全文获取类型
收费全文 | 15650篇 |
免费 | 1318篇 |
国内免费 | 927篇 |
专业分类
化学 | 5886篇 |
晶体学 | 154篇 |
力学 | 1071篇 |
综合类 | 144篇 |
数学 | 7529篇 |
物理学 | 3111篇 |
出版年
2023年 | 93篇 |
2022年 | 169篇 |
2021年 | 226篇 |
2020年 | 351篇 |
2019年 | 353篇 |
2018年 | 350篇 |
2017年 | 413篇 |
2016年 | 413篇 |
2015年 | 331篇 |
2014年 | 546篇 |
2013年 | 1075篇 |
2012年 | 599篇 |
2011年 | 755篇 |
2010年 | 637篇 |
2009年 | 867篇 |
2008年 | 744篇 |
2007年 | 833篇 |
2006年 | 742篇 |
2005年 | 779篇 |
2004年 | 860篇 |
2003年 | 771篇 |
2002年 | 691篇 |
2001年 | 580篇 |
2000年 | 558篇 |
1999年 | 438篇 |
1998年 | 381篇 |
1997年 | 377篇 |
1996年 | 333篇 |
1995年 | 292篇 |
1994年 | 323篇 |
1993年 | 238篇 |
1992年 | 227篇 |
1991年 | 160篇 |
1990年 | 128篇 |
1989年 | 109篇 |
1988年 | 105篇 |
1987年 | 112篇 |
1986年 | 105篇 |
1985年 | 104篇 |
1984年 | 91篇 |
1983年 | 30篇 |
1982年 | 70篇 |
1981年 | 63篇 |
1980年 | 68篇 |
1979年 | 94篇 |
1978年 | 75篇 |
1977年 | 80篇 |
1976年 | 54篇 |
1974年 | 21篇 |
1973年 | 24篇 |
排序方式: 共有10000条查询结果,搜索用时 78 毫秒
211.
Itsuo Furuoya 《Catalysis Surveys from Japan》1999,3(1):71-73
The vapor phase catalytic reaction between aromatic carboxylic acid and acetic acid was investigated. Many metal oxides catalyzed the reaction between 2methylbenzoic acid (OTA) and acetic acid (AA) to produce 2methylacetophenone (OMA), and weakly acidic oxides such as Th, U, Ce, and La oxide exhibited higher yield of OMA. The OMA yield depended on the catalyst support. SiO2, Al2O3, TiO2, and ZrO2 with a surface area of less than 200 m2 g–1 appeared to be suitable as industrial catalyst supports. CeO2 on Al2O3was chosen as an industrial catalyst for the synthesis of OMA because of higher productivity, longer catalyst life, and lifting of legal restrictions on catalyst handling. This catalyst system can also be applied to the syntheses of acetophenone, nitroacetophenone, and chloroacetophenone. 相似文献
212.
E. M. Afsah M. M. Abou-Elzahab M. T. Zimaity G. R. Proctor 《Monatshefte für Chemie / Chemical Monthly》1984,115(8-9):1065-1070
When -keto-ester1 a was reacted with dimethyl acetylenedicarboxylate ring expansion occurred to give substituted cyclooctadienones.Michael reactions of the title compounds1 with unsaturated ketones gave adducts, some of which underwent further cyclization reactions. A new route to -tetralone ring system10 via cyclization of the intermediateMichael adduct9 is described.
Michael- und Ringerweiterungsreaktionen von 6-Carboethoxy-3,5-diaryl-2-cyclohexen-1-onen
Zusammenfassung Bei der Reaktion von -Keto-ester1 a mit Dimethyl-acetylendicarboxylat wurden unter Ringerweiterung substituierte Cyclooctadienone erhalten. DieMichael-Reaktion der Titelverbindung1 mit ungesättigten Ketonen ergab Addukte, von denen einige weitere Cyclisierungsreaktionen eingingen. Es wird ein neuer Weg zum -Tetralonsystem10 über die Cyclisierung des intermediärenMichael-Addukts9 beschrieben.相似文献
213.
