934 resultados para mild mthod
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This paper addresses the design of algorithms for the collective optimization of a cost function defined over average quantities in the presence of limited communication. We argue that several meaningful collective optimization problems can be formulated in this way. As an application of the proposed approach, we propose a novel algorithm that achieves synchronization or balancing in phase models of coupled oscillators under mild connectedness assumptions on the (possibly time-varying and unidirectional) communication graphs. © 2006 IEEE.
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We study the problem of finding a local minimum of a multilinear function E over the discrete set {0,1}n. The search is achieved by a gradient-like system in [0,1]n with cost function E. Under mild restrictions on the metric, the stable attractors of the gradient-like system are shown to produce solutions of the problem, even when they are not in the vicinity of the discrete set {0,1}n. Moreover, the gradient-like system connects with interior point methods for linear programming and with the analog neural network studied by Vidyasagar (IEEE Trans. Automat. Control 40 (8) (1995) 1359), in the same context. © 2004 Elsevier B.V. All rights reserved.
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The growth and toxin content of the dinoflagellate Alexandrium tamarense ATHK was markedly affected by culture methods. In early growth phase at lower cell density static or mild agitation methods were beneficial to growth, but continuous agitation or aeration, to some extent, had an adverse effect on cell growth. Static culture in 2 L Erlenmeyer flasks had the highest growth rate (0.38 d(-1)) but smaller cell size compared with other culture conditions. Cells grown under aerated conditions possessed low nitrogen and phosphorus cell yields, namely high N and P cell-quota. At day 18, cells grown in continuous agitated and 1 h aerated culture entered the late stationary phase and their cellular toxin contents were higher (0.67 and 0.54 pg cell(-1)) compared with cells grown by other culture methods (0.27-0.49 pg cell(-1)). The highest cell density and cellular toxin content were 17190 cells mL(-1) and 1.26 pg cell(-1) respectively in an airlift photobioreactor with two-step culture. The results indicate that A. tamarense could be grown successfully in airlift photobioreactor by a two-step culture method, which involved cultivating the cells statically for 4 days and then aerating the medium. This provides an efficient way to enhance cell and toxin yield of A. tamarense.
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This article considers constant-pressure autoignition and freely propagating premixed flames of cold methane/air mixtures mixed with equilibrium hot products at high enough dilution levels to burn within the moderate to intense low oxygen dilution (MILD) combustion regime. The analysis is meant to provide further insight on MILD regime boundaries and to identify the effect of hot products speciation. As the mass fraction of hot products in the reactants mixture increases, autoignition occurs earlier. Species profiles show that the products/reactants mixture approximately equilibrates to a new state over a quick transient well before the main autoignition event, but as dilution becomes very high, this equilibration transient becomes more prominent and eventually merges with the primary ignition event. The dilution level at which these two reactive zones merge corresponds well with that marking the transition into the MILD regime, as defined according to conventional criteria. Similarly, premixed flame simulations at high dilutions show evidence of significant reactions involving intermediate species prior to the flame front. Since the premixed flame governing equations system demands that the species and temperature gradients be zero at the "cold" boundary, flame speed cannot be calculated above a certain dilution level. Up to this point, which again agrees reasonably well with the transition into the MILD regime according to convention, the laminar burning velocity was found to increase with hot product dilution while flame thickness remained largely unchanged. Some comments on the MILD combustion regime boundary definition for gas turbine applications are included. Copyright © Taylor & Francis Group, LLC.
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Tin disulfide (SnS2) nanocrystalline/amorphous blended phases were synthesized by mild chemical reaction. Both X-ray diffraction and transmission electron microscopy measurements demonstrate that the as-synthesized particles presented very small size, with a diameter of only a few nanometers. The photoluminescence (PL) spectrum suggests efficient splitting of photo-generated excitons in poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylenevinylene] (MDMO-PPV) and SnS2 hybrid films. Organic/inorganic hybrid solar cells comprising MDMO-PPV and SnS2 were prepared, giving photovoltage, photocurrent, fill factor and efficiency values of 0.702 V, 0.549 mA/cm(2), 0.385 and 0.148%, respectively, which suggests that this phase-blended inorganic semiconductor can also serve as a promising solar energy material. (C) 2009 Elsevier Ltd. All rights reserved.
