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reaction pathway     
相关语句
  反应途径
     ②Signal transduction of interleukin receptor: JAK-STAT pathway, Ras-MAPK cascade reaction pathway and p13k pathway.
     ②白细胞介素受体的信号转导:包括JAK-STAT途径、Ras-MAPK级联反应途径和p13k途径。
短句来源
     The analysis along IRC indicated that the breakage of C—H bond and formation of H—O bond was a concerted process, and furthermore along the reaction pathway there existed a vibrational mode which lead to successful reaction. The domain of the reaction promoted by the vibrational mode was S=-0.35—0.85 (amu)~(1/2)Bohr.
     沿内禀反应坐标(IRC)的分析指出,C—H键断裂和H—O键生成是以协同方式进行的,且在反应途径上存在一个引导反应进行的振动模式,这一振动模式引导反应进行的区间为S=-0.35~0.85(amu)1/2Bohr;
短句来源
     Transition state for the isomerization is studied by using reaction pathway method.
     用反应途径法(reaction pathway)得到了甲酸顺反异构化的过渡态。
短句来源
     A possible reaction pathway for 2,4-D degradation by H2O2 involving all intermediates detected was proposed.
     通过GC-MS、HPLC、IC分析,检测出中间产物2,4-二氯苯酚、乙醇酸、乙醛酸、苯醌、顺丁烯二酸、草酸等,并推出O_3/H_2O_2氧化降解2,4-D的反应途径
短句来源
     The reaction pathway in which OH radical generated from the interaction of Fe 2+ with H 2O 2 was investigated theoretically at the B3LYP/6-311G ** level. The role of ferrous ion in the radical generation was studied.
     利用B3LYP方法 ,在 6 3 11G 基组下研究了气相中Fe2 +与H2 O2 作用生成OH自由基的反应途径 ,探讨了铁离子对生成羟基自由基所起的作用 .
短句来源
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  反应路径
     In-Situ Transient DRIFTS Studies of the Reaction Pathway of n-Butane Selective Oxidation over (VO)_2P_2O_7 Catalysts
     (VO)_2P_2O_7催化剂上正丁烷选择氧化反应路径的原位瞬态DRIFTS研究
短句来源
     A reaction pathway in CuO/CeO_2 system for COwas proposed involving surface reaction at the copper-CeO_2 interface.
     提出CuO/CeO_2体系中CO 氧化的反应路径,反应涉及Cu-CeO_2界面反应。
短句来源
     TREATMENT OF ALCOHOLS WASTEWATER USING UPERCRITICAL WATER OXIDATION (Ⅱ) REACTION PATHWAY AND KINETICS
     超临界水氧化法处理醇类废水(Ⅱ)反应路径及动力学
短句来源
     Study on the reaction pathway and kinetics of ethanol wastewater disposal by supercritical water oxidation
     乙醇废水的超临界水氧化反应路径及动力学研究
短句来源
     At the G2∥UMP2/6 311+G ** level, the reaction pathway of Cl with HCOOH oxidation reaction was discussed in this paper. The dominant initial step is Cl atom attacking H on C in trans formic acid through a barrier hight of 16 7 kJ/mol to form cis HOCO radical R1a.
     用从头算UMP2方法采用 6 3 11+G 基组详细研究了Cl原子与甲酸反应的最佳反应路径 ,对所有驻点都进行了G2单点能校正 ,结果表明 :在Cl与HCOOH反应的过程中 ,Cl原子主要夺取trans HCOOH中C端的H原子 ,产生cis HOCO基团 ,反应的势垒为 16 7kJ/mol.
短句来源
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  反应通道
     The main reaction pathway is CH3CF2O2 +HO2→IM1→TS1→CH3CF2OOH+O2, the corresponding activation energy is 77.21 kJ·mol-1, and the main products are O2 and CH3CF2OOH.
     通道CH3CF2O2+HO2邛IM1邛TS1邛CH3CF2OOH+O2的活化能为77.21kJ·mol-1,活化能较低,为主要反应通道,其产物是O2和CH3CF2OOH.
