全文获取类型
收费全文 | 4688篇 |
免费 | 153篇 |
国内免费 | 37篇 |
专业分类
化学 | 3371篇 |
晶体学 | 46篇 |
力学 | 121篇 |
数学 | 655篇 |
物理学 | 685篇 |
出版年
2023年 | 19篇 |
2022年 | 41篇 |
2021年 | 59篇 |
2020年 | 86篇 |
2019年 | 94篇 |
2018年 | 59篇 |
2017年 | 51篇 |
2016年 | 123篇 |
2015年 | 110篇 |
2014年 | 96篇 |
2013年 | 196篇 |
2012年 | 326篇 |
2011年 | 374篇 |
2010年 | 151篇 |
2009年 | 149篇 |
2008年 | 319篇 |
2007年 | 291篇 |
2006年 | 330篇 |
2005年 | 292篇 |
2004年 | 247篇 |
2003年 | 240篇 |
2002年 | 195篇 |
2001年 | 61篇 |
2000年 | 47篇 |
1999年 | 34篇 |
1998年 | 41篇 |
1997年 | 58篇 |
1996年 | 78篇 |
1995年 | 43篇 |
1994年 | 39篇 |
1993年 | 43篇 |
1992年 | 38篇 |
1991年 | 19篇 |
1990年 | 28篇 |
1989年 | 23篇 |
1988年 | 33篇 |
1987年 | 29篇 |
1986年 | 20篇 |
1985年 | 56篇 |
1984年 | 37篇 |
1983年 | 20篇 |
1982年 | 39篇 |
1981年 | 29篇 |
1980年 | 25篇 |
1979年 | 29篇 |
1978年 | 22篇 |
1977年 | 19篇 |
1976年 | 19篇 |
1974年 | 14篇 |
1973年 | 13篇 |
排序方式: 共有4878条查询结果,搜索用时 15 毫秒
31.
A phase transition in NaOD has been observed calorimetrically near 150 K. The estimated enthalpy of the transition is 200(75) . This phase transition has no corresponding analog in the protonated material, NaOH, down to 10 K. Other physical techniques also reveal the phase transition but give slightly varying values for the transition temperature. These techniques include 23Na nuclear quadrupole resonance, 23Na nuclear magnetic resonance and 2D magnetic resonance. The resonance experiments indicate that the phase transition is a continuous one and that in the lower temperature phase there is one sodium and deuterium crystal Iographic site per cell. X-ray powder diffraction of the low temperature phase indicates that it is probably monoclinic with am = 3.388(1)A, bm = 11.34(1)A, cm = 3.418(1)A,β = 90.52° and V = 131 .4Å3. The volume of the unit cell is greater at the lower temperature than at the higher temperature. The 23Na pure quadrupole resonance frequency at 77 K is 1.784(2) MHz with an asymmetry parameter of 0.82(5). 相似文献
32.
The reaction of phenyl lithium acetylide () with 2,6-diphenylpyrylium perchlorate () is solvent dependent. With diethyl ether as solvent, the isolated product differed from that previously reported and is reassingned as 2,6-diphenyl-4-phenylacetylenyl-4-pyran (). On the other hand, in THF the title compound () was obtained; its structure confirmed by single-crystal x-ray crystallography. 相似文献
33.