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High amounts of acid compounds in bio-oil not only lead to the deleterious properties such as corrosiveness and high acidity, but also set up many obstacles to its wide applications. By hydrotreating the bio-oil under mild conditions, some carboxylic acid compounds could be converted to alcohols which would esterify with the unconverted acids in the bio-oil to produce esters. The properties of the bio-oil could be improved by this method. In the paper, the raw bio-oil was produced by vacuum pyrolysis of pine sawdust. The optimal production conditions were investigated. A series of nickel-based catalysts were prepared. Their catalytic activities were evaluated by upgrading of model compound (glacial acetic acid). Results showed that the reduced Mo-10Ni/gamma-Al2O3 catalyst had the highest activity with the acetic acid conversion of 33.2%. Upgrading of the raw bio-oil was investigated over reduced Mo-10Ni/gamma-Al2O3 catalyst. After the upgrading process, the pH value of the bio-oil increased from 2.16 to 2.84. The water content increased from 46.2 wt.% to 58.99 wt.%. The H element content in the bio-oil increased from 6.61 wt.% to 6.93 wt.%. The dynamic viscosity decreased a little. The results of GC-MS spectrometry analysis showed that the ester compounds in the upgraded bio-oil increased by 3 times. it is possible to improve the properties of bio-oil by hydrotreating and esterifying carboxyl group compounds in the bio-oil.
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盆栽试验方法研究充分供水(W)、适度干旱(M)和严重干旱(D)三种条件下,不同株型的两个大豆品种晋大74和晋豆24在混播和单播时的籽粒产量及生物量构成。结果表明:晋大74品种具有较高的植株生物量和较强竞争能力,在单播时籽粒产量较低,而竞争能力较低的晋豆24品种在单播时籽粒产量却较高,这一结论将对大豆株型设计提供一定的科学依据。
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何首乌为常用中药,由何首乌及含何首乌的中成药制剂所引起的不良反应也时见报道,科学阐明不良反应的物质基础并提出解决方案对何首乌的使用十分重要。本论文研究了何首乌炮制前后KM小鼠肝脏毒性基因表达谱、生物活性及化学成分的变化。所获结果支持何首乌炮制的目的是减毒、改性(改变药效),何首乌生、熟异治的观点。制首乌对抑郁症的效果显著优于生首乌,这与本草所记载的何首乌炮制后补肝肾、益精血,归肝、肾经一致。 主要结果如下: 1、 生、制首乌的毒理基因芯片研究结果 何首乌的不良反应主要表现在肝损害方面。本研究建立了生何首乌和制何首乌不同剂量的肝毒性作用模型,体重指标统计发现生何首乌各剂量组平均体重显著下降,中剂量组(10 g/kg.d)体重下降20 %,高剂量组(20 g/kg.d)体重下降42%,50%动物死亡,提示动物机体能量代谢障碍;基因芯片研究结果表明何首乌是CYP450的抑制剂,生何首乌相对于制何首乌CYP3A4、CYP4A5显著下调,导致毒性成分在体内的吸收增加,服用大剂量的生何首乌后产生明显的肝毒性;主要对以下六条Pathway产生影响:①PPAR signaling pathway,主要毒性靶基因有RXRB CYP7a1、Acadl、Apoa2、Cyp4a、 FABP2 、MAPKKK5等基因。②Calcium signaling pathway,主要毒性靶基因有CAMK2B、CACNA1F、S100A1、 F2R、Ryr1、Slc8a2、Camk4 ③Neuroactive ligand-receptor interaction,主要毒性靶基因有Chrm4、 Ntsr2 、 GABRR1、 GRIK3、F2R等基因。④Wnt signaling pathway,主要毒性靶基因有Daam2、Rac1 等基因。⑤Complement and coagulation cascades,主要毒性靶基因有F2R、Serpina1b、Cfi 、FGA等基因。⑥Oxidative hosphorylation,主要毒性靶基因有Atp5e、NDUFA1等基因。生何首乌毒性明显强于制首乌,且生何首乌水煎液的毒性大于生何乌首丙酮提取物的毒性,这一结果表明,何首乌主要的毒性成分很可能并不仅仅是传统所认为的以大黄素为代表的蒽醌类化合物,而是何首乌中大量存在的有效组分二苯乙烯苷与大黄素相互作用的结果,这一研究结果与前述的何首乌对肝药酶的影响是一致的。后续生、制首乌的化学成分差异研究表明,炮制后二苯乙烯苷含量明显降低:生首乌为5.512 %、清蒸制首乌为3.811 %、豆制首乌为3.538 %,大黄素的含量炮制后显著升高,生首乌为0.094 %、清蒸制首乌为0.119 %、豆制首乌为0.126 %。 2 生、制首乌药效差异研究结果 本文采用慢性中等强度不可预知应激刺激模型(chronic unpredictable mild stress, CUMS)和动物行为绝望实验法,研究生、制首乌抗抑郁活性的差异,制首乌(5 g/kg.d)与模型组相比有显著差异(P< 0.01),生首乌制首乌(5g/kg.d)与模型组相比无显著差异,这一结果表明制首乌抗抑郁活性显著优于生首乌。 