短句来源
     Comparatively,the reaction pathway:CH+NO→IM6(cis)→TS8(cis-trans)→IM7(trans)→TS9→N+HCO was the main pathway and its activation energy was 144.6 kJ/mol.
     理论分析表明,反应通道CH+NO→IM6→TS8→IM7→TS9→N+HCO控制步骤的活化能最低(144.6 kJ/mol),为主要反应通道.
短句来源
     Comparing the two pathways' activation energies, one can find that the main reaction pathway is NO+OH→IM1→TS2→IM2(HNO_2) and the main product is HNO_2.
     研究发现,通道NO+OH→IM1→TS2→IM2(HNO2)是NO与OH自由基反应的主反应通道,其主要产物是HNO2.
短句来源
     From the research on the mechanism of the reaction between HCO radical and NO_2, one can see that the reaction has several pathways and many steps, and activation energies of these pathways' control steps are 112.49 and 291.49 kJ·mol~(-1), respectively. Relatively, the pathway: HCO+NO_2→CO+HONO has the smallest activation energy, which is the main reaction pathway.
     从对HCO自由基与NO2的反应机理的研究结果看,HCO自由基与NO2反应的几条通道控制步骤的活化能分别为112.49和291.49kJ·mol-1,反应HCO+NO2→HONO+CO的活化能较低为主反应通道.
短句来源
     Furthermore, we obtained the energy barriers of two reactions with QCISD(T)/6-311G * and are corrected by zero-point energy. The information along the two reaction paths was gained. It is found that the reaction NH 2+CH 4NH 3+CH 3 is main reaction pathway.
     在 QCISD( T) /6 -31 1 G*水平下进行了单点能计算 ,并进行了零点能校正 ,结果表明 ,反应 NH2 + CH4NH3 + CH3 是主要的反应通道 .
短句来源
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  反应历程
     Reaction Pathway of Normal Paraffin Hydroisomerization over Pt/SAPO-11 Catalyst
     正构烷烃在Pt/SAPO-11催化剂上的临氢异构化反应历程(英文)
短句来源
     It was found that the carburizing reaction pathway of NiO-MoO_3 was NiO-MoO_3→Ni-MoO_xC_y→Ni-Mo_2C in CH_4/H_2 mixture,and its carburizing temperature decreased with the increase of Ni/Mo atom ratio.
     NiO作为助剂添加到MoO3中后,NiO-MoO3在CH4/H2气氛中的还原碳化反应历程为NiO-MoO3→Ni-MoOxCy→Ni-Mo2C,相应的还原碳化温度降低。 随Ni/Mo原子比的增大,制备的NiO-MoO3在CH4/H2气氛中还原碳化的温度降幅增大。
短句来源
     STUDY ON REACTION PATHWAY IN COMMERCIAL RISER OF RESIDUUM CATALYTIC CRACKING UNIT
     重油催化裂化装置提升管内反应历程研究
短句来源
     EXPERIMENTAL SIMULATION OF REACTION PATHWAY IN COMMERCIAL FCC RISER PROCESSING HEAVY OIL
     重油催化裂化工业提升管内反应历程的实验模拟
短句来源
     The analysis of the reaction products with GC / MS shows that the main products are benzoic acid(28.4%)and benzophenone(33.4%) while dibenzyl ethanedinone is scanty. So it is believed that the reaction proceeds via carbon cation electrophilic substitution reaction-free radical substitution reaction pathway.
     反应产物的GC/MS检测结果表明,苯甲酸(28.4%)和二苯甲酮(33.4%)是主要产物,而二苯乙二酮的量却很少,推测该反应经历了碳正离子亲电取代-自由基取代反应历程
短句来源
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  reaction pathway
It was shown that the reaction pathway and efficiency of the photochemical processes observed for a given radical cation in different matrices with similar physical and chemical characteristics could considerably differ.
      
