全文获取类型
收费全文 | 6030篇 |
免费 | 202篇 |
国内免费 | 60篇 |
专业分类
化学 | 4480篇 |
晶体学 | 43篇 |
力学 | 220篇 |
综合类 | 2篇 |
数学 | 849篇 |
物理学 | 698篇 |
出版年
2024年 | 11篇 |
2023年 | 66篇 |
2022年 | 315篇 |
2021年 | 310篇 |
2020年 | 212篇 |
2019年 | 234篇 |
2018年 | 223篇 |
2017年 | 174篇 |
2016年 | 309篇 |
2015年 | 206篇 |
2014年 | 219篇 |
2013年 | 570篇 |
2012年 | 365篇 |
2011年 | 391篇 |
2010年 | 243篇 |
2009年 | 211篇 |
2008年 | 264篇 |
2007年 | 270篇 |
2006年 | 213篇 |
2005年 | 191篇 |
2004年 | 167篇 |
2003年 | 144篇 |
2002年 | 153篇 |
2001年 | 56篇 |
2000年 | 68篇 |
1999年 | 45篇 |
1998年 | 31篇 |
1997年 | 46篇 |
1996年 | 41篇 |
1995年 | 35篇 |
1994年 | 40篇 |
1993年 | 31篇 |
1992年 | 32篇 |
1991年 | 31篇 |
1990年 | 44篇 |
1989年 | 29篇 |
1988年 | 25篇 |
1987年 | 27篇 |
1986年 | 27篇 |
1985年 | 33篇 |
1984年 | 22篇 |
1983年 | 20篇 |
1982年 | 27篇 |
1981年 | 20篇 |
1980年 | 16篇 |
1979年 | 17篇 |
1978年 | 11篇 |
1977年 | 13篇 |
1976年 | 9篇 |
1975年 | 6篇 |
排序方式: 共有6292条查询结果,搜索用时 15 毫秒
31.
Zayed MA Fahmey MA Hawash MF 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(5):799-805
In the present work diazepam (Dz) drug was investigated using thermal analyses (TA) measurements (TG/DTG) in comparison with EI mass spectral (MS) fragmentation at 70 and 20 eV. Semi-empirical MO calculations, MNDO procedure, have been carried out on diazepam both as neutral molecule and the corresponding positively charged molecular ion. These include molecular geometry, bond order, charge distribution, heats of formation and ionization energy. Thermogravimetric and kinetic analysis, reveal a high response of the drug to the temperature variation with very fast rate. It is completely decomposed in the temperature range between 204 and 340 degrees C with average kinetic energy (KE) at 164.69 kJ mol(-1). On the other hand, diazepam can easily fragmented at low energy after ionization by electron energy at 9.56 eV. The losses of CO gas molecules followed by chlorine gas from the entity of diazepam (both neutral and charged molecular ion) as the best selected pathway were observed in both mass spectra (MS) and thermal analyses (TA). MNDO calculation was applied to declare both TA and MS observations. 相似文献
32.
Mohamed El Guendouzi Abderrahim Dinane Abdelfetah Mounir 《Journal of solution chemistry》2002,31(2):119-129
The mixed aqueous electrolyte system of ammonium and lithium chlorides has been studied by the hygrometric method at 25°C. The relative humidities of this system are measured at total molalities from 0.3 to 6 mol-kg– 1 for different ionic-strength fractions y of NH4Cl with y = 0.33, 0.50, and 0.67. The data obtained allow the deduction of new water activities and osmotic coefficients. The experimental results are compared with the predictions of the ECA (extended composed additivity) law proposed in our previous work. The Zdanovskii–Stokes–Robinson (ZSR), the Robinson–Stokes (RS), Reilly–Wood–Robinson (RWR), the Pitzer, and the Lietzke–Stoughton (LS II) models are also compared with our results. Predictions made using these models are, in general, consistent with our results. From these measurements, new Pitzer mixing ionic parameters are determined and used to predict the solute activity coefficients in the mixture for different ionic-strength fractions. 相似文献
33.
