甲酰基化羰基化合成3,4-二甲基苯甲醛

以邻二甲苯和CO为原料、粉状无水AlCl4为催化剂、1，2-二氯乙烷为溶剂，利用甲酰基化与羰基化分步反应，在n（A1C13）：n（邻二甲苯）-1．0：1、CO压力1．5MPa、-5℃以下甲酰基化反应6h、-5～0℃羰基化反应50min的较佳工艺条件下，可以得到纯度≥98．0％的3，4-二甲基苯甲醛。

改善产物同分异构体的加氢甲酰基化方法

美国联碳化学品及塑料科技公司公开了一种连续加氢甲酰基化方法（CN101657407，2010．2．24）。该方法用于在提高产物醛的正／支链（N／I）同分异构体比率的灵活性和稳定性的情况下制备醛的混合物。所述方法包括：使一种或多种烯键式不饱和化合物、一氧化碳和氢在有机多亚磷酸酯配体和有机单亚磷酸酯配体的存在下接触，

甲酰基取代的焦脱镁叶绿酸衍生物的合成及其光谱分析

从叶绿素-a或者叶绿素-b开始,制备出焦脱镁叶绿酸-a甲酯或者焦脱镁叶绿酸-b甲酯,通过四氧化锇氧化和空气氧化反应,在二氢卟吩周环上的7-位和12-位上引进甲酰基结构,完成了一系列具有叶绿素基本碳架的二氢卟吩醛的合成.根据甲酰基取代的不同位置和四吡咯大环分子色基的结构特点,解释了所得叶绿素类二氢卟吩的紫外-可见光谱的变化原因及规律,对相应的红外光谱和核磁共振氢谱进行了归属.

Aspartame的合成中间体——N-甲酰基-L-天冬氨酸酐的合成研究

研究了由L-天冬氨酸和甲酸反应制备Aspartame的重要中间体——N-甲酰基-L-天冬氨酸酐的方法。通过考察反应物的配比、反应温度及反应时间等对反应的影响,确定了最佳反应条件,使N-甲酰基-L-天冬氨酸酐的合成收率达到98％。

氨基甲酰乙基微纤化纤维素的制备及改性

采用氨基甲酰乙基化反应对阔叶浆进行预处理,再经机械研磨得到了微纤化纤维素,最后分别在酸性和碱性条件下用次氯酸钠对其进行了改性。探讨了预处理条件对产物中氨基甲酰乙基和羧乙基含量的影响,并对预处理产物、微纤化纤维素和次氯酸钠改性产物的结构和热稳定性进行了表征。结果表明,预处理过程中丙烯酰胺和氢氧化钠用量以及反应温度会影响产物中氨基甲酰乙基和羧乙基的含量,经研磨后可得到直径为亚微米级的氨基甲酰乙基微纤化纤维素,再经次氯酸钠改性后可得到N-氯氨甲酰化纤维素产品,改性后纤维素产品的初始分解温度和最大失重温度均明显降低,但其残留率显著增加。

基于DNA桥连氧化石墨烯的Fpg荧光检测

甲酰胺嘧啶DNA糖基化酶(Fpg)可特异性识别并切除由鸟嘌呤损伤产生的8-oxoG碱基以修复DNA序列,因此对Fpg进行定量检测可以反映鸟嘌呤受损程度,为污染物毒性效应评价提供技术手段.基于不同长度的DNA桥连氧化石墨烯(GO)强度不同的原理,以及GO优异的荧光淬灭能力,构建了DNA桥连GO基荧光传感器.该传感器在不同浓度Fpg下,特异性识别和切除8-oxoG碱基,产生短链DNA,其上修饰的荧光基团不能被GO有效淬灭,因而产生荧光信号.该荧光信号与Fpg浓度在一定范围内呈线性关系,可实现Fpg的定量检测,检测的线性范围为0~0.4 U/mL,检出限为0.014 U/mL,并表现出良好的特异性识别能力.采用加标回收法对稀释后胎牛血清中的Fpg进行了检测,回收率为93.5%~111%.其为Fpg快速检测提供了可行的方法,为DNA鸟嘌呤损伤评价提供了一种有效的技术手段.

