5-乙酰基-2,3-二氢苯并呋喃的合成

采用邻溴苯酚为初始原料,在相转移催化剂作用下经烷基化合成2-(2-氯乙氧基)-1-溴苯(1),通过生成格氏试剂合成2,3-二氢苯并呋喃(2),由傅-克酰基化反应合成5-乙酰基-2,3-二氢苯并呋喃(3)。反应过程以薄层色谱法监控,并通过元素分析、1HNMR对各中间体的组成和结构进行了确证和表征。     

5-硝基二氢苊在无显影气相光刻中的光致诱蚀作用的研究——5-硝基二氢苊的光氧化反应

5-硝基二氢苊的光氧化作用在无显影气相光刻中起着重要作用。我们通过红外,核磁共振、色质联用等手段对其光氧化产物进行了分析,并合成了有关化合物进行对照,确认5-硝基二氢苊的主要光氧化产物是5-硝基苊、5-硝基二氢苊酮、羟基-5-硝基二氢苊。     

过表达脑红蛋白对SH-SY5Y细胞损伤的神经保护作用及其机制

目的探讨过表达脑红蛋白(neuroglobin,NGB)对水溶性β-淀粉样蛋白片段1-42(beta-amyloid1-42,Aβ1-42)诱导的神经母细胞瘤SH-SY5Y细胞损伤的神经保护作用及其机制。方法将质粒pEGFP-NGB转染经Aβ1-42诱导损伤的SH-SY5Y细胞,MTT法检测NGB对损伤细胞存活率的影响;JC-1染色法检测NGB对损伤细胞线粒体膜电位的影响;免疫细胞化学法及Western blot法分别检测损伤细胞中细胞色素C(cytochrome C,cytoC)和caspase-3、caspase-9的表达水平。结果过表达NGB可明显提高Aβ1-42诱导损伤的SH-SY5Y细胞的存活率(P<0.05),抑制损伤细胞线粒体膜电位的降低(P<0.01),使损伤细胞内cytoC和caspase-3、caspase-9蛋白的表达水平均明显降低(P<0.05)。结论 NGB可通过抑制与细胞凋亡密切相关的cytoC、caspase-3和caspase-9等蛋白的表达而发挥其神经保护作用。本实验为阿尔茨海默病(Alzheimer disease,AD)的治疗提供了实验依据。     

潘多拉唑中间体2-巯基-5-二氟甲氧基-1-氢-苯并咪唑的合成工艺改进

2-硝基-4-二氟甲氧基苯胺在Raney-Ni催化下被水合肼还原,还原产物不经分离直接用于制备标题化合物,总收率达到94％。方法操作简便,安全可靠,适合于工业化生产。对另外几种取代的邻硝基苯胺进行了相同的还原试验,也取得了理想的结果,这为寻找新的具有生理活性的质子泵抑制剂提供了一条安全、有效的途径。     

5-氯-2，3-二氢茚-1-酮的合成

对茚虫威关键中间体5-氯-2,3-二氢茚-1-酮的合成进行了研究。以3-氯苄基氯为原料,经亲核取代、水解、脱羧、酰氯化和付氏酰基化等5步反应生成目标产物,产率42％。     

过表达脑红蛋白对水溶性β-淀粉样蛋白片段1-42诱导SH-SY5Y细胞线粒体损伤的保护作用及其机制

目的观察过表达脑红蛋白(neuroglobin,NGB)对水溶性β-淀粉样蛋白片段1-42(Amyloid-beta 1-42,Aβ_(1-42))诱导SH-SY5Y细胞线粒体损伤的保护作用,并探讨其机制。方法体外培养SH-SY5Y细胞,经Aβ_(1-42)预处理后转染质粒p EGFP-NGB及空载体p EGFP-N1,同时设空白对照组(未转染)。MTT法、流式细胞术及JC-1染色法分别检测过表达NGB对Aβ_(1-42)诱导损伤的SH-SY5Y细胞存活率、细胞凋亡及线粒体膜电位的影响,采用相应试剂盒检测细胞内半胱氨酸蛋白酶3(caspase 3)、caspase 9、ATP及细胞色素C(cytochrome C,cyto C)氧化酶活性;Western blot法检测细胞中cyto C、凋亡蛋白酶激活因子-1(apoptosis protease activating factor-1,Apaf-1)、caspase 3及caspase 9蛋白的表达水平。结果过表达NGB可显著提高Aβ_(1-42)诱导损伤SH-SY5Y细胞的存活率(P0.001)及细胞中cyto C氧化酶、ATP的活性(P0.01);可显著抑制损伤细胞的凋亡(P0.05)、线粒体膜电位的降低(P0.001)及细胞中caspase 3、caspase 9的活性(P0.01);可明显降低损伤细胞内cyto C、Apaf-1、caspase 3及caspase 9蛋白的表达水平(P0.05)。结论 NGB可显著抑制Aβ_(1-42)诱导的SH-SY5Y细胞损伤,促进其增殖,其机制可能与NGB恢复线粒体功能及抑制cyto C触发细胞凋亡密切相关。     

