全文获取类型
收费全文 | 4767篇 |
免费 | 324篇 |
国内免费 | 617篇 |
专业分类
化学 | 3717篇 |
晶体学 | 96篇 |
力学 | 42篇 |
综合类 | 32篇 |
数学 | 659篇 |
物理学 | 1162篇 |
出版年
2023年 | 65篇 |
2022年 | 153篇 |
2021年 | 126篇 |
2020年 | 97篇 |
2019年 | 205篇 |
2018年 | 254篇 |
2017年 | 113篇 |
2016年 | 133篇 |
2015年 | 120篇 |
2014年 | 172篇 |
2013年 | 306篇 |
2012年 | 192篇 |
2011年 | 268篇 |
2010年 | 246篇 |
2009年 | 364篇 |
2008年 | 327篇 |
2007年 | 296篇 |
2006年 | 272篇 |
2005年 | 244篇 |
2004年 | 228篇 |
2003年 | 177篇 |
2002年 | 242篇 |
2001年 | 149篇 |
2000年 | 111篇 |
1999年 | 81篇 |
1998年 | 87篇 |
1997年 | 59篇 |
1996年 | 71篇 |
1995年 | 71篇 |
1994年 | 84篇 |
1993年 | 71篇 |
1992年 | 56篇 |
1991年 | 30篇 |
1990年 | 28篇 |
1989年 | 22篇 |
1988年 | 25篇 |
1987年 | 16篇 |
1986年 | 15篇 |
1985年 | 10篇 |
1984年 | 13篇 |
1983年 | 6篇 |
1982年 | 11篇 |
1981年 | 14篇 |
1980年 | 10篇 |
1979年 | 18篇 |
1978年 | 12篇 |
1977年 | 7篇 |
1976年 | 9篇 |
1975年 | 6篇 |
1973年 | 5篇 |
排序方式: 共有5708条查询结果,搜索用时 187 毫秒
201.
On irradiation in the presence of propen‐2‐yl isocyanate ( 4 ), six‐membered cyclic enones 3 are converted into regio‐ and stereoisomeric mixtures of [2+2] cycloadducts 5 – 10 ; the preferentially formed HT products, 5 – 8 , can be converted into the corresponding bicyclic amines by acid hydrolysis, whereas, under these conditions, the regioisomeric HH‐isocyanato derivatives undergo a retro‐Mannich reaction. 相似文献
202.
Warrener Ronald N. Malpass John R. Butler Douglas N. Sun Guangxing 《Structural chemistry》2001,12(3-4):291-304
The thermal addition of N-carbobenzyloxyisoindole (N-Z isoindole) 11a, generated by the reaction of 3,6-di(2-pyridyl)-s-tetrazine 9 with N-Z 7-azabenzonorbornadiene 8a, onto dimethyl tricyclo[4.2.1.02.5]nona-3,7-diene-3,4-dicarboxylate 17 occurred site selectively at the cyclobutene -bond to form a stereoisomeric mixture of 1 : 1-adducts 18 and 19, in which the bent-frame isomer 19 was dominant (ratio 5 : 1). In contrast, N-benzyl tetrafluoroisoindole 11c reacted with 17 only under high-pressure conditions (14 kbar, RT, 4 days) to afford 1 : 1-adducts at the cyclobutene site, in which the extended-frame isomer 18c was dominant and the accompanying bent-frame product 19c reverted to starting materials soon after isolation. These same stereoselectivities were used to prepare "windscreen wiper" compound 28c having two mobile N-benzyl substituents attached to a rigid scaffold by the reaction of N-benzyl tetrafluoroisoindole 11c with tetramethyl tetracyclo[4.4.1.0.2,5.07.10]undeca-3,8-diene-3,4,7,8-tetracarboxylate 23. Cavity bis-(cyclobutene-1,2-diester) 6 reacted with N-benzyl tetrafluoroisoindole 11c twice over to produce cavity structure 36 with two O- and two N-benzyl bridges on the inner face, whereas the narrower cavity bis-alkene 32 stopped at the 1 : 1-addition stage. The dynamics of the Z-group in the dual adducts 26a–28a are discussed briefly and key adducts and cavity systems have been structurally evaluated by X-ray crystallography, VT NMR, and molecular modeling. 相似文献
203.
Summary Two methods of instrumental neutron activation analysis for the determination of selenium in steels, based on respectively77mSe (t
1/2
= 17.5 s) and75Se (t
1/2 = 120 d) are presented. Good agreement is obtained by application of both methods on a series of steels containing selenium at the 0.1% level. Interferences and advantages associated with either method are discussed.
Bestimmung von Selen in Stahl durch Neutronenaktivierung und Ge(Li)--Spektrometrie
Zusammenfassung Zwei Methoden werden beschrieben, die auf der Messung von77mSe (t 1/2 = 17,5 s) bzw.75Se (t 1/2 = 120 d) beruhen. Bei der Anwendung auf Stähle mit Selengehalten in der Größenordnung von 0,1 % wurden gut übereinstimmende Werte erhalten. Störungen und Vorteile der Methoden werden diskutiert.相似文献
204.