Polymethylenebis [acetamides] Analogues.Synthesis and Differentiation-Inducing Activity on HL-60 Cells

报导了一系列多亚甲基双［酰胺］类化合物的合成，由－摩尔多亚甲基二甲酰氯分别和二摩尔２－氨基噻唑啉及５－氨基－１－甲基吡啶酮反应制得。测定了其体外对ＨＬ－６０人早幼粒白血病细胞的分化诱导活性，初步结果表明：Ｎ，Ｎ｀－双吡啶酮基六二甲酰胺和Ｎ，Ｎ｀－双噻唑啉基八亚甲基二甲酰胺分别在０．１ｍｍｏｌ／Ｌ和０．５ｍｍｏｌ／Ｌ浓度时，诱导分化百分率可达６０％。此浓度下细胞存活率分别为２６％及２２％，其有效诱导浓度比ＨＭＢＡ低十倍。

Effects of histone acetylation and DNA methylation on p21^(WAF1)regulation

Cell cycle progression is regulated by interactions between cyclins and cyclin-dependent kinases (CDKs). p21(WAF1) is one of the CIP/KIP family which inhibits CDKs activity. Increased expression of p21(WAF1) may play an important role in the growth arrest induced in transformed cells. Although the stability of the p21( WAF1) mRNA could be altered by different signals, cell differentiation and numerous influencing factors. However, recent studies suggest that two known mechanisms of epigenesis, i.e.gene inactivation by methylation in promoter region and changes to an inactive chromatin by histone deacetylation, seem to be the best candidate mechanisms for inactivation of p21( WAF1). To date, almost no coding region p21(WAF1) mutations have been found in tumor cells, despite extensive screening of hundreds of various tumors. Hypermethylation of the p21(WAF1) promoter region may represent an alternative mechanism by which the p21(WAF1/CIP1) gene can be inactivated. The reduction of cellular DNMT protein levels also induces a corresponding rapid increase in the cell cycle regulator p21(WAF1) protein demonstrating a regulatory link between DNMT and p21(WAF1) which is independent of methylation of DNA. Both histone hyperacetylation and hypoacetylation appear to be important in the carcinoma process, and induction of the p21(WAF1) gene by histone hyperacetylation may be a mechanism by which dietary fiber prevents carcinogenesis. Here, we review the influence of histone acetylation and DNA methylation on p21(WAF1) transcription, and affection of pathways or factors associated such as p 53, E2A, Sp1 as well as several histone deacetylation inhibitors.

Homogeneous Acetylation of Cellulose at Relatively High Concentrations in an Ionic Liquid

At relatively high cellulose mass concentrations(8%,10%,and 12%),homogeneous acetylation of cellulose was carried out in an ionic liquid,1-allyl-3-methylimidazolium chloride(AmimCl).Without using any catalyst,cellulose acetates(CAs)with the degree of substitution(DS)in a range from 0.4 to 3.0 were synthesized in one-step.The effects of reaction time,temperature and molar ratio of acetic anhydride/anhydroglucose unit(AGU) in cellulose on DS value of CAs were investigated.The synthesized CAs were characterized by means of FT-IR, NMR,and solubility,mechanical and thermal tests.After the acetylation,the used ionic liquid AmimCl was easily recycled and reused.This study shows the potential of the homogeneous acetylation of cellulose at relatively high concentrations in ionic liquids in future industrial applications.