5-氯-2,3-二氢-1-茚酮的合成研究

以3-氯丙酰氯、氯苯、三氯化铝、浓硫酸为原料合成5-氯-2,3-二氢-1-茚酮,对影响反应的主要因素进行了研究,优化了条件,优化后的反应条件为:氯代酮合成:n(三氯化铝)∶n(氯苯)∶n(3-氯丙酰氯)=1.1∶4∶1,滴加温度为5℃,滴加时间2h,保温温度60℃,保温时间3h;5-氯茚酮合成:搅拌速度小于100r/min,n(H2SO4)∶n(氯代酮)=36.8∶1,滴加时间4h,溶剂为石油醚(90-120℃)。此工艺原料价廉易得,产品纯度高,总收率达50.6%,产品纯度达98%。     

2-氯-6，7-二氢喹啉-8（5H）-酮的合成研究

2-氯-6,7-二氢喹啉培（5H）-酮是四氢喹啉是一个重要的含氮杂环化合物。文章以2-氯-5,6,7,8-四氢喹啉为原料,经氧化、酯化、水解反应后得到2．氯-5,6,7,8-四氢喹啉-8-醇,再经Anelli氧化后得到总收率为57,8％的目标产物。所得化合物的结构均经核磁和质谱确证。     

6,7-二氢-5H-环戊烯并[b]吡啶的合成工艺改进

以1-氨基-2-氰基环戊烯(ACCP)为起始原料,经乙酰化、闭环、水解、氯化及脱氯等5步反应制得标题化合物。该方法反应条件温和,原料廉价易得,操作简便,适合工业化生产,总收率可达58.5%。     

短暂前脑缺血再灌注对大鼠海马脑区脑源性神经营养因子蛋白及mRNA表达的影响

目的探讨短暂前脑缺血再灌注(transient forebrain ischemia-reperfusion,I/R)对脑源性神经营养因子(brainderived neurotrophic factor,BDNF)蛋白及mRNA表达的影响,为进一步探索大鼠海马CA1区神经元损伤机制提供新的思路。方法将雄性SD大鼠随机分为control组、sham组和I/R组,利用Western blot和荧光定量PCR分析I/R后大鼠BDNF蛋白及mRNA表达的变化;染色质免疫共沉淀(chromatin immunoprecipitation,ChIP)试验检测I/R后大鼠BDNF基因启动子上H3K27的乙酰化水平。结果与control组相比,sham组大鼠CA1和CA3区BDNF蛋白和m RNA表达差异无统计学意义(P> 0. 05)。与sham组相比,I/R组大鼠CA1区BDNF蛋白表达显著下降(P <0. 001),而CA3区BDNF蛋白表达增高(P <0. 05);I/R组大鼠CA1区BDNF mRNAⅠ、Ⅱ和Ⅵ的表达均显著增高(P <0. 01),而mRNAⅣ的表达...     

Spatial organization of retinal ganglion cells in turtle,Pseudemys

Single-unit receptive fields were investigated in retinal-ganglion-cell axons to moving or flashing colored-light spots. All of the cells were sensitive to moving stimuli; about 40% were directionally selective. Retinal-ganglion-cell axons in general had very low spontaneous activities. Most receptive fields had silent surround regions. These cells were usually most sensitive to red light, but when dark-adapted, many cells also showed a high sensitivity to green and blue light. Under conditions of light adaptation, receptive fields to red light were little affected but receptive fields to green and blue lights disappeared. Fields were either circular, oval, or bar-shaped. Adaptation, wavelength, and velocity affected the receptive field organization and response profiles. The mutability and complexity of receptive field organization, the presence of bar-shaped fields and directionally selective cells, and multiple photoreceptor input to ganglion cells are indicative of retinas with particularly high integrative capacities, more so than in many other vertebrates.     