本文比较了生、制首乌对四氧嘧啶糖尿病模型小鼠血糖的影响的差异,生首乌(5 g/kg.d)与模型组相比有显著差异(P< 0.01),制首乌(5 g/kg.d)与模型组相比无显著差异,这一结果表明生首乌降糖活性优于制首乌。这一结果与历代中医古书中生首乌治疗消渴症(糖尿病)的记载一致。 3生、制首乌化学成分差异的研究结果 本文选用HPLC-DAD指纹图谱技术结合药效成分含量测定来研究生、制首乌化学成分的差异。炮制后,何首乌中的主要化学成分并未消失,只是其含量发生了改变。炮制后二苯乙烯苷含量明显降低:生首乌为5.512 %、清蒸制首乌为3.811 %、豆制首乌为3.538 %,大黄素的含量炮制后显著升高,生首乌为0.094 %、清蒸制首乌为0.119 %、豆制首乌为0.126 %。 综上所述,炮制前后何首乌中二苯乙烯苷和大黄素含量比的变化可能是何首乌炮制减毒、改性的物质基础。 根据上述结果我们建立了生、制首乌的质量控制新模式。 In recent years, some adverse drug reactions (ADR) about some traditional Chinese medicine were reported at times. As a Chinese medicine most in use, the ADRs of Radix Polygoni multiflori (RPM) and the medicines containing the RPM were also mentioned. The resolution of the problems caused by the ADRs is very important for the use of the RPM as a medicine. The process (or preparation) is a significant feature for the clinical use of the Chinese medicine and an important technology for the safe use and good effect of the Chinese medicine. By processing, the toxicity of the Chinese medicine can be reduced, its properties can be changed and curative effect can be enhanced at the same time. The changes of the gene expression profiles for KM mice hepatotoxic effects, and the change of the biological activity and the chemical composition after being processed of the RPm were studied in the present dissertation. The RPm heatotoxicity mechanism and the toxicity target genes were explained on the gene level for the first time. With the antidepressant activity, and the hypoglycemic effect as the target, the differences on the pharmacodynamics between the processed RPm and unprocessed RPm, for the first time, were investigated. The results obtained show that the antidepressant activity of the processed RPM is far higher than the ones of unprocessed RPm. As we know, the results were reported for the first time. The quality control systems (QCS) for the processed and the unprocessed RPm were founded. The HPLC-DAD was used in the systems founded on the basis of the toxicology and the pharmacodynamics experiments. As we know, the OCSs were reported for the first time. The above-mentioned experimental results confirm that the unique process theory of the traditional Chinese medicine (TCM) used for the process of the Radix Polygoni multiflori (RPm) is correct, i.e after being processed the toxicity of the RPm decreases and its Pharmacodynamic effects change. It is known to author that there have been no similar reports in the literatures up to now. The main experimental results are summarized as follows: 1 The results on the mice toxicology gene chip for the unprocessed and processed RPm The KM mice hepatotoxic model caused by the RPm at the different dosages was established in the present study. The results obtained show that the mouse average body weight obviously decreased in the groups at the different dosages of the unprocessed RPm: the 10 g/kg.d .group decreased 20%; 20 g/kg.d. group decreased 42%, and 50% mice died at 20 g/kg.d. group. The main experimental results on the mice toxicology gene chip The RPm is the CYP450 inhibitor. As compared with the processd RPm, the CYP3A4, CYP4A5 of the unprocessed RPm demonstrate the marked