Kinetics of 2-Methyl-6-acetyl-naphthalene Liquid Phase Catalytic Oxidation

In this paper, a kinetics model for the liquid-phase oxidation of 2-methyl-6-acetyl-naphthalene to 2,6-naphthalene dicarboxylic acid catalyzed by cobalt-manganese-bromide is proposed. The effects of the reaction temperature, catalyst concentration and ratio of catalyst on the lime evolution of the experimental concentration for the constituents including raw material, intermediates and product are investigated. The model parameters are determined in a nonlinear optimization, minimizing the difference between the simulated and experimental time evolution of the product composition obtained in a semi-batch oxidation reactor where the gas and liquid phase were well nuxed. The kinetics data demonstrate that the model is suitable to the liquid-phase oxidation of 2-methyl-6-acetyl-naphthalene to 2,6-naphthalene dicarboxylic acid.

Mixed hetero-/homogeneous TiO_(2)/N-hydroxyimide photocatalysis in visible-light-induced controllable benzylic oxidation by molecular oxygen

Homogeneous and heterogeneous types of catalysis are frequently considered as separate disciplines or even opposed to each other.In the present work,a new type of mixed het-ero-/homogeneous catalysis was demonstrated for the case of selective alkylarene oxidation by molecular oxygen.The proposed catalytic system consists of two widely available components:N-hydroxyphthalimide(NHPI,a homogeneous organocatalyst for free-radical chain reactions)and nanosized TiO_(2)(heterogeneous UV-active photoredox catalyst).The interaction of NHPI with TiO_(2) allows for a shift from UV to visible light photoredox activity and generation of phthalimide-N-oxyl(PINO)radicals that diffuse into the solution where NHPI/PINO-catalyzed free-radical chain reaction can proceed without the additional light input providing a fundamental increase in energy efficiency.The NHPI/TiO_(2) ratio controls the selectivity of oxidation affording preferential formation of hydroperoxide or ketone from alkylarene.

Transcriptional changes in epigenetic modifiers associated with gene silencing in the intestine of the sea cucumber,Apostichopus japonicus(Selenka),during aestivation

The sea cucumber, Apostichopusjaponicus, undergoes aestivation to improve survival during periods of high-temperature. During aestivation, the metabolic rate is depressed to reduce the consumption of reserved energy. We evaluated the role of epigenetic modification on global gene silencing during metabolic rate depression in the sea cucumber. We compared the expression of epigenetic modifiers in active and aestivating sea cucumbers. The expression of three genes involved in DNA methylation and chromatin remodeling （DNA （cytosine-5）-methyltransferase l, Methyl-CpG-binding domain protein 2）, and Chromodomain-helicase-DNA-binding protein 5） was significantly higher during aestivation （Days 20 and 40）. Similarly, we observed an increase in the expression of genes involved in histone acetylation （Histone deacetylase 3） and Histone-binding protein RBBP4） during the early （Days 5 and 10） and late phases （Days 20 and 40） of aestivation. There was no change in the expression of KAT2B, a histone acetyltransferase. However, the expression of histone methylation associated modifiers （Histone-arginine methyltransferase CARMER and Histone-lysine N-methyltransferase MLL5） was significantly higher after 5 d in the aestivating group. The results suggest that the expression of epigenetic modifiers involved in DNA methylation, chromatin remodeling, histone acetylation, and histone methylation is upregulated during aestivation. We hypothesize that these changes regulate global gene silencing during aestivation in A. japonicus.

Selective aerobic oxidation promoted by highly efficient multi-nitroxy organocatalysts

Selective oxidation with molecular oxygen as the sole oxidant under mild conditions is of crucialimportance for the long‐term sustainable exploitation of available feedstocks and the formation ofrequired intermediates for organic synthesis and industrial processes.Among the developed oxidationprotocols,innovative strategies using hydroxyimide organocatalysts in combination with metallicor metal‐free cocatalysts have attracted much attention because of the good activities andselectivities of such catalysts in the oxo functionalization of hydrocarbons.This method is based onthe reaction using N‐hydroxyphthalimide,which was first reported by Ishii’s group in the1990s.Although the important and wide‐ranging applications of such catalysts have been summarizedrecently,there are no reviews that focus solely on oxidation strategies using multi‐nitroxy organocatalysts,which have interesting properties and high reactivities.This review covers the concisesynthetic methods and mechanistic profiles of known multi‐nitroxy organocatalysts and summarizessignificant advances in their use in efficient aerobic oxidation.Based on a combination of experimentaland theoretical results,guidelines for the future rational design of multi‐nitroxy organocatalystsare proposed,and the properties of various model multi‐nitroxy organocatalysts are predicted.The present overview of the advantages,limitations,and potential applications of multi‐nitroxyorganocatalysts can provide useful tools for researchers in the field of selective oxidation.

