimum activity.

Malone顺性灌肠治疗神经性大便失禁

目的:评价Malone顺性灌肠治疗神经性大便失禁的临床疗效。方法:1998年10月～1999年12月间对14例伴有大便失禁的脊髓拴系综合征患者(4～13岁)施行Malone手术,术后间断经阑尾造瘘口插管灌肠。对手术效果及肛门功能分别进行量化评分。结果:14例随访时间6个月～1年,2例造瘘口闭塞。余12例手术效果评分为21.4±1.3;肛门功能临床主观评分5郾05±0郾76,较术前(1郾23±0.64)明显增加(P<0郾01),其中优9例,良3例,差2例。结论:Malone顺性灌肠是治疗神经性大便失禁的有效方法,可明显提高患儿的生活质量。

Comparsion of the Effects of Succinate and NADH on Postmortem Metmyoglobin Redcutase Activity and Beef Colour Stability

In two experiments, the effects of succinate and NADH（reduced nicotinamide adenine dinucleotide） on metmyoglobin reductase activity and electron transport chain-linked metmyoglobin reduction were investigated and compared. In experiment 1, metmyoglobin（MetMb）, substrate and inhibitors were incubated with mitochondria. Comparsion of the effects of succinate and NADH on MetMb reduction was investigated. The MetMb percentage in sample treated with 8 mol L-1 succinate decreased by about 69% after 3 h incubation, and the effect was inhibited by the addition of 10 mol L-1 electron transfer chain complex II inhibitor malonic acid; the MetMb percentage in samples treated with 2 mol L-1 NADH decreased by 56% and the effect was inhibited by the addition of 0.02 mol L-1 electron transport chain complex I inhibitor rotenone. These results indicated that electron transport chain played an important role in MetMb reduction. Both complex II and complex I take part in the MetMb reduction in mitochondria through different pathways. NADH-MetMb reduction system was less stable than succinateMetMb system. In experiment 2, the beef longissimus dorsi muscle was blended with different concentrations of succinate or NADH. Enhancing patties with higher concentration of succinate or NADH improved colour stability in vacuum packaged samples（P〈0.05）. These results verified that mitochondria electron transport chain is related to the MetMb reduction in meat system.

一种新的血吸虫传播指数的构建及其应用

血吸虫传播指数可以通过数学模型直接对血吸虫的流行概况进行总体评估和预报。因此基于血吸虫流行传播机理,提出用极端气温对以往"改良Malone血吸虫传播指数"模型进行改进,参照前人洪青标等的研究成果,构建了"再改良Malone血吸虫传播指数"模型;然后引用世界粮农组织(FAO)与中国科学院地理科学与资源研究所的气象资料,用新模型对中国血吸虫病疫区内血吸虫传播指数的空间差异进行了定量计算和分等划区;用流行区与非流行区传播指数界线900为准,新模型将旧模型的河南省南部、安徽省北部、江苏省北部由原来的传播等级"中"转变成了"低"与"很低";还意外地发现了中国东部血吸虫病流行与并非流行区的界线与中国东部1月份-2℃等温线吻合得非常好。最后讨论了本研究作为一个"气象模型"的计算结果与现实血吸虫病疫情之间还有一些因子需要考虑,并提出了模型本身在计算过程中存在的一些问题和今后改进的方向。

Synthesis and Crystal Structure of a Ternary Complex:[Ni(phen)_2(pmal)]·8H_2O

A new ternary complex [Ni（phen）（pmal）]·8H2O （phen = 1,10-phenanthroline, pmal^2- = phenethyl malonic acid） has been synthesized by the reaction of nickel acetate, phen and phenethyl malonic acid. Elemental analysis, IR spectra and X-ray single-crystal diffraction were carried out to determine the composition and crystal structure. Crystal data for this complex： triclinic system, space group PI^-, a = 10.387（5）, b = 13.112（6）, c = 14.229（6） °A, α= 76.176（7）, β = 83.778（8）, γ = 71.770（6）°, C35H42N4O12Ni, Mr= 769.44, Z = 2, F（000） = 808, V = 1786.1°A^3, Dc = 1.431 g/cm^3,μ= 0.612 mm^-1, the final R = 0.0653 and wR = 0.1033 for 9379 （Rint = 0.0244） independent reflections and 4730 observed reflections （I〉 2σ（I））. Structural analysis shows that the coordination geometry of Ni（Ⅱ） is a distorted octahedron. A novel two-dimensional structure is constructed from （H2O）4 and （H2O）12 water clusters, and the complex forms a 3-D network supramolecular structure by hydrogen bonds and π-π stacking of neighboring phens.

Synthesis and Crystal Structure of a Macrocycle[Cu(dadm)(mal)(H_(2)O)]_(2)·2H_(2)O

The reaction of 4,4?-diaminodiphenylmethane (dadm), malonic acid (H2mal) and Cu(NO3)2 in aqueous solution results in a discrete binuclear Cu(II) macrocycle: [Cu(dadm)(mal)- (H2O)]22H2O. It crystallizes in monoclinic, space group P21/c with a = 15.231(3), b = 11.847(2), c = 9.801(2) ? b = 106.75(3)o, V = 1693.5(6) 3, Z = 2, C32H40Cu2N4O12, Mr = 799.76, Dc = 1.568 g/cm3, ?(MoKa) = 0.71073 ? = 1.325 mm-1, F(000) = 828, the final R = 0.0531 and wR = 0.1244 for 3421 observed reflections with I > 2s(I). Each Cu(II) is coordinated by two oxygen atoms from a mal ligand, two nitrogen atoms from two dadm ligands and a water oxygen atom to form a triangle bipyramidal motif. The title compound possesses a distorted macrocycle enclosed by dadm with approximate dimensions of 8.3 ??5.9 ?