downregulation, which leads to the increase of the poison absorbtion into the body with the result that the unprocessed RPm yields the marked hepatotoxication. The hepatotoxication was produced because the following 6 pathways were affected: ①PPAR signaling pathway, the chief toxicity target genes are RXRB, CYP7a1, Acadl, Apoa2, Cyp4a, FABP2 and MAPKKK5 etc. ②Calcium signaling pathway, the chief toxicity target genes are CAMK2B, CACNA1F, S100A1, F2R, Ryr1,Slc8a2 and Camk4 etc. ③Neuroactive ligand-receptor interaction, the chief toxicity target genes are Chrm4, Ntsr2, GABRR1, GRIK3 and F2R etc. ④Wnt signaling pathway, the chief toxicity target genes are Daam2, Rac1 etc. ⑤Complement and coagulation cascades, the chief toxicity target genes are F2R, Serpina1b, Cfi and FGA etc. ⑥Oxidative phosphorylation, the chief toxicity target genes are Atp5e, NDUFA1 etc. The above experimental results, for the first time , demonstrate on the gene level that the unprocessed Rpm toxicity is far stronger than the processed RPm one, and the toxicity of the water decoction of the unprocessed RPm is greater than the one of its acetone extracts, which shows that the chief toxicity components of the RPm are probably not only the anthraquinones, for example, the emodin, but the complex compounds produced by the interaction between the emondin and the stilbene glucoside which is the largest component of the unprocessed RPm. The result is accordance with the above effect of the RPm on the hepatic drugenzyme. Aftter being processed, in fact, the content of the stibene glucoside in the RPm markedly decreases. 2. The results on the pharmacodynamic differences between the unprocessed and processed RPm The results obtained show that the effects of processing on RPm pharmacodynamic behaviour received in the Chinese Material Medica are correct. It is known to author that this is the first experimental result in the research materials now available. The chief results are as follows: For the treatment of the antidepressant, the curative effect of the processed RPm is far better than the one of the unprocessed RPm. By contrast with the above results, the hypoblycemic effect of the unprocessed RPm is better than the one of the processed RPm. 3. The results on the Chemical Composition The results obtained by using HPLC-DAD fingerprint and by the determination of effective component content show that the main chemical components in the RPm after being processed do not disappear, but their contents change. The contents of the stilbene glucoside (SG) and emodin in the different samples were determined as follows: SG contents 5.512 % for the unprocessed RPm 3.811 % for the processed RPm (Steamed) 3.588 % for the processed RPm (black soybean) Emodin contents 0.094 % for the unprocessed RPm 0.119 % for the processed RPm (Steamed) 0.126 % for the processed RPm (black soybean) The combination of above experimental results on the toxicity, the pharmacodynamics and the chemical composition indicates that the changes of the content ratio of SG/emodin may be the substance base of the toxicity decrease and pharmacodynamic changes of the RPM by the processing.