From Bench to Bedside： Targeting Epigenetics for Cancer Therapy

The initiation and progression of cancer not only involves genetic abnormalities, but also epigenetic alterations, such as DNA methylation and histone modifications. Epigenetics refers to the heritable changes that do not involve any structural changes in the target gene, i.e., DNA sequence and protein sequence. Thus, these epigenetic aberrations are potentially reversible, allowing the malignant cells to revert to a state with more normal characteristics. The use of epigenetics is emerging as an effective and promising approach to treat cancer. Epigenetic drugs, which target two well- known epigenetic pathways, namely, DNA methyltransferases and histone deacetylases, are already being applied for the cancer treatment. In the current study, an overview regarding the under-standing of epigenetic alterations in the development of cancer and the current state of epigenetic drug discovery is provided.

Epigenetic modification regulates both expression of tumor-associated genes and cell cycle progressing in human colon cancer cell lines: Colo-320 and SW1116

The aim of this study is to assess the effects of DNA methylation and historic acetylation, alone or in combination, on the expression of several tumor-associated genes and cell cycle progression in two established human colon cancer cell lines: Colo-320 and SW1116. Treatments with 5-aza-2'-deoxycytidine (5-aza-dC) and trichostatin A, alone or in combination, were applied respectively. The methylation status of the CDKN2A promoter was determined by methyla-tion-specific PCR, and the acetylated status of the histones associated with the p21WAF1 and CDKN2A genes was examined by chromatin immunoprecipitation. The expression of the CDKN2A, p21WAF1, p53, p73, APC, c-myc, c-Ki-ras and survivin genes was detected by real-time RT-PCR and RT-PCR. The cell cycle profile was established by flow cytometry. We found that along with the demethylation of the CDKN2A gene promoter in both cell lines induced by 5-aza-dC alone or in combination with TSA, the expression of both CDKN2A and APC genes increased. The treatment of TSA or sodium butyrate up-regulated the transcription of p21WAF1 significantly by inducing the acetylation of histones H4 and H3, but failed to alter the acetylation level of CDKN2A-associated histones. No changes in transcription of p53, p73, c-myc, c-Ki-ras and survivin genes were observed. In addition, TSA or sodium butyrate was shown to arrest cells at the G1 phase. However, 5-aza-dC was not able to affect the cell cycle progression. In conclusion, regulation by epigenetic modification of the transcription of tumor-associated genes and the cell cycle progression in both human colon cancer cell lines Colo-320 and SW1116 is gene-specific.

Enhancing the activity,selectivity,and recyclability of Rh/PPh_(3) system‐catalyzed hydroformylation reactions through the development of a PPh_(3)‐derived quasi‐porous organic cage as a ligand

In contrast to heterogeneous network frameworks(e.g.,covalent organic frameworks and metal‐organic frameworks)and porous organic polymers,porous organic cages(POCs)are soluble molecules in common organic solvents that provide significant potential for homogeneous catalysis.Herein,we report a triphenylphosphine‐derived quasi‐porous organic cage(denoted as POC‐DICP)as an efficient organic molecular cage ligand for Rh/PPh_(3) system‐catalyzed homogeneous hydroformylation reactions.POC‐DICP not only displays enhanced hydroformylation selectivity(aldehyde selectivity as high as 97%and a linear‐to‐branch ratio as high as 1.89)but can also be recovered and reused via a simple precipitation method in homogeneous reaction systems.We speculate that the reason for the high activity and good selectivity is the favorable geometry(cone angle=123.88°)and electronic effect(P site is relatively electron‐deficient)of POC‐DICP,which were also demonstrated by density functional theory calculations and X‐ray absorption fine‐structure characterization.