再生反应器液面高度对热再生电池性能的影响

热再生过程是热再生电池（thermally regenerative battery,TRB）系统的重要部分,本文研究了TRB的热再生过程对产电过程的影响,并通过降低热再生液面高度来强化换热过程和提升热再生性能。结果表明,采用再生电解液的TRB最大功率密度仅有12 W/m²,相比于初始电解液的TRB（最大功率密度为29.6 W/m²）降低了59%;降低加热液面高度可减小再生液平均热阻和受热温差,有效地强化了热再生性能;当热再生液面高度降低至1 cm后,热再生后TRB性能显著提升（27.0 W/m²）,与原性能相比仅下降8.7%。后续有望通过构建薄液膜热再生反应器来进一步强化热再生过程及提升电池热再生性能。     

负载型ZSM-5分子筛催化剂再生方法研究

吡啶合成中所用的催化剂为负载铅ZSM-5分子筛（Pb-ZSM-5）,活性很好,但反应过程中催化剂很易发生积炭失活。通过对O₂烧炭再生、水蒸汽再生和甲醇再生处理的催化剂进行评价以及进行BET、XRD和TPD 表征,结果表明,甲醇再生方法效果明显,提高了催化剂的寿命。催化剂再生过程要抑制“飞温”现象发生。     

再生时间对甲醇制烯烃催化剂水蒸气再生过程的影响

对甲醇制烯烃（MTO）过程失活催化剂采用水蒸气再生不仅可以减少二氧化碳排放,而且能提高低碳烯烃选择性,具有很好的应用前景。本文针对工业MTO过程使用的SAPO-34分子筛催化剂,研究了再生时间对水蒸气再生过程的影响。采用XRD、NH₃-TPD、TGA、FTIR、GC-MS以及N₂物理吸脱附表征手段对再生催化剂样品的晶体结构、酸性、残炭性质以及结构参数进行了表征,并考察再生催化剂的MTO反应性能。结果表明,再生时间越长,再生催化剂上残炭量越低,其酸性、比表面积和孔结构等能较好地恢复,在MTO反应中表现出更长的催化寿命。在再生过程中,催化剂上的残炭物种由芘、菲等大分子量的有机物转变为对MTO具有反应活性的萘等小分子有机物;但是可溶性残炭物种随着再生时间的延长而减少,从而使得初始低碳烯烃选择性有所降低。     

The Involvement of RhoA and Wnt-5a in the Tumorigenesis and Progression of Ovarian Epithelial Carcinoma

Background

Ras homolog gene family member A (RhoA) is involved in Wnt-5a–induced migration of gastric and breast cancer cells. We investigated the roles of RhoA and Wnt-5a in ovarian carcinoma.

Methods

RhoA and Wnt-5a mRNA and protein expression in normal fallopian tube epithelium, benign tumors, primary ovarian carcinomas, and metastatic omentum were quantified. RhoA or Wnt-5a was knocked down in OVCAR3 ovarian carcinoma cells using siRNAs and cell phenotype and expression of relevant molecules were assayed.

Results

RhoA and Wnt-5a mRNA and protein expression were found to be significantly higher in metastatic omentum than in ovarian carcinomas, benign tumors, and normal fallopian tube epithelium (p < 0.05), and positively associated with differentiation and FIGO staging (stage I/II vs. stage III/IV) in ovarian carcinoma (p < 0.05). RhoA and Wnt-5a expression were positively correlated in ovarian carcinoma (p = 0.001, R² = 0.1669). RhoA or Wnt-5a knockdown downregulated RhoA and Wnt-5a expression; reduced cell proliferation; promoted G₁ arrest and apoptosis; suppressed lamellipodia formation, cell migration, and invasion; and reduced PI3K, Akt, p70S6k, Bcl-xL, survivin, and VEGF mRNA or protein expression.

Conclusions

This is the first demonstration that RhoA and Wnt-5a are associated with ovarian carcinogenesis and apoptosis inhibition; there might be positive correlation between RhoA and Wnt-5a expression. RhoA is a potential tumorigenesis, differentiation, and progression biomarker in ovarian carcinoma.     