Syntheses, characterization, and luminescence of two lanthanide complexes [Ln_2(acetate)_6(H_2O)_4]·4H_2O (Ln=Tb(1), Sm(2))

Two dinuclear compounds [Ln2（acetate）6（H2O）4]-4H2O （Ln=Tb（1）, Sm（2）） were obtained by the hydrothermal reaction of Ln2O3 with malonic acid at 150 ℃. Both compounds were characterized by elemental analyses, infrared spectra, and single crystal X-ray diffraction. The results showed that complexes 1 and 2 were isomorphous and crystallize in triclinic space group P 1. The coordination geometry around Ln（Ⅲ） ions in the complexes 1 and 2 was a distorted tricapped trigonal prism with a nine coordination. In the crystal, the molecular organization was further stabilized by well-defined weak hydrogen bonding interactions between the neutral dinuclear molecular units that led to the formation of a three-dimensional network. The fluorescence properties of the two complexes 1 and 2 in organic solvents were also studied. The results show that the ligand acetate favored energy transfer to the emitting energy level of Tb（Ⅲ） in complex 1. Some factors that influence the fluorescent intensity were also discussed in the article.

A Facile Solid-phase Synthesis of 3-Carboxycoumarins

Carboxycoumsrins were synthesized via the solid phase synthesis conviently. The resin bound cyclic malonic ester reacted with o-methoxy or o-hydroxybenzaldehydes. Then cyclization was processed under H2SO4 to afford the products in excellent purities and yields.

Synthesis,Characterization and Thermal Decomposition Behaviour of Tri-aquo Lanthanum(Ⅲ)Malonate Bimalonate

A new complex of malonic acid with lanthanum,La(Hmal)·(mal)·3H_2O,was synthesized and characterized by elemental analysis and IR spectra.The thermal decomposition process and their kinetic parameters n and E_a were studied by means of TG and DTG.All of the intermediate and end products were determined and characterized by the mass loss in TG curve,elemental analysis and IR spectra.

Convenient Solid-phase Synthesis of Benzothiazole Derivatives

Resin-bound cyclic malonic ester l reacted with aryl isothiocynate, then was treated with bromine, followed by cleavage from the resin under perchloric acid to give benzothiazoles 4.

可控性Malone顺行灌肠的护理体会

大便失禁和顽固性便秘是小儿肛门直肠畸形术后常见的问题,至今仍是一个难以解决的课题。1990年Malone等[1]提出应用顺行灌肠的方法进行肠道管理,可有效解决失禁及便秘的问题。我们根据2013年8月至2016年8月15例行Malone顺行灌肠（malone antegrade continence enema,MACE）患儿的护理经验,讨论护理对于Malone顺行灌肠的重要性。

The Study of Influence of Silica and Polyethilene Glycols Organic-Inorganic Compounds on Free-Radical Processes in Vitro

In this study investigation of influence of hybrid nanosilica-polyethylene glycols materials (molecular weight 1500, 6000 and 15000), prepared by sol-gel synthesis, on lipid peroxidation and antioxidant activity of human serum in vitro was performed. Methods included chemiluminescence analysis and quantitative malonic dialdehyde estimation. It was revealed that nanosilica-PEG materials with different molecular weight had certain biological activity. Powders of SiO2-PEG 1500 and SiO2-PEG 6000 manifest prooxidant effects, whereas mesoporous (calcine) powders produced antioxidant effects in blood serum in vitro.

消炎三号方对进展期白癜风抗氧化作用的临床研究

目的:探究白癜风发病的氧化应激机制及中药方剂消炎三号方治疗进展期白癜风的抗氧化作用原理。方法:检测和比较稳定期白癜风患者、健康对照组、消炎三号方治疗进展期白癜风患者前后外周血中丙二醛(MalonicDialdehyde,MDA)、过氧化氢酶(Catalase,CAT)的水平。结果:外周血中,进展期白癜风患者较稳定期患者与健康对照组,其MDA水平明显偏高(P<0.05)、CAT水平明显偏低(P<0.05)。稳定期患者和健康对照组之间外周血MDA、CAT水平无差异性(P>0.05)。经消炎三号方治疗三个月后,进展期患者外周血MDA水平明显下降(P<0.05),CAT水平明显增高(P<0.05),与稳定期及健康对照组无差异性(P>0.05)。结论:氧化应激在白癜风发病之初发挥重要作用,消炎三号方可保护黑素细胞抵抗氧化应激损伤。

Ionic liquids as efficient phase-transfer catalysts for the solid base-promoted monoalkylation of diethyl malonate

Ionic liquids （ILs） based on 1,3-dialkylimidazolium and tetraalkylammonium cations were employed as a series of efficient, environmentally benign phase-transfer catalysts （PTCs） for the base-promoted monoalkylation of diethyl malonate. The influence of various heterogeneous bases on yields was studied. Good yields and high selectivity were obtained. Solvent-free, mild reaction condition, short reaction time, and easy purification were the merits of this method. The catalytic system （IL-hase） could also be recycled after the extraction of products with ether.

Novel chiral thioureas for highly enantioselective Michael reactions of malonates to nitroalkenes

Highly efficient Michael addition reactions of malonates to nitroalkenes catalyzed by novel chiral thioureas derived from optically pure BINOL and amino acids are reported. Various trans-nitroalkenes reacted with malonates affording the desired products in up to 95% yield with excellent enantioselectivities （up to 97% ee）.