低共熔混合锂盐相图的绘制及应用 总被引:3,自引:0,他引:3
采用热分析法对不同组成的混合锂盐二元体系进行研究, 绘制了混合锂盐体系的步冷曲线和T-x相图, 结果表明体系均为具有最低共熔点的二元体系. LiOH-LiNO3、LiOH-LiCl、LiOH-Li2CO3及LiNO3-LiCl体系的最低共熔点分别为175.7、294.5、418.2及221.6 ℃. 利用低共熔混合物LiNO3-LiOH为锂盐与不同前驱体反应, 制备出了层状结构良好的锂离子电池正极材料LiNiO2、LiNi0.8Co0.2O2及LiNi1/3Co1/3Mn1/3O2. X射线衍射分析表明, 合成的材料具有规整的层状NaFeO2结构, 且XRD衍射峰强度之比I(003)/I(104)>2.0, 电性能测试表明, 在2.7-4.3 V(vs Li/Li+)的电压范围内进行0.1C倍率充放电, LiNiO2、LiNi0.8Co0.2O2、LiNi1/3Co1/3Mn1/3O2首次充电比容量分别达168.0、225.4、194.0 mAh·g-1, 放电比容量分别为138.4、165.8、157.7 mAh·g-1. 相似文献
214.
Toshio Koizumi Jun Sakamoto Yasuhiko Gondo Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》2002,40(14):2487-2494
The palladium(0)‐catalyzed polyaddition of bifunctional vinyloxiranes [1,4‐bis(2‐vinylepoxyethyl)benzene ( 1a ) and 1,4‐bis(1‐methyl‐2‐vinylepoxyethyl)benzene ( 1b )] with 1,3‐dicarbonyl compounds [methyl acetoacetate ( 4 ), dimethyl malonate ( 6 ), and Meldrum's acid ( 8 )] was investigated under various conditions. The polyaddition of 1 with 4 was carried out in tetrahydrofuran with phosphine ligands such as PPh3 and 1,2‐bis(diphenylphosphino)ethane (dppe). Polymers having hydroxy, ketone, and ester groups in the side groups ( 5 ) were obtained in good yields despite the kinds of ligands employed. The number‐average molecular weight value of 5b was higher than that of 5a . The polyaddition of 1b and 6 was affected by the kinds of ligands employed. The corresponding polymer 7b was not obtained when PPh3 and 1,2‐bis(diphenylphosphino)ferrocene were used. The polyaddition was carried out with dppe as the ligand and gave polymer 7b in a good yield. The molecular weight of the polymer obtained from 1b and 8 was much higher than those of polymers 5b and 7b . The polyaddition with Pd2(dba)3 · CHCl3/dppe as a catalyst (where dba is dibenzylideneacetone) produced polymer 9b in a 92% yield (number‐average molecular weight = 45,600). The stereochemistries of all the obtained polymers were confirmed as an E configuration by the coupling constant of the vinyl proton. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2487–2494, 2002 相似文献
215.
Bredikhina Z. A. Pashagin A. V. Savel"ev D. V. Bredikhin A. A. 《Russian Chemical Bulletin》2001,50(3):436-439
Nonracemic -blockers, viz., (S)-propranolol and (S)-timolol, were prepared from (S)-glycidol in three steps consisting in the reaction with SOCl2 followed by the reaction of the resulting (4S)-4-chloromethyl-2-oxo-1,3,2-dioxathiolanes with the corresponding phenol and the final cleavage of (4R)-aryloxymethyl sulfites under the action of amines in DMF. 相似文献
216.