Thermolysis of benzannulated enyne-isocyanates 13 and enyne-isocyanates 36 and 37 promoted the cycloaromatization reactions to generate in situ O,4-didehydro-2-hydroxyquinolines and O,4-didehydro-2-hydroxypyridines, respectively, as reactive intermediates. These cycloaromatized intermediates could be captured either as biradicals and/or as zwitterions depending on the nature of the substituent at the alkynyl terminus. The intermediate derived from cycloaromatization of 13a bearing a phenyl substituent could be regarded as biradical 14, which then abstracts hydrogen atoms from gamma-terpinene leading to 2(1H)-quinolinone 15. Alternatively, the same intermediate could also be regarded as zwitterion 14', which then undergoes an initial hydride abstraction from gamma-terpinene followed by protonation to produce 15. The presence of a 2-phenylethyl substituent in 13b and 37a or a 2-methylphenyl substituent in 37b also allowed the resulting intermediates to be captured intramolecularly either as biradicals or as zwitterions, producing 2(1H)-quinolinone 19, 2(1H)-pyridone 39, and benzopyranopyridine 43, respectively. On the other hand, with a 2-methoxyphenyl, a 2-(dimethylamino)phenyl, or a 3-methoxypropyl substituent, the chemical behavior of the cycloaromatized adduct could be best accounted for in terms of a zwitterionic intermediate leading to benzofuro[3,2-c]quinolin-6(5H)-one (20), 5,11-dihydro-11-methyl-6H-indolo[3,2-c]quinolin-6-one (25), benzofuro[3,2-c]pyridin-1(2H)-one 44, 2,5-dihydro-2,5-dimethyl-1H-pyrido[4,3-b]indol-1-one 46, and related compounds. Interestingly, thermolysis of 37f bearing a 2-(methoxymethyl)phenyl substituent at the alkynyl terminus produced the unexpected benzopyranopyridine 56 as the major product in a process involving the cleavage of the bond between the methoxyl oxygen and the adjacent methylene carbon. The efficiency and selectivity of the cycloaromatization reaction could also be enhanced by the introduction of 1.1 to 10 equiv of dimethylphenylsilyl chloride to the reaction mixture to capture the resulting zwitterion. 相似文献
34.
Analytical techniques for the detection of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazatetracyclo(5.5.0.05,9.03,11)dodecane (CL-20) in water and soil are developed by adapting methods traditionally used for the analysis of nitroaromatics. CL-20 (a new explosives compound) is thermally labile, exhibits high polarity, and has low solubility in water. These constraints make the use of specialized sample handling, preparation, extraction, and analysis necessary. The ability to determine the concentrations of this new explosive compound in environmental matrices is helpful in understanding the environmental fate and effects of CL-20; understanding the physical, chemical, and biological fate of CL-20; and can be used in developing remediation technologies and determining their efficiency. The toxicity and mobility of new explosives in soil and groundwater are also of interest, and analytical techniques for quantitating CL-20 and its degradation products in soil and natural waters make these investigations possible. 相似文献
35.
Bisfunctionalized m-phenylene ethynylene imine oligomers were polymerized in the polar solvent acetonitrile, resulting in high-molecular weight poly(m-phenylene ethynylene imine)s. It is hypothesized that this polymerization, which proceeds through the reversible metathesis of imine bonds, is driven by the folding of the long m-phenylene ethynylene imine chains. Upon conducting the polymerization in a series of solvents in which the m-phenylene ethynylene oligomers exhibit different folding stabilities, it was possible to correlate the molecular weight of the resulting poly(m-phenylene ethynylene imine)s with the helical stability of the corresponding oligomers. The polymerization was also demonstrated to be reversible and responsive to solvent and temperature changes. 相似文献
36.
Harding WW Tidgewell K Schmidt M Shah K Dersch CM Snyder J Parrish D Deschamps JR Rothman RB Prisinzano TE 《Organic letters》2005,7(14):3017-3020
[reaction: see text] Two new neoclerodane diterpenes, salvinicins A (4) and B (5), were isolated from the dried leaves of Salvia divinorum. The structures of these compounds were elucidated by spectroscopic techniques, including (1)H and (13)C NMR, NOESY, HMQC, and HMBC. The absolute stereochemistry of these compounds was assigned on the basis of single-crystal X-ray crystallographic analysis of salvinicin A (4) and a 3,4-dichlorobenzoate derivative of salvinorin B. 相似文献
37.