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胺及其衍生物是很多重要生物活性分子的结构单元,是合成天然产物和手性药物的重要中间体。 直接还原胺化由于其合成步骤简单而成为制备二级胺和三级胺的简便方法。为了发展一种较为简便的直接还原胺化反应,我们把研究的重点放在开发一种简便实用的有机小分子催化方法上。由文献调研可知,现已报道的直接还原胺化方法大多是催化醛或酮与一级胺或者脂肪二级胺的直接还原胺化,而醛或酮与芳香二级胺的直接还原胺化却尚无报道。在本文中,我们发现用简单的四甲基乙二胺(TEMED)在室温下以二氯甲烷为溶剂即可催化三氯氢硅对酮和芳香二级胺之间的直接还原胺化反应,并取得了高达92%的收率。该反应条件温和,底物普适性广,各种类型的酮均可以与芳香二级胺进行直接还原胺化,并且得到比较满意的收率。 同时,我们从手性Sulfoximine出发,设计和合成了一系列的Sulfoximine类新衍生物,并将其应用于间接还原胺化反应中。遗憾的是我们并没有得到预期的不对称催化效果。 Amines and their derivatives are basic structural motifs in natural products and pharmaceuticals and highly versatile building blocks for various organic substrates. Direct reductive amination (DRA) is a convenient method for the preparation of secondary and tertiary amines owing to its operational simplicity. In an effort to develop a simple and convenient procedure for direct reductive amination reaction, we focused our study on search for a mild and efficient organocatalytic system. In the literature, there are many reports concerning DRA between aldehydes or ketones and either primary amines or secondary aliphatic amines. But there are no reports concerning DRA between aldehydes or ketones and secondary aromatic amines. In this study, we have developed a highly practical method for the synthesis of tertiary amines by the direct reductive amination of ketones and secondary aromatic amines with tetramethylethylenediamine (TEMED) as the catalyst using HSiCl3 as the reducing agent in dichloromethane (affording up to 92% yield). This method can be carried out under mild conditions and is compatible with many functional groups. A variety of ketones were efficiently aminated with secondary aromatic amines to afford the corresponding amines in good to excellent yields. Starting from chiral sulfoximine, we designed and synthesized a series of new sulfoximine derivatives and tested their efficiencies as asymmetric organocatalysts for the reduction of imines, which, unfortunately, only exhibited low catalytic activity and enantioselectivity.
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手性胺是合成天然产物和手性药物的重要中间体,亚胺的不对称催化还原是制备光学活性手性胺的最直接有效的方法之一。但是,由于C=N双键的反应活性较弱以及容易发生E/Z异构等问题,亚胺的不对称催化还原具有很大的挑战性,既具有高对映选择性又具有宽广底物普适性的催化剂很少。 本文分别由手性脯氨酸、哌啶酸、哌嗪酸以及氨基醇出发,设计和合成了一系列结构新颖、合成简便、性能优良的酰胺类有机小分子路易斯碱催化剂,以廉价的三氯氢硅为氢源,用这些催化剂催化亚胺不对称还原,得到了非常优良的收率、对映选择性和前所未有的底物普适性。 文献研究认为,除N-甲酰基外,分子内含有芳香酰胺是能催化亚胺还原的有机小分子路易斯碱催化剂具有较高对映选择性的必要条件,我们研究发现N-甲酰脯氨酸非芳香酰胺类催化剂(包括结构简单的C2-对称型脯氨酰胺类催化剂),对N-芳基酮亚胺的还原可获得达86%的对映选择性,远高于同类芳香酰胺催化剂,证明N-甲酰非芳香酰胺类路易斯碱催化剂在亚胺还原中也能得到高的对映选择性。 在进一步研究中,我们以手性六元哌啶酸为模板,分别设计合成了N-甲酰哌啶酸芳香酰胺和N-甲酰哌啶酸非芳香酰胺两类催化剂,其中芳香酰胺催化剂(S)-N-(甲酰基)哌啶-2-酸-1-萘基酰胺(28)和非芳香酰胺催化剂(2S,1'S,2'S)-N-(甲酰基)-哌啶-2-酸(1',2'-二苯基-2'-乙酰氧基-乙基)酰胺(30)显示出非常优良的催化活性和对映选择性,对于N-芳基芳香酮亚胺的还原,无论是缺电子体系还是富电子体系,绝大部分都能得到很高的收率(达98%)和对映选择性(达96% ee)。特别值得一提的是30对一些脂肪族亚胺和α,β-不饱和亚胺的还原,虽然底物为E/Z混合物,也能得到很高的收率(达93%)和对映选择性(达95% ee),这样的底物普适性在过渡金属催化体系中也是前所未有的。 现有的催化亚胺还原的高对映选择性催化体系大多仅适用于甲基酮亚胺底物,对位阻较大的非甲基酮亚胺很难获得好的结果。我们以L-哌嗪酸为模板设计和合成出的(S)-N-(甲酰基)-哌嗪-2-酸-4-对叔丁基苯磺酰基-苯基酰胺不但对N-芳基甲基酮亚胺有很好的对映选择性(达90% ee),而且对于大位阻的N-芳基非甲基酮亚胺有更好的对映选择性(达97% ee)。该催化剂与30在底物普适性方面具有很好的互补性。 我们还设计了基于1,2-二苯基氨基醇为模板的新型N-甲酰路易斯碱有机小分子催化剂,首次发现结构简单的N-甲酰(1S,2R)二苯基氨基醇能较好的催化N-芳基酮亚胺,最高可以得到82%的对映选择性。 针对我们设计合成的结构新颖、性能优良的催化剂,我们对催化机理进行了探讨和解释,提出了几个假想的机理模型。 