Mechanism of Aromatic Hydrocarbon Acylation by Substituted Benzoic Acids: A Novel Reaction Pathway
      
The high selectivity over tungsten sulfide catalysts is suggested to be due to the reaction pathway through thiophene protonation mediated with the surface SH groups and to the inhibition of hydrogenolysis.
      
At I/Ol = 14, isobutane alkylation with butenes is the main reaction pathway, which results in the complete conversion of the butenes to C8 alkylation products.
      
The effect of methyl substituent in the pyridine molecule on the reaction pathway was evaluated.
      
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In a previous paper we reported that under flashes of the same duration and intensity, the nonoyclic PSP [FMN, Vit. K or Fe (CN)_6~≡ system] requires a longer dark time than the cyclic PSP (PMS system) to produce maximum flash yields (MFY) indicating that a longer dark reaction pathway exists in the former system. There were indications that they may differ also in the photochemical reaction paths, since their behavior toward o-phenanthroline (a photochemical inhibitor) is different. It was also...

In a previous paper we reported that under flashes of the same duration and intensity, the nonoyclic PSP [FMN, Vit. K or Fe (CN)_6~≡ system] requires a longer dark time than the cyclic PSP (PMS system) to produce maximum flash yields (MFY) indicating that a longer dark reaction pathway exists in the former system. There were indications that they may differ also in the photochemical reaction paths, since their behavior toward o-phenanthroline (a photochemical inhibitor) is different. It was also reported that the noncyclic PSP has a higher MFY than the cyclic and both are affected by temperature. But the light flashes formerly used were rather long and interpretation was difficult. It is desirable to compare the two systems under shorter flashes of high intensity.These conditions were obtained by using natural sunlight reflected by a rotating mirror. The rapidly passing beam was focussed by a convex lens to the reaction vessel (Fig. 1). Flashes of 3.3×10~(-4) sec. with dark interval of 0.16 sec. could be obtained and the intensity was found to be saturating (Table 1). Long light flashes were obtained with rotating disc as in the previous paper. Preparation of reaction mixtures and analytic procedures were as earlier described.The following results were obtained:(1) Under short flashes (3.3 x 10~(-4) sec.)similar MFY are found in both cyclic and noncyclic PSP systems [PMS, Vit. K, FMN, Fe (CN)_6~≡]. And the MFY is not significantly affected by temperature (Table 2).(2) The concentration of o-phenanthroline for 50% inhibition of the MFY is 4.5×10~(-5) M in the PMS system and 0.95×10~(-5) M in the Vit. K (Fig. 2), FMN and Fe(CN)_6~≡ systems (Fig. 3).(3) In continuous light of low intensity (250lux) the concentration of o-phenanthroline for 50% inhibition of PSP is 0.95×10~(-5)M for the Vit. Kand 4.5×10~(-5) M for the PMS systems, being the same as in short flashes of saturating intensity. But in continuous light of high intensities (100,000lux) the concentration of the inhibitor required is higher in both cases. It is still higher if the temperature is increased from 5 to 30℃ (Fig. 2 and 4, Table 3). The temperature quotient (Q_(10) for the PMS system is 1.2 and for the Vit. K system 2.6.(4) The inhibition of MFY by o-phenanthroline is not affected by flash intensity (Vit. K system, Fig. 5) but is decreased by increasing flash duration (Fig.6 and 7).Two conclusions are tentatively drawn from the above results. (A) o-phenanthroline inhibits primarily the photochemical reaction center. The decreases in inhibition affected by longer flash durations and in continuous light by higher light intensities and higher temperatures are probably due to the increased rate of dark reactions leading to a more rapid turnover, i. e. repetition of the photochemical reaction center. (B) The same MFY in both cyclic (PMS) and noncyclic (Vit. K etc.) PSP shows that the number of phosphorylation site is the same in both systems. The higher sensitivity toward o-phenanthroline in the later system indicates that it has probably two photochemical reaction centers, one of which is concerned with O_2 evolution which is lacking in the former system.

