全文获取类型
收费全文 | 8090篇 |
免费 | 335篇 |
国内免费 | 622篇 |
专业分类
化学 | 4886篇 |
晶体学 | 250篇 |
力学 | 87篇 |
综合类 | 60篇 |
数学 | 2349篇 |
物理学 | 1415篇 |
出版年
2024年 | 12篇 |
2023年 | 66篇 |
2022年 | 71篇 |
2021年 | 114篇 |
2020年 | 148篇 |
2019年 | 178篇 |
2018年 | 99篇 |
2017年 | 119篇 |
2016年 | 133篇 |
2015年 | 142篇 |
2014年 | 176篇 |
2013年 | 669篇 |
2012年 | 492篇 |
2011年 | 645篇 |
2010年 | 590篇 |
2009年 | 715篇 |
2008年 | 645篇 |
2007年 | 579篇 |
2006年 | 471篇 |
2005年 | 367篇 |
2004年 | 349篇 |
2003年 | 286篇 |
2002年 | 373篇 |
2001年 | 165篇 |
2000年 | 156篇 |
1999年 | 141篇 |
1998年 | 124篇 |
1997年 | 117篇 |
1996年 | 121篇 |
1995年 | 100篇 |
1994年 | 91篇 |
1993年 | 56篇 |
1992年 | 64篇 |
1991年 | 40篇 |
1990年 | 23篇 |
1989年 | 11篇 |
1988年 | 13篇 |
1985年 | 39篇 |
1984年 | 20篇 |
1983年 | 22篇 |
1982年 | 24篇 |
1981年 | 47篇 |
1980年 | 31篇 |
1979年 | 17篇 |
1978年 | 25篇 |
1977年 | 33篇 |
1976年 | 28篇 |
1975年 | 23篇 |
1974年 | 24篇 |
1973年 | 22篇 |
排序方式: 共有9047条查询结果,搜索用时 21 毫秒
111.
纳米α-FeOOH催化剂一段法脱除COS和H2S性能的研究 总被引:11,自引:1,他引:11
利用均相沉淀法、氨水滴定法制备纳米α-FeOOH粒子,以该粒子为活性组分制备催化剂,利用微反-色谱联用活性评价技术,在常压、空速10 000 h-1、25 ℃~60 ℃温度范围内考察了纳米α-FeOOH催化剂对COS催化水解的活性。采用热重法对纳米α-FeOOH催化剂脱除H2S的性能进行了研究。结果表明:纳米α-FeOOH催化剂对COS水解在低温度、大空速下具有高的活性,系列Ⅰ和系列Ⅱ催化剂分别在60 ℃和40 ℃~45 ℃时COS转化率达到100%。在60 ℃时各种催化剂吸附H2S的能力最强,最高饱和硫容可达到21.72w%。催化剂表面能量分布不均匀,COS催化水解在低温时存在补偿效应。 相似文献
112.
Lam WH Jia G Lin Z Lau CP Eisenstein O 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(12):2775-2782
Theoretical calculations on the metathesis process, [Tp(PH3)MR(eta 2-H[bond]CH3)] --> [Tp(PH3)M(CH3)(eta 2-H[bond]R)] (M=Fe, Ru, and Os; R=H and CH3), have been systematically carried out to study their detailed reaction mechanisms. Other than the one-step mechanism via a four-center transition state and the two-step mechanism through an oxidative addition/reductive elimination pathway, a new one-step mechanism, with a transition state formed under oxidative addition, has been found. Based on the intrinsic reaction coordinate calculations, we found that the trajectories of the transferring hydrogen atom in the metathesis processes studied are similar to each other regardless of the nature of reaction mechanisms. 相似文献
113.
Pentacoordinate complex cations of the general formula [(C6F5)2SbL3]3+ stabilized as solid salts in combination with tetraphenylborate (BPh4), tetrafluorobroate (BF4) anions, where L=DMSO, Ph3AsO, PyO, DMF, α-, β- and γ-picoline have been isolated. The newly formed complexes were characterized by elemental analysis, molar conductance measurements, solid-state IR and and NMR. From these results, a five-fold coordination around antimony was required. 相似文献
114.
115.
A spectrophotometric study on a direct picric acid reaction for creatinine in severely jaundiced serums is described. A problem appears to be caused by the oxidation of bilirubin which minimizes rising absorbance when using continuous measurement. Simple examples of interferences with the kinetic mode are shown along with the hitherto unreported interference of the drug, Cephalothin, which also undergoes a picric acid reaction. A procedure in which a delta absorbance is obtained after decolorization of the Jaffé complex by acidification is shown as one available means for obviating the bilirubin effect. However, the theory that Jaffé-reactive interferences do not decolorize with the same acid treatment is not totally applicable when the drug, Cephalothin, is present. 相似文献
116.