Catalytic enantioselective reduction of imines represents one of the most straightforward and efficient methods for the preparation of chiral amines, an important intermediate for the synthesis of natural products and chiral drugs. However, asymmetric reduction of imines remains a big challenge and highly enantioselective catalysts with a satisfactorily broad substrate scope remain elusive. Factors contributing to the difficulty of this transformation include the weak reactivity of the C=N bond and the existence of inseparable mixtures of E/Z isomers. Starting from chiral proline, pipecolinic acid, piperazine-2-carboxylic acid and 1,2-diphenyl amino alcohol, a series of structurally simple and easily prepared amides were developed as highly effective Lewis basic organocatalysts for the asymmetric reduction of imines with trichlorosilane as the reducing agent, which promoted the reduction of N-aryl imines with high yields and excellent enantioselectivities with an unprecedented substrate spectrum. In the literature, it has been believed that besides the N-formyl group, the existence of an arylamido group in the structure of Lewis basic organocatalysts is a prerequisite for obtaining high enantioselectivity in the catalytic reduction of imines. However, we found that the N-formyl-L-prolinamides bearing non-arylamido groups, including structurally simple C2-symmetric tetraamides, could also work as effective Lewis basic catalysts to promote the asymmetric reduction of ketimines with high enantioselectivities (up to 86% ee), which are even more enantioselective than the analogues with arylamido groups. In further studies, we developed novel N-formamides with arylamido groups and non-arylmido groups as Lewis basic catalysts using the commercially available L-pipecolinic acid as the template. The catalysts (S)-1-formyl-piperidine-2-carboxylic acid naphthylamide 28 and (2S,1'S,2'S)-acetic acid 2-[(1-formyl-piperidine-2-carbonyl) -amino]-1,2-diphenyl-ethyl ester 30 were found to promote the reduction of a broad range of N-aryl imines in high yields (up to 98%) and excellent ee values (up to 96%) under mild conditions. Furthermore, catalyst 30 also exhibited high enantioselectivities (up to 95% ee) for the challenging aliphatic ketimines and α,β-unsaturated imines despite that these imines exist as E/Z isomeric mixtures. The broad substrate spectrum of this catalyst is unprecedented in catalytic asymmetric imine reduction, including transition-metal-catalyzed hydrogenation processes. Many of the currently available highly enantioselective catalytic systems only tolerate methyl ketimines, which gave poor results for bulkier non-methyl ketimines. Starting from L-piperazine-2-carboxylic acid, we developed (S)-4-(4-tert- butylbenzenesulfonyl)-1-formyl-N-phenyl-piperazine-2-carboxamide as highly enantioselective Lewis basic catalysts for the hydrosilylation of both methyl ketimines and steric bulky non-methyl ketimines. Moreover, higher enantioselectivities were obtained for non-methyl ketimines than methyl ketimines under the catalysis of this catalyst. Thus, this catalyst system complements with 30 in terms of the substrate scope. We also found that easily accessible (1R,2S)-N-formyl-1,2-diphenyl- 2-aminoethanol worked as an effective Lewis basic catalyst in the enantioselective hydrosilylation of ketimines, affording high enantioselectivities (up to 82% ee) for a broad range of ketimines. To rationalize the high efficiencies of the structurally novel catalysts we developed, several catalytic models have been proposed.