在暗間隔0.16秒的3.3×10~(-4)秒閃光下,比較了PMS,Vit.K,FMN及Fe(CN)_6~≡光合磷酸化反应系統的每閃最高产量以及温度的影响,并观察邻二氮杂菲对这些反应系統每閃最高产量抑制的差异,以及在閃时延长时,它对閃光产量抑制程度的变化,得到結果如下: (1)在短閃光下,PMS,Vit.K,FMN及Fe(CN)_6~≡光合磷酸化反应系統的每閃最高产量都极接近,温度的影响也不太显著。(2)邻二氮杂菲对Vit.K,FMN及Fe(CN)_6~≡非循环光合磷酸化反应系統的每閃最高产量的50%抑制濃度都在0.96×10~(-5)M/左近,而对PMS系統的每閃最高产量的50%抑制濃度則力4.5×10~(-5)M。(3)邻二氮杂菲对PMS及Vit.K这两种类型的光合磷酸化反应系統在連續弱光下反应速度的50%抑制濃度与对这两反应系統的每閃最高产量的50%抑制濃度相同,即分别为4.5×10~(-5)M及0.95×10~(-5)M;同样温度(5℃)而光强增加到100000米烛光,则对这两反应系统反应速度的50%抑制浓度提高到依次为14.0×10~(-5)M及2.3×10~(-5)M。如果再把温度从5℃提升到30℃...

在暗間隔0.16秒的3.3×10~(-4)秒閃光下,比較了PMS,Vit.K,FMN及Fe(CN)_6~≡光合磷酸化反应系統的每閃最高产量以及温度的影响,并观察邻二氮杂菲对这些反应系統每閃最高产量抑制的差异,以及在閃时延长时,它对閃光产量抑制程度的变化,得到結果如下: (1)在短閃光下,PMS,Vit.K,FMN及Fe(CN)_6~≡光合磷酸化反应系統的每閃最高产量都极接近,温度的影响也不太显著。(2)邻二氮杂菲对Vit.K,FMN及Fe(CN)_6~≡非循环光合磷酸化反应系統的每閃最高产量的50%抑制濃度都在0.96×10~(-5)M/左近,而对PMS系統的每閃最高产量的50%抑制濃度則力4.5×10~(-5)M。(3)邻二氮杂菲对PMS及Vit.K这两种类型的光合磷酸化反应系統在連續弱光下反应速度的50%抑制濃度与对这两反应系統的每閃最高产量的50%抑制濃度相同,即分别为4.5×10~(-5)M及0.95×10~(-5)M;同样温度(5℃)而光强增加到100000米烛光,则对这两反应系统反应速度的50%抑制浓度提高到依次为14.0×10~(-5)M及2.3×10~(-5)M。如果再把温度从5℃提升到30℃,则50%抑制浓度更提高到25.0×10~(-5)M及4.0×10~(-5)M。(4) 邻二氮杂菲对Vit.K系统的短闪光的每闪最高产量的抑制程度不受闪光光强影响,然而当闪光的闪时增加时,抑制剂对闪光产量的抑制程度则随闪时增加而减少。由此推论,邻二氮杂菲的抑制部位与光合磷酸化反应的光化作用中心有关,增加闪光闪时,或在连续光下增加光强,或在饱和光下提高温度都使光化作用中心增加重复利用而使抑制剂的抑制作用减弱。循环(PMS)及非循环(Vit.K,FMN,Fe(CN)_6~≡)光合磷酸化反应系统的闪光产量相同,而对邻二氮杂菲的敏感程度却相差很大的现象,可以用放氧及磷酸化各有一光化作用中心解释之。非循环光合磷酸化反应系统包括有放氧及磷酸化两个,而循环光合磷酸化反应系统则仅需磷酸化一个光化作用中心。

When Knorr-Paal condensation is to be employed in synthetic work, the experimental conditions must be designed according to the two feasible reaction pathways and four possible catalytic conditions which we have so far discovered in mechanism studies. For the condensation with strongly nucleophilic amine no catalyst or only basic catalyst should be used while for that with weakly nucleophilic amine or with one of considerable sterlc resistance an acid catalyst ought to be applied. And then the reaction...