Jeffrey C. Evans Simon K. Jackson Christopher C. Rowlands Martin D. Barratt 《Tetrahedron》1985,41(22):5191-5194
Under acid conditions aqueous solutions of chloramine-T form nitrogen-centred radicals via loss of the chlorine atom. The nitrogen radicals produced have been studied by ESR spectroscopy using the spintrapping method. Adducts of the spin trap phenyl-t-butyl nitrone are oxidized by chloramine-T in acid media to give a paramagnetic product in which the unpaired electron interacts with two inequivalent nitrogen atoms. The spin trap 5,5-dimethyl-2-pyrrolidine-1 -oxide is oxidized rapidly to 5,5-dimethyl-2-pyrrolidone-1-oxyl by chloramine-T under acid onditions. The water soluble trap α-4-pyridyl-1-oxide-N-t-butyl nitrone forms a stable nitroxide adduct with a nitrogen radical of chloramine-T in acid solution. Identical results were obtained with chloramine-B (sodium salt of N-chlorobenzene sulfonamide), indicating the involvement of the N-chloramine group in radical formation. 相似文献
38.
A synthetically useful protocol has been developed for the preparation of highly functionalized N-alkenyl-benzimidazol-2-ones. Reaction of commercially available o-phenylenediamines with variously substituted cyclic ketones provides spiro-benzimidazolines. Treatment of these spiro-benzimidazolines with triphosgene in the presence of potassium carbonate results in rapid rearrangement and formation of N-alkenyl-benzimidazol-2-ones in modest to excellent yield for the two-step sequence. Extension of this methodology toward the preparation of a μ opiate receptor antagonist and droperidol, a potent antiemetic and antipsychotic agent, currently a marketed pharmaceutical is also described. Upon treatment of spiro-benzimidazolines with triphosgene in the presence of sodium triacetoxyborohydride, N-alkyl-benzimidazol-2-ones were formed. 相似文献
39.
Sequence-specific phenylacetylene oligomers consisting of functionalized monomers (hexyl benzoate, hexyl phenyl ether, benzonitrile, and tert-butylphenyl) are synthesized in gram quantities using solid-phase methods. Growing oligomers are attached to a divinylbenzene cross-linked polystyrene support by the 1-aryl-3-propyl-3-(benzyl-supported) triazene moiety. This linkage is obtained by reaction of arenediazonium tetrafluoroborate salts with a n-propylamino-modified Merrifield resin. Condensation strategies are described, producing oligomers with higher yields and simplified procedures compared to solution-phase methods. Terminal acetylene is protected with a trimethylsilyl group. After deprotection of the resin-bound terminal acetylene, an aryl iodide monomer or an aryl iodide-terminated oligomer is coupled to the supported oligomer using a palladium(0) catalyst. The cycle can be repeated to produce sequence-specific oligomers of varying length and functionality. The resulting oligomers are liberated from the polymer support by cleavage of the 1-aryl-3-propyl-3-(benzyl-supported) triazene group by reaction with iodomethane producing an aryl iodide. 相似文献
40.
Plieger PG Ehler DS Duran BL Taylor TP John KD Keizer TS McCleskey TM Burrell AK Kampf JW Haase T Rasmussen PG Karr J 《Inorganic chemistry》2005,44(16):5761-5769
The ligand 4,5-dicarboxyimidazole (H(2)DCI) and its methyl derivative 1-methyl-4,5-dicarboxyimidazole (H(2)MDCI) have been shown to bind to Be(II) forming a zwitterionic species that has been structurally characterized. A new dicarboxyimidazole-based polymer has been prepared and its Be-binding properties have been studied using NMR ((1)H and (9)Be) and fluorescence spectroscopy; it represents a rare example of beryllium binding to a polymer. Models of the mononuclear and polymeric Be(II)-binding sites have been studied using density functional theory (DFT), and the (9)Be NMR chemical shifts of these model materials have been calculated for the purpose of direct comparison to experimentally observed values. Differences in the binding modes of the mononuclear and polymeric species are discussed. 相似文献