Facile Conversion of Alcohols to Olefins by Tosylation and Subsequent SiO_2-promoted β-elimination

A convenient and effective procedure was developed for the conversion of alcohol to olefin by tosylation and subsequent β-elimination promoted by silica gel in this study. Treatment of the alcohols with p-toluenesulfonyl chloride in pyridine at 0℃ af- fords tosylates which undergo β-elimination with silica gel in dichloromethane or chloroform at room temperature, yielding olefins with high productivity.

Vilsmeier-Haack Reagent： Synthesis of 2-Chloro-3-Formyl-1,8-Naphthyridine and Transformation into Different Functionalities

A simple and regioselective synthesis of 2-chloro-3-formyl-l,8-naphthyridine （1） through V ilsmeier-Haack cyclization of N-（pyridine-2-yl） acetamide has been reported. The reaction of compound （1） with sodium sulphide gives thione （2） and the reaction of compound （1） with Na2S/DMF followed by reaction with alkyl halide in one pot afforded thioether （3 and 4）. New naphthyridone （5） was synthesized from the action of acetic acid and POCI3 in compound （1）. The condensation of compounds （1 and 8） with hydroxylamine and aniline leads to the formation of compounds （6, 7 and 9）. The 2-chloro-3-formyl-l,8-naphthyridine was treated with sodium azide underwent cyclization to afford tetrazolo （l,5-a） （l,8-naphthyridine-4-carbaldehyde （8）. The azitidinone （10 and 12） and thioazolidinone （11 and 13） were synthesized from shift base intermediates by using chloroacetyl chloride and thioglycolic acid. The formyl group in compound （1） is subjected to cyano （14） and 3-alkoxycarbonyl （15）, respectively. The ester （15） was treated with hydrazine hydrate in ethanol to give acid hydrazide （16） then converted to thio semicarbazide （17） by their reaction with ammonium thiocyanate. New thiadiazolo （18）, triazolo （19） and oxadiazolo （20） have been prepared. The structures of synthesized compounds have been confirmed by suitable spectroscopic techniques such as IR （infrared spectrometry） and ^1H NMR （proton nuclear magnetic resonance）.

Highly Efficient Asymmetric Transcyanation of Acetyltrimethylsilane with Acetone Cyanohydrin Catalyzed by (R)-Oxynitrilase from Prunus Japonica Seed Meal

Highly efficient asymmetric transcyanation of acetyltrimethylsilane with acetone cyanohydrin in an aqueous/organic biphasic system catalyzed with （R）-oxynitrilase from defatted Prunus Japonica seed meal for the preparation of optically active （R）-2-trimethylsilyl-2-hydroxyl-propionitrile was successfully carried out for the first time. For better understanding of the reaction, various influential variables were examined with respect to the initial reaction rate, the substrate conversion and the product enantiomeric excess （e.e.）. Diisopropyl ether was found to be the best organic phase for this reaction among all the organic solvents tested. The optimal concentrations of Prunus Japonica seed meal powder, acetyltrimethylsilane and acetone cyanohydrin, volume ratio of aqueous phase to organic phase, buffer pH value and the reaction temperature were 34.5g·L^-1 and 14mmol· L^-1, 28mmol· L^-1, 13% （by volume）, 5.0 and 30℃, respectively, while the initial reaction rate, the substrate conversion and the product enantiomeric excess were 1.34 mmol·L^-1·h^-1, 99.0% and 99.0%, respectively. The comparative study demonstrated that silicon atom in substrate showed great effect on the reaction and acetyltrimethylsilane was a much better substrate for （R）-hydroxynitrile lyase from Prunus Japonica seed than its carbon analogue 3,3-dimethyl-2-butanone.