When Knorr-Paal condensation is to be employed in synthetic work, the experimental conditions must be designed according to the two feasible reaction pathways and four possible catalytic conditions which we have so far discovered in mechanism studies. For the condensation with strongly nucleophilic amine no catalyst or only basic catalyst should be used while for that with weakly nucleophilic amine or with one of considerable sterlc resistance an acid catalyst ought to be applied. And then the reaction rate will be at its maximum when the ratio of the aminium salt formed with the catalytic acid to the free amine is close to one (i. e. when the pH of the reaction medium is close to the pK_a of the amine). Therefore, for very unreactive amines Lewis acid has to be prosent before a perceptible reaction can be started. Since every step in this reaction course is reversible to a considerable extent, measures should be taken to break the unfavorable equillibria and to avoid excessive side reactions. Seven kinds of difficult cases met in synthetic work were cited from the literature and possible ways of how to circumvent these difficulties were discussed.

在Knorr—Paal缩合合成工作中,最好按我们已发现的两种可能反应过程和四种催化情况考虑合成的条件。强亲核性胺的缩合无须用催化剂或可用碱性催化剂;弱亲核胺或具有较大空间位阻的胺的缩合则必须用酸性催化剂。反应速率以催化酸所形成的铵盐与游离胺的比率接近1时达极大值(此时介质的pH接近于胺的pK_a)。故反应活性很差的胺必需用Lewis酸催化才能引起反应。因本反应中各步均有颇强的可逆性,宜采取措施以打破其不利的化学平衡和避免过多的副反应。本文还讨论了文献中谈到的、在合成上遇到的七种困难情况和绕过这些困难的叮能途径。

Mechanism of condensation of formaldehyde with isobutene on the solid acid-basic catalyst has been investigated by means of the approximate molecular orbital method of MINDO/2. The geometrical configurations of various intermediate species adsorbed on the solid acid-basic catalyst were optimized with SIMPLEX method. According to the experimental facts and the general principles of quantum chemistry, calculations and discussions were made for the eight states (see Fig. 4) in the course of the condensation reaction....

Mechanism of condensation of formaldehyde with isobutene on the solid acid-basic catalyst has been investigated by means of the approximate molecular orbital method of MINDO/2. The geometrical configurations of various intermediate species adsorbed on the solid acid-basic catalyst were optimized with SIMPLEX method. According to the experimental facts and the general principles of quantum chemistry, calculations and discussions were made for the eight states (see Fig. 4) in the course of the condensation reaction. For the following three parts, the quantum chemical calculations were performed: ( 1 ) the effects of the acidic and basic property of catalysts on the reactivity of formaldehyde, ( 2 ) the effects of the acid-basic property of catalysts on the reactivity of isobutene, and ( 3 ) the possible reaction pathways of the condensation between formaldehyde and isobutene on the acid-basic catalysts. Calculation results indicate that ( 1 ) the formaldehyde is mainly adsorbed on the acidic sites, and ( 2 ) the cooperative action of acidic and basic sites is important in the condensation reaction of the formaldehyde with isobutene, this action promotes the reduction of the repulsive energies in the first stage of the condensation reaction, increases the selectivity of the condensation reaction, and prevents the methyl group of isobutene from thermal decomposition. Calculations have also shown that the most important transition state is the form of "enol" structure formed in the course of condensation. The dehydration process proceeds via an oxygen of formaldehyde and basic site to capture two hydrogens of methyl group of isobutene respectively. The calculated energy barrier is rather satisfactory.

运用近似分子轨道理论MINDO/2方法,对甲醛和异丁烯在酸碱固体催化剂表面上的缩合反应进行了量子化学计算,按照SIMPLEX方法实现各种酸碱吸附态以及反应过程中各状态能量的几何构型最优化。根据本所甲醛和异丁烯气相一步合成异戊二烯的实验和量子化学一般原理,设计了由八个状态组成的反应途径,较详细地讨论了它们的反应机理。 计算结果指出:反应中甲醛均以酸吸附为主。体系中适量的碱性物质产生的酸碱协同效应,对于降低反应的初始排斥能是重要的,并且有利于提高反应选择性,防止异丁烯甲基的热分解。计算还指出:本反应的中间过渡态主要是形成一种“类烯醇互变”的状态,该脱水过程是由甲醛上的氧和碱性中心分别夺取异丁烯的甲基上两个氢。计算得到的势能位垒比较满意。

 
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