2-Substituted secondary alcohol o-DPPB esters (o-DPPB=ortho-diphenylphosphanylbenzoyl) have been prepared and their o-DPPB-directed diastereoselective hydroformylation examined. It was found that the diastereoselectivity increased as a function of the steric demand of the substituents both at the stereogenic center and in the alkene 2-position. Hydrolytic cleavage of the o-DPPB group afforded-via the lactols 29-the corresponding lactones 30, the relative configurations of the vicinal stereogenic centers of which were ascertainable by 2D-NOESY spectroscopy. In addition, a crystal structure analysis of the hydroformylation product 2 d provided further confirmation of the relative configuration. Replacement of the ester carbonyl group of the o-DPPB by a methylene unit resulted in significantly worse diastereoselectivity in the course of the hydroformylation (34-->35), which indicates a decisive role for the ester carbonyl function. All the experimental observations were combined in a model of the origin of the 1,2-asymmetric induction during the title reaction. The key feature is the consideration of diastereomeric trigonal-bipyramidal rhodium-hydrido-olefin complexes I and II, capable on the basis of the Hammond postulate of acting as good models for the transition states of the selectivity-determining hydrometalation step. Investigation of these complexes by force-field methods indicated good correlation between theoretically predicted and experimentally determined diastereoselectivities. 相似文献
117.
在三乙胺的作用下,利用(S)-3-羟甲基-1,2,3,4-四氢异喹啉((S)-TicOL)和Ph2PCl缩合,得到六元N-杂环配体(S)-TIAMPP.研究了(S)-TIAMPP与Rh(I)形成的手性催化剂[Rh((S)-TIAMPP)(COD)]BF。在脱氢氨基酸的衍生物中不对称催化加氢的对映选择性和适应性,以及该催化剂对N-苯甲酰基脱氢肉桂酸甲酯加氢过程中温度、压力、反应溶剂、底物与催化剂比例(S/C)对光学收率的影响.结果表明,在S/C=100,15℃,1.0MPa的甲醇溶液中,反应24h,[Rh((S)-TIAMPP)(COD)]BF。对N-苯甲酰基脱氢肉桂酸甲酯加氢的光学收率可达到96%. 相似文献
118.
Frey PA 《Chemical record (New York, N.Y.)》2001,1(4):277-289
Research on the mechanism of action of coenzyme B12, adenosylcobalamin, as a graduate student introduced the author to the field of organic free radicals in enzymology. Twenty years later, related work on S-adenosylmethionine (SAM) as a "poor man's coenzyme B12" was initiated in a detailed analysis of the mechanism of action of lysine 2,3-aminomutase (LAM). The interconversion of L-lysine and L-beta-lysine is catalyzed by LAM, which requires SAM, pyridoxal-5'-phosphate (PLP), and a [4Fe-4S] cluster as coenzymes. The mechanism of this reaction has been delineated as a radical isomerization, in which radical formation is initiated by the [4Fe-4S]-dependent cleavage of the SAM into methionine and the 5'-deoxyadenosyl radical. The mechanism of this process is discussed, together with the role of this radical in hydrogen abstraction from lysine to initiate the substrate radical isomerization. The chemistry underlying the functions of SAM, PLP, and [4Fe-4S] in the action of LAM is novel in all respects, except for the formation of a lysine-PLP aldimine at the active site. Of the four free radicals in the mechanism, three have been characterized by EPR spectroscopy. In the suicide inactivation of adenosylcobalamin-dependent dioldehydrase (DDH) by glycolaldehyde, the formation of cob(II)alamin and 5'-deoxyadenosine is accompanied by the conversion of glycolaldehyde to cis-ethanesemidione radical at the active site. The cis-ethanesemidione radical has been characterized by EPR spectroscopy. Its exceptional stability at the active site is the basis for the inactivation of DDH by glycolaldehyde. 相似文献
119.
John A. Bishop 《Analytica chimica acta》1973,63(2):305-311
Four different methods for the calculation of the formation constants of fluorescing complexes are discussed. The methods were used to determine constants for the complexes of aluminum(III), gallium(III) and indium(III) with 8-quinolinol-5-sulfonate anion. 相似文献
120.
Thomas Kauffmann 《Angewandte Chemie (International ed. in English)》1997,36(12):1258-1275
Hitherto there was no reaction known that permits transformations of R1R2-CO → 0.5 R1R2R3C–CR1R2R3 in one step. This type of additive–reductive carbonyl dimerization is now possible using alkoxy(alkyl)tungsten(v) complexes with aromatic, heteroaromatic or α,β-unsaturated aldehydes and ketones. When a corresponding phenyl complex was employed in a test experiment, it was revealed that an aliphatic ketone could be used as the substrate in this reaction. A second interesting type of reaction is the transformation of CH3 ligands into μ-CH2 ligands, which occurs during the treatment of MeLi or Me3Al with molybdenum or tungsten chlorides (oxidation states VI and V, for Mo additionally IV) at low temperatures with liberation of CH4. Here, the question arises as to whether the intermediate involved has a terminal CH2 ligand (Schrock carbene complex) or a μ-CH3 ligand (CH3 bound by a two-electron three-center bond to two metal atoms). Of all the μ-CH2 complexes obtained, those which were synthesized by the action of MeLi on molybdenum chlorides can be recommended as reagents for carbonylmethylenation of aldehydes and ketones. They display high selectivity, very low basicity, a surprising resistance to protons, they are readily available, can be easily modified and, as regards their selective behavior, they have been investigated more thoroughly than other readily accessible carbonylmethylenation reagents of comparable selectivity. The results of NMR spectroscopic investigations on the structure of the μ-CH2 complexes, and associated reaction mechanisms are discussed. A survey of carbonylmethylenation reagents, which have been reported in the literature, permits comparisons to be made with carbonylmethylenating molybdenum and tungsten complexes. 相似文献