3-Amino-2-methyl-4(3H)-quinazolinone has been doubly lithiated, on nitrogen and in the 2-methyl group, with n-butyllithium. The lithium reagent thus obtained reacts with a variety of electrophiles (D(2)O, benzophenone, cyclohexanone, cyclopentanone, acetophenone, benzaldehyde, tetraisopropylthiuram disulfide (TITD)) to give the corresponding 2-substituted derivatives in very good yields. Reactions of the dilithio reagent with 2 molar equiv of methyl iodide or phenyl isocyanate give disubstituted derivatives. Double lithiation of the 2-ethyl and 2-propyl analogues have been achieved using LDA, and subsequent reactions with most electophiles are then similar. In the reaction of the dianion of the 2-ethyl compound with TITD, deamination from position 3 takes place with the formation of the 2-substituted derivative. In reactions with prochiral ketones, the dianion of the 2-ethyl compound gives very high diastereoselectivity. Lithiation and subsequent reactions of 3-(methylamino) analogues take place in a similar manner, thus providing access to a range of substituted 3-(methylamino)-2-alkyl-4(3H)-quinazolinones by a general procedure. Lithiation of 3-(dimethylamino)-2-ethyl-4(3H)-quinazolinone did not take place under similar conditions. Lithiation of 3-amino-2-unsubstituted-4(3H)-quinazolinone was also unsuccessful. 相似文献
34.
Spectrophotometric studies have been made to investigate the reaction of Nickel and Lead with 2-carboxy-2'-hydroxy-5'-sulfoformazyl-benzene (zincon) in 50%(v/v) ethanol-water at 25 degrees C and an ionic strength of 0.1 M NaClO4. A complete picture of the complexation equilibria in the pH range (4.2-12.0) for nickel and (1.9-11.5) for lead are presented. Simple, rapid, selective and sensitive methods for the spectro-photometric determination of nickel and lead has been developed based on the color reaction of their complexes with zincon. The methods allow the determination of 4.69 microg mL(-1) of nickel at pH = 6.3 (lambdamax = 665 nm) and 10.3 microg ml(-1) of lead at pH = 5.6 (lambdamax = 610 nm). The apparent molar absorptivities were epsilon = 1.3 x 10(4) L mol(-1) cm(-1) for nickel and epsilon = 0.6 x 10(4) L mol(-1) cm(-1) for lead. The interference of a large number of foreign ions and complexing agents has been studied. Thiosulphate, as masking agent allows the simultaneous determination of nickel and lead in the presence of high concentrations of copper. Ascorbic acid, sodium cyanide and or sodium fluoride provide the elimination of many other interferences. The methods have been applied successfully to the simultaneous determination of nickel and lead in an aluminium and non-ferrous alloy. 相似文献
35.
Brahim Lakhrissi Mohamed Massoui El Mokhtar Essassi Vincent Lequart Nicolas Joly Patrick Martin Grard Goethals 《Journal of heterocyclic chemistry》2004,41(6):1011-1014
Reaction of 1,5‐benzodiazepin‐2,4‐dione with 3‐O‐substituted‐5,6‐anhydro‐1,2‐isopropylidene‐α‐D‐glucofuranose gave the unexpected N,N'‐di‐glucofuranosyl benzimidazol‐2‐one by a novel rearrangement and ring closure reaction. A mechanism is proposed. 相似文献
36.
Bakhsh M. Majid R. El-Awady Abbas A. Khalifa Mohamed A. 《Transition Metal Chemistry》2000,25(1):52-59
Kinetic studies of ligand substitutions of the six-coordinated RuII pseudo-macrocyclic complex [Ru(CHDH)2- (PPh3)2] (CHDH=cyclohexanedione-dioximato) have been spectrophotometrically investigated in a variety of solvents and at 70, 80, 85 and 90°C. The reactions studied are of the form:[(PPh3)Ru(CHDH)2(PPh3)] + L =[(PPh3)Ru(CHDH)2L] + PPH3
where L is imidazole, pyridine, piperidine or thiophene or a solvent molecule (PhCl, PhMe, MeCN, DMSO or DMF). The solvolysis reactions with chlorobenzene and toluene proceed to an equilibrium position favoring the bis-triphenylphosphine complex. All other reactions proceed to completion. From a mechanistic point of view the reactions were found to proceed through the formation of a five coordinate intermediate that possesses little or no discriminating ability towards the incoming nucleophiles. The rate data were thus interpreted in terms of a dissociative (D) or dissociative interchange (Id) mechanism. Activation parameters H and S are reported. Preliminary studies on the solvatochromic behavior of [Ru(CHDH)2(PPh3)2] and the corresponding mixed complexes are discussed. 相似文献
37.
