全文获取类型
收费全文 | 2814篇 |
免费 | 134篇 |
国内免费 | 663篇 |
专业分类
化学 | 3390篇 |
晶体学 | 33篇 |
力学 | 11篇 |
综合类 | 26篇 |
物理学 | 151篇 |
出版年
2024年 | 2篇 |
2023年 | 17篇 |
2022年 | 67篇 |
2021年 | 56篇 |
2020年 | 65篇 |
2019年 | 58篇 |
2018年 | 66篇 |
2017年 | 104篇 |
2016年 | 103篇 |
2015年 | 88篇 |
2014年 | 130篇 |
2013年 | 332篇 |
2012年 | 160篇 |
2011年 | 163篇 |
2010年 | 164篇 |
2009年 | 158篇 |
2008年 | 173篇 |
2007年 | 185篇 |
2006年 | 182篇 |
2005年 | 186篇 |
2004年 | 152篇 |
2003年 | 150篇 |
2002年 | 104篇 |
2001年 | 94篇 |
2000年 | 90篇 |
1999年 | 94篇 |
1998年 | 69篇 |
1997年 | 60篇 |
1996年 | 66篇 |
1995年 | 54篇 |
1994年 | 39篇 |
1993年 | 39篇 |
1992年 | 34篇 |
1991年 | 20篇 |
1990年 | 8篇 |
1989年 | 13篇 |
1988年 | 14篇 |
1987年 | 7篇 |
1986年 | 4篇 |
1985年 | 5篇 |
1984年 | 5篇 |
1983年 | 2篇 |
1982年 | 7篇 |
1981年 | 2篇 |
1980年 | 7篇 |
1979年 | 4篇 |
1978年 | 5篇 |
1977年 | 2篇 |
1976年 | 1篇 |
1970年 | 1篇 |
排序方式: 共有3611条查询结果,搜索用时 0 毫秒
71.
采用均相反应的方法合成了6个含羟基芳基或氨基芳基的磷酰胺酯衍生物:[(ClCH_2CH_2)_2NP(O)(OPh)(XArY)](X:O,NH;Y:m或p-OH或NH_2).用元素分析、红外光谱、氢核磁共振谱及质谱证实了它们的组成及结构. 相似文献
72.
G. G. Danagulyan G. A. Panosyan L. G. Sahakyan 《Chemistry of Heterocyclic Compounds》2007,43(8):996-1000
The interaction of the iodomethylates of pyrimidinyl-2-acetic acid derivatives with monosubstituted hydrazines, in addition
to the products of a Kost-Sagitullin rearrangement, leads also to N-substituted triazoles. The structure of the triazoles
was demonstrated by NOESY NMR experiments. The structure of the reaction products was determined on the basis of the response
observed in the spectra between the methyl group protons of the triazole ring and the spatially close proton of the substituent
in position 1 and a conclusion was drawn on the direction of the primary attack of nucleophile in the recyclization process
of the pyrimidinium salts into a 1,2,4-triazole.
__________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1175–1179, August, 2007. 相似文献
73.
[60]Fullerene-fused pyrazolines 1 were prepared by the reaction of C60 with alky diazoacetates under the solid-state high-speed vibration milling conditions as well as in toluene solution. Pyrazolines 1 were stable in refluxing toluene and its thermolysis process in 1,2-dichlorobenzene was investigated, the decomposition rates and activation energies of pyrazolines 1 were obtained. The current work demonstrated that the liquid-phase reaction of C60 with alkyl diazoacetates undergoes via 1,3-dipolar cycloaddition pathway at room temperature, or proceeds via carbene mechanism at a temperature of refluxing toluene, thus clarifies the previous ambiguity of its reaction mechanism. 相似文献
74.
M Suguna LakshmiB.S.R Reddy 《European Polymer Journal》2002,38(4):795-801
New epoxide and cyanate ester resins with an aromatic ester backbone namely 1,3-[di-(4-glycidyloxy diphenyl-2,2′-propane)]-isophthalate (DGDPI) and 1,4-[di-(4-cyanato diphenyl-2,2′-propane)]-terephthalate (DCDPT) were synthesized and the intermediates were characterized by IR, 1H-/13C-NMR spectroscopic methods. The cured products from DGDPI and DHDPI exhibited higher Tg compared with standard epoxy system. The increase in the Tg may be due to the cyanate ester and rigid aromatic backbones present in the curing system. 相似文献
75.