V. V. Lipson S. M. Desenko V. V. Borodina M. G. Shirobokova T. M. Karnozhitskaya V. I. Musatov S. V. Kravchenko 《Chemistry of Heterocyclic Compounds》2005,41(2):216-220
The cyclocondensation of methylcinnamates and arylidene derivatives of Meldrums acid with 3-amino-5-methylthio-1,2,4-triazole in DMF gives 2-methylthio-4,5,6,7-tetrahydro-1,2,4-triazolo[1,5-a]-pyrimidin-5-ones. The reaction involving arylidene derivatives of Meldrums acid or its synthetic equivalents in ethyl acetate with a catalytic amount of pyridine gives a mixture of 2-methylthio-4,5,6,7-tetrahydro-1,2,4-triazolo[1,5-a]pyrimidin-5- and -7-ones.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 246–251, February, 2005. 相似文献
205.
Li2Br(NH2): The First Ternary Alkali Metal Amide Halide The pseudobinary system LiNH2/LiBr was investigated by X-ray methods. The crystal structure of the compound Li2Br(NH2) was solved by single crystal data: Li2Br(NH2): Pnma, Z = 8, a = 12.484(2) Å, b = 7.959(1) Å, c = 6.385(1) Å, Z(Fo) with (Fo)2 ≧ 3σ(Fo)2 = 348, Z (parameter) = 51, R/Rw = 0.019/0.021 Li2Br(NH2) crystallizes in a new type of structure. To one another isolated chains of [Li2Li4/2(NH2)22+] show the motif of closest rod packing. They are connected via bromide ions in a distorted cubic primitive arrangement. 相似文献
206.
锂离子电池PMMA-VAc聚合物电解质的制备与性质研究 总被引:5,自引:0,他引:5
以甲基丙烯酸甲酯(MMA)和醋酸乙烯酯(VAc)为单体, 用乳液聚合法合成聚甲基丙烯酸甲酯-醋酸乙烯酯聚合物(PMMA-VAc), 并以此聚合物制备了新型聚烯烃膜支撑的聚合物膜及聚合物电解质. 用红外光谱(FTIR)、凝胶色谱(GPC)、差热和热重分析(DSC/TG)、扫描电镜(SEM)及电池充放电实验等方法研究了聚合物、聚合物膜和聚合物电解质的性质. 红外光谱结果表明, MMA与VAc通过各自的C=C双键打开聚合成PMMA-VAc. PMMA-VAc易于分散在混合碳酸酯溶剂中并形成凝胶, 凝胶粘度随PMMA-VAc浓度的增加而增加, 当浓度为4%时成膜效果最佳. PMMA-VAc膜具有大量的微孔结构, 具有极强的吸液性能. PMMA-VAc膜具有良好的热稳定性: 在380 ℃范围内保持稳定. 聚烯烃膜支撑的PMMA-VAc膜室温下的离子电导率为1.85×10-3 S•cm-1, 用作为锂离子电池的聚合物电解质时, 电池具有良好的循环稳定性和倍率性能. 相似文献
207.
Maria Ochsenkühn-Petropulu Petros Tarantilis John Tsarouchis Klaus Ochsenkühn George Parissakis 《Mikrochimica acta》1998,129(3-4):233-238
Large area coatings (>10cm2) of the high temperature superconductor YBa2Cu3O7–x (x = 0.1 – 0.2) (YBCO) have been prepared by scale up an electrophoretic deposition technique using silver sheets and Si-wafers coated with Ag or Au as substrates. Several parameters, like the kind of the solvent, the applied voltage, the distance between the electrodes, the initial concentration of the suspension and the temperature during the electrophoresis were investigated in order to attain high deposition rates, as well as uniform YBCO coatings with the proper stoichiometry. To obtain a strongly adherent and dense coating a subsequent appropriate sintering and annealing procedure has been developed. The coatings obtained were characterized for their stoichiometry and superconducting properties by X-ray diffraction (XRD), Raman spectroscopy and magnetic measurements. The homogeneity and thickness of the films and the average grain size of the deposited particles have been investigated by optical and scanning electron microscopy (SEM). 相似文献
208.
多种维生素的高效液相色谱分离及应用 总被引:6,自引:0,他引:6
在SpherisorbC18柱上,采用含Li2SO4-己烷磺酸钠-三乙胺的水溶液作流动相,同时分离测定四种水溶性维生素:B1、B2、B6及烟酰胺。四种化合物的回收率在99.2%~99.9%之间,RSD为0.16%~0.49%(n=5)。方法应用于常见的复合维生素药物制剂的含量测定,结果满意。 相似文献
209.
N. A. Talzhanov D. T. Sadyrbekov F. M. Smagulova R. M. Mukanov V. A. Raldugin M. M. Shakirov A. V. Tkachev G. A. Atazhanova B. I. Tuleuov S. M. Adekenov 《Chemistry of Natural Compounds》2005,41(2):178-181
Chemical components from the aerial part of the Kazakhstan population of Artemisia pontica, from which the rarely encountered flavonoids 7-O-methyl- and 4′,7-di-O-methyl-esters of apigenin were isolated for the first time, were identified. The complete chemical composition of the essential oil was established using GC-MS.__________Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 143–145, March–April, 2005. 相似文献
210.
利用半经验AM1方法计算了基态与第一激发态7-羟基喹啉的两种异构体及其与甲醇等溶济分子形成1:2桥式氢键化合物的结构与稳定性。在基态,烯醇式结构比酮式结构稳定;而在第一激发态酮式比烯醇式稳定。1:2桥式氢键的形成使得酮式能量降低比烯醇式多。烯醇式1:2桥式氢键化合物呈交叉式结构,酮式1:2桥式氢键化合物呈折叠式结构,激发态的形成对氢键结构影响不大。在7-羟基喹啉羟基(或羰基)的邻位和间位引入取代基后,对喹啉环和桥式氢键结构的影响均不明显。 相似文献