Effect of epinephrine and dibutyryl cyclic AMP on Δ5-desaturation activity of rat liver microsomes

The effect of epinephrine and dibutyryl cyclic AMP on the oxidative desaturation of [1-¹⁴C]-eicosatrienoic acid to arachidonic acid of rat liver microsomes has been studied. Epinephrine, at a dose of 1 mg/kg/body weight, produced a significant decrease on Δ5-desaturation activity 3 hr after the injection. This effect was maintained up to 12 hr and reached the control values 48 hr after the hormone administration. Dibutyryl cyclic AMP treatment for 24 hr (5 mg/8 hr/100 g body weight) also produced a significant decrease of the conversion of eicosatrienoic acid to arachidonic acid in rat liver microsomes. The effect of epinephrine on Δ5-desaturation activity was postulated to be evoked through an increase of the intracellular concentration of cyclic AMP.     

Effect of mineral salts on adsorption and regeneration of activated carbon

The successful application of activated carbon for the treatment of wastewater is very much tied to the adsorption loading and efficient regeneration of the carbon. This paper is concerned with the extent to which these steps can be improved when a mineral salt is present. A series of three-step processing sequences was carried out involving first an adsorption, then a regeneration, and finally a second adsorption. JXC 6/8 activated carbon (Carbon Products Division of Union Carbide Corporation) was used as the adsorbent for the removal of sodium benzenesulfonate from water. The salts had more effect when the salt treatment occurred simultaneously with adsorption than when salt impregnation was carried out prior to the adsorption. Calcium chloride had the greatest effect and potassium carbonate, the least. Concerning regeneration, potassium carbonate offered no improvement in adsorptive capacity after regeneration. In the cases of zinc chloride and calcium chloride, the most effective scheme was that in which impregnation was carried out simultaneously with regeneration. However, there was some improvement when the adsorption was carried in the presence of a salt. No improvement was found when the impregnation occurred prior to either regeneration or adsorption.     

Effect of trace additives on the efficiencyof peroxydisulfate regeneration

Direct chemical oxidation (DCO) is an emerging technology in which the organic components of hazardous or mixed waste streams are mineralized to carbon dioxide by the nearly omnivorous oxidant peroxydisulfate. Following treatment, the expended oxidant may be electrochemically regenerated to lower costs and minimize secondary waste; however, due to the varied contents of potential waste streams, trace chemical species may slowly accumulate in the system. To verify that the electrochemical recycling step was not adversely affected, the effect that several species have on the efficiency of this peroxydisulfate regeneration step has been measured. The organic additives formaldehyde, formic acid, and oxalic acid were tested, as well as the inorganic ions phosphate, nitrate, fluoride, chloride and thiocyanate. Changes in the peroxydisulfate formation potential in the presence of these additives were measured using chronopotentiometry, with current densities from 0.5 to 2.0 Acm–2, and additive concentrations of 0.1mm to 0.1m. Also, a real-time technique using a rotating disc electrode was developed to measure these additives' effect on the formation kinetics of peroxydisulfate. In addition, the effect that various additives had on the rate of electrochemical peroxydisulfate generation was measured in a large-scale electrolysis cell. None of the additives caused a significant reduction in the potential or the efficiency of the peroxydisulfate generation step, although the presence of formic acid appeared to increase the efficiency. In addition, the presence of thiocyanate completely blocks the reduction of peroxydisulfate on platinum. This information is currently being applied in scale-up testing of this technology for use in treating hazardous waste or the organic components of mixed waste.     

Effect of dietary fatty acids on Δ5 desaturase activity and biosynthesis of arachidonic acid in rat liver microsomes

The effect of different fatty acids supplemented to a fat-free diet on the activity of Δ5 desaturase was studied. Fat-free diet produces a reduction in the conversion of eicosa-8,11,14-trienoic acid to arachidonic acid. The addition of thecis-ω6 acids, linoleic, γ-linolenic or arachidonic to the diet produces an increase of eicosatrienoic acid desaturation, shifting Δ5 desaturase activity towards the controls on a balanced diet. This reactivation is apparently produced by induction of enzyme biosynthesis since linoleate effect was suppressed by simultaneous cycloheximide injection. On the contrary, no changes in Δ5 desaturation activity were found when the diet was supplemented with palmitic or 9-trans,12-trans-linoleic acid. The changes on the activity of Δ5 desaturase were compared with the fatty acid composition of plasma and liver microsomes.