Novel polymer supported IBX esters and amides were prepared in two steps, which were the coupling of 2-iodobenzoic acid to a hydroxy or amino polystyrene followed by activation of the intermediate product. These polymer supported reagents were tested as oxidants by the conversion of a series of alcohols to the corresponding aldehydes or ketones. We found that the polymer supported IBX amides displayed excellent oxidative activity, in that they oxidized benzyl alcohol to benzaldehyde completely within 1 h at an oxidant to alcohol ratio of 2 to 1. 相似文献
76.
Summary The retention, enantionselectivity and enantiomeric elution order of racemic propranolol (PP) and its ester derivatives (O-acetyl,-propionyl,-butyrul and-valeryl PP) on an 1-acid glycoprotein (AGP)-bonded column have been investigated by changing eluent composition (eluent pH, buffer concentration, type and content of organic modifier). The retention of these cationic solutes, PP and its ester derivatives, was influenced by eluent pH, ionic strength and organic modifier content. The enantioselectivity was dependent on eluent pH and type of organic modifier. Reversal of the enantiomeric elution order of ester derivatives of PP (O-propionyl-butyryl) and-valeryl PP) occurred around eluent pH 6–7. These results suggst that chiral recognition or binding properties may be altered by the change in eluent composition, espeically eluent pH and type of organic modifier. 相似文献
77.
I. V. Ukrainets L. V. Sidorenko O. V. Gorokhova S. V. Shishkina 《Chemistry of Heterocyclic Compounds》2006,42(6):776-781
Alkaline hydrolysis of the ethyl ester of 4-(cyanoethoxycarbonylmethyl)-2-oxo-1,2-dihydroquinoline-3-carboxylic acid is accompanied
by decarboxylation with loss of two molecules of CO2 and leads to 4-methyl-2-oxo-1,2-dihydroquinoline-3-carboxylic acid.
__________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 887–893, June, 2006. 相似文献
78.
M. Fujiwara T. Okano T. -H. Nakashima A. A. Nakamura G. Sugihara 《Colloid and polymer science》1997,275(5):474-479
For a sodium salt of α-sulfonatomyristic acid methyl ester (14SFNa), one of the α-SFMe series surfactants, critical micellization
concentration (CMC), solubility and degree of counterion binding (β) were determined by means of electrocon-ductivity measurements
at different temperatures (at every 5 °C) ranging from 15 to 50 °C. The phase diagram of 14SFNa in pure water was constructed
from the CMC- and solubility-temperature data, in which the Krafft temperature (critical solution temperature) was found around
0 °C. The changes in the Gibbs energy, ΔG
0
m, enthalpy, ΔH
0
m, and entropy, ΔS
0
m, upon micelle formation as a function of temperature were evaluated taking βvalues into calculation.
Received: 28 August 1996 Accepted: 5 November 1996 相似文献
79.
Michael I. Rosenthal Anthony W. Czarnik 《Journal of inclusion phenomena and macrocyclic chemistry》1991,10(1):119-126
The ability of cyclodextrins to effect rapid transacylations of bound substrates has been well studied. One important difference between cyclodextrin and enzyme-mediated transacylation is the pH required. Because the pK
a of a cyclodextrin secondary-side hydroxyl group is about 12, transacylations are accelerated in the presence of cyclodextrin under basic conditions (pH > 10.5). In 1988, our group reported the synthesis of cyclodextrin with attached cyclen-Co(III) complexes; significant acceleration in the reaction withp-nitrophenyl acetate was observed only with the primary side derivative. Of course, metalloenzymes utilize M2+ and not M3+ catalytic centers; in addition, large rate accelerations in the transacylations of both activated and unactivated substrates have been observed previously in systems utilizing M2+ ions (e.g., Zn, Cu, Ni) as well as M3+ ions (e.g. Co, Ir, Cr). In this paper, we describe the ability of CD-cyclen-M2+ conjugates to transacylate activated esters, amides, and phosphates. In addition, the ability of the apoenzyme mimic to effect transacylations was examined. 相似文献
80.
S. G. Mikhalenok N. M. Kuz'menok A. M. Zvonok 《Chemistry of Heterocyclic Compounds》2005,41(8):977-986
It was established that, in addition to ethyl 4-aryl-3-(2,3-epoxyalkanoyl)-4,5-dihydro-1H-pyrazole-5-carboxylates, the reaction
of diazoacetic ester with β-arylacryloyloxiranes also gives ethyl 4-aryl-3(5)-(3-hydroxy-2-methylalkanoyl)-1H-pyrazole-5(3)-carboxylates.
The latter are formed from the tautomeric ethyl 4-aryl-5-(2,3-epoxyalkanoyl)-4,5-dihydro-1H-pyrazole-3-carboxylates as a result
of intramolecular oxidative-reductive disproportionation.
__________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, 1150–1160, August, 2005. 相似文献