R. Abu-Eittah Maher M. Hamed A. A. Mohamed 《International journal of quantum chemistry》1991,39(2):211-226
The electronic absorption spectra of 2-, 3-, and 4-vinylpyridines and 1,2-(2,3-dipyridyl), 1,2-(2,4-dipyridyl), 1,2-(3,4-dipyridyl), and 1,2-(4,4-dipyridyl) ethylenes have been investigated in polar and nonpolar solvents. A correlation has been made between the geometry of the molecule and the observed spectrum. Molecular orbital calculations have been carried out using the INDO/S? CI procedure and a limited geometry optimization. The solvent effect at the MO level has been calculated. MO calculations predicted the existence of nπ* transitions that were not observed experimentally. The wave functions of the different CI states were calculated. The experimental transition energy as well as oscillator strength corresponded satisfactorily with the calculated ones. The observed transitions were assigned according to the results of MO calculations. 相似文献
38.
Combination of an ultrasonic nebulizer and plasma excitation sources for spectrochemical analysis offers desirable features of low detection limits, high sample throughput, wide dynamic range of operation, acceptable precision and accuracy, and simultaneous quantitative analytical capabilities. Moreover, the ultrasonic nebulizer does not require sample preconcentration. Recently we have developed a three-phase plasma arc (TPPA) for atomic emission spectrochemical analysis. In the present work, to increase the analytical utility of the three-phase plasma system, an ultrasonic nebulizer was used for sample introduction. The effects of the argon gas flow rate, current, excitation temperature have been studied. The analytical calibration curves are obtained for Ca, Cr, Fe, Mg and Mn, and detection limits have been calculated. The present technique is used to determine the concentration of the elements Ca, Cr, Fe, Mg and Mn in airborne samples. 相似文献
39.
The conversion of amorphous tricalcium phosphate with different hydration ratio into apatite in water at 25 °C has been studied by microcalorimetry and several physical-chemical methods. The hydrolytic transformation was dominated by two strong exothermic events. A fast, relatively weak, wetting process and a very slow but strong heat release assigned to a slow internal rehydration and the crystallization of the amorphous phase into an apatite. The exothermic phenomenon related to the rehydration exceeded the crystalline transformation enthalpy. Rehydration occurred before the conversion of the amorphous phase into apatite and determined the advancement of the hydrolytic reaction. The apatitic phases formed evolved slightly with time after their formation. The crystallinity increased whereas the amount of HPO42− ion decreased. These data allow a better understanding of the behavior of biomaterials involving amorphous phases such as hydroxyapatite plasma-sprayed coatings. 相似文献
40.
Mohamed S. A. El‐Gaby Ahmed M. Sh El‐Sharief Ahmed A. Atalla Abu‐Bakr A. A. M. El‐Adasy 《中国化学会会志》2004,51(2):327-333
The novel cyanothioformamides 2a‐d were prepared by treatment of isothiocyanatosulfonamides 1a‐d with potassium cyanide at room temperature. Cyclocondensation of compounds 2b,c with phenyl isocyanate as electrophile furnished the corresponding imidazolidines 3a,b . The reactivity of compound 3a towards some nitrogen nucleophiles was investigated. Thus, the thiosemicarbazone 4 and imidazo[4,5‐b]quinoxaline 6 were synthesized by condensation of compound 3a with thiosemicarbazide and o‐phenylenediamine, respectively. Treatment of 3a with hydrochloric acid afforded compound 7 . Our investigation was extended to include the reactivity of cyanothioformamide 2 towards o‐aminophenol, anthranilic acid, and o‐phenylenediamine and yielded the corresponding heterocycles 9 , 11 and 13 derivatives, respectively. Structures of the synthesized compounds were established by their elemental analysis and spectral data. 相似文献