RExOy.nH2O对氟离子的吸附性能 总被引:3,自引:0,他引:3
La、Ce等稀土水含氧化物对阴离子的吸附性早有研究「‘-‘1,但从混合轻稀土氯化物制得的水合氧化物吸附F一的研究报道较少.为探讨难溶金属水合氧化物的除氟性能,本文以混合轻稀土氯化物为原料,制得其水含氧化物(RExOy·nH。O),采用高聚物造粒,研究了粒状RExOy·nH。O对F一的吸附性能及吸附机理.所用混合轻稀土氯化物由包头钢铁稀土公司提供,其主要组成(以氧化物计)为:CeO。(50%)、Nd。O3(25%)、La。O。(15%)、P36Oll(8%).聚丙烯睛分子量为(2.5~5)X10‘.其它试剂为分析纯.RExO.·nH。O参照文… 相似文献
217.
The reaction of M2(O2CBu(t))4 (M = Mo, W) with a dicarboxylic acid in toluene yields compounds of general formula [M2]-O2C-X-CO2-[M2] ([M2] = M2(O2CBu(t))3; X = conjugated spacer). The M2 units are electronically coupled via interactions between the M2 delta and dicarboxylate pi* orbitals, and the magnitude of this coupling is revealed by electronic structure calculations and spectroscopic data. These compounds show intense metal to ligand charge transfer (MLCT) absorptions in the visible region of the electronic spectrum that are temperature and solvent dependent. Evidence of electronic coupling is seen in their cyclic voltammograms, which show two successive one-electron oxidations. The extent of electronic coupling in the mixed valence radical cations [M2]-O2C-X-CO2-[M2]+, generated by oxidation with one equivalent of AgPF6 or FeCp2PF6, is evaluated by EPR and UV-vis-NIR spectroscopic data, and delocalized behavior is observed in compounds with W2 units separated by up to 13.6 angstroms. The simplicity of the frontier M2 orbital interactions with the bridge pi orbitals provides a convenient system with which to study electron transfer in mixed valence systems, as compared to the extensively studied, but more complicated, dinuclear t(2g)6/t(2g)5 mixed valence compounds. Oligomeric and polymeric compounds incorporating M2 units have also been synthesized, having general formula [M2(O2CR)2(O2C-Thio-CO2)]n (Thio = n-hexyl substituted ter- and quinque-thiophenes). They can be deposited as thin films by spin coating, and show photoluminescence and electroluminescence. These metallo-polythiophenes show potential for application in electronic materials. ( 相似文献
218.
V. A. Yanchenko A. M. Demchenko M. O. Lozinskii 《Chemistry of Heterocyclic Compounds》2004,40(4):516-518
We propose a method for obtaining derivatives of 7H-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazine by alkylation of 4-amino-5-methyl-4H-1,2,4-triazole-3-thiol by substituted -chloroacetanilides, followed by cyclization of the intermediate by phosphorus oxychloride. 相似文献
219.
Hiromu Hayashi 《Catalysis Surveys from Japan》1999,3(1):43-52
Additive telluromolybdates, MoO3·2TeO2 and MIIO·TeO2·MoO3 (MIITeMoO6; MII = Co, Mn, Zn), converted ethyl lactate selectively to pyruvate in a vaporphase fixedbed flow system at 250–300 °C. A synergy in activity was observed for binary TeO2–MoO3, and crystalline Te2MoO7 was suggested as the active species. The Rietveld analysis of powder XRD patterns of ternary CoTeMoO6 revealed the layer structure quite different from that of the reference Te2MoO7, but tellurium was again located adjacent to molybdenum linked through lattice oxygen. 相似文献
220.
The main product of the reaction of 1-methylcyclobutanol with Pb(OAc)4 in benzene is 1-phenyl-4-pentanone; the use of Mn(OAc)3 in acetic acid gives a mixture of 2,9-decanedione and methyl propyl ketone; 1-(chloro-, bromo-, thiocyano-, or cyano)-4-pentanone is formed in the presence of the systems Pb(OAc)4-metal halide or Mn(OAc)3-metal halide.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 12, pp. 2760–2763, December, 1992. 相似文献