全文获取类型
收费全文 | 4093篇 |
免费 | 105篇 |
国内免费 | 15篇 |
专业分类
化学 | 2469篇 |
晶体学 | 69篇 |
力学 | 137篇 |
数学 | 411篇 |
物理学 | 1127篇 |
出版年
2023年 | 31篇 |
2022年 | 40篇 |
2021年 | 26篇 |
2020年 | 37篇 |
2019年 | 62篇 |
2018年 | 50篇 |
2017年 | 54篇 |
2016年 | 110篇 |
2015年 | 74篇 |
2014年 | 118篇 |
2013年 | 232篇 |
2012年 | 202篇 |
2011年 | 302篇 |
2010年 | 206篇 |
2009年 | 195篇 |
2008年 | 231篇 |
2007年 | 251篇 |
2006年 | 219篇 |
2005年 | 178篇 |
2004年 | 148篇 |
2003年 | 129篇 |
2002年 | 91篇 |
2001年 | 47篇 |
2000年 | 51篇 |
1999年 | 53篇 |
1998年 | 48篇 |
1997年 | 36篇 |
1996年 | 40篇 |
1995年 | 44篇 |
1994年 | 36篇 |
1993年 | 36篇 |
1992年 | 45篇 |
1991年 | 31篇 |
1990年 | 38篇 |
1989年 | 28篇 |
1988年 | 25篇 |
1987年 | 39篇 |
1986年 | 34篇 |
1985年 | 43篇 |
1984年 | 44篇 |
1983年 | 29篇 |
1982年 | 42篇 |
1981年 | 52篇 |
1980年 | 29篇 |
1979年 | 41篇 |
1978年 | 43篇 |
1976年 | 27篇 |
1975年 | 25篇 |
1974年 | 22篇 |
1973年 | 23篇 |
排序方式: 共有4213条查询结果,搜索用时 11 毫秒
81.
A general route for the synthesis of highly substituted aryl cyclopentanes has been developed involving Diels-Alder reaction of asymmetric dienes prepared from (+)-camphoric acid followed by aromatization of the resulting cyclohexene derivatives. Employing this protocol enantiospecific synthesis of (+)-herbertene and (+)-cuparene has been accomplished. 相似文献
82.
J. Dutta A. Chatterjee S. Basu 《Journal of Radioanalytical and Nuclear Chemistry》1994,181(2):433-439
A radiochemical solvent extraction method for the determination of iron(III) employing the chelating extractant malonic anilide (MA), synthesized in our laboratory, has been described. Effects of different parameters on the extraction of iron(III) from 2M hydrochloric acid into a mixed organic solvent (methyl isobutyl ketone (TIBK) and diethyl ether) have been studied in detail. The method was applied for the estimation of iron content in several fruits using the principle of substoiciometric isotope dilution analysis. 相似文献
83.
Cimas A Rayón VM Aschi M Barrientos C Sordo JA Largo A 《The Journal of chemical physics》2005,123(11):114312
The singlet potential-energy surface for the N(2D)+CH2F(2A') reaction has been studied employing both second-order M?ller-Plesset and density-functional theories. The energies of the involved species have been refined using the Gaussian-2, complete basis set, and coupled-cluster singles and doubles (triples) methods. The reaction proceeds through the formation of an initial intermediate, which does not involve any activation barrier. Based on the energy profile for the singlet potential-energy surface, the preferred product should be the most exothermic one, namely, HCN+HF, followed by HNC+HF and FCN+H2. This result seems in contradiction with a computational study of the kinetics of the title reaction in terms of the statistical theories, which leads to the prediction that the production of HNC+HF should be the dominant channel. Consequently, a limited molecular-dynamics study has been carried out, concluding that in fact the system behaves in a nonstatistical way. According to the molecular-dynamics study, the most exothermic channel, HCN+HF, should be the dominant one. An analysis of the possible role of the singlet surface in the reaction of N(4S) with CH2F(2A') has also been carried out. The computational study shows that the microcanonical coefficients for the nonadiabatic channels are much smaller than the competing adiabatic ones. Therefore, the reaction of N(4S) with CH2F(2A') should proceed on the triplet surface without spin change. 相似文献
84.
Intramolecular [2 + 2] photocycloaddition of alkenes with a furano sugar placed between them have been investigated under both copper(I)-catalyzed and sensitized conditions. The copper(I)-catalyzed photocycloaddition of the dienes 4a, 4b, and 4c led to unexpected formation of the thermodynamically less stable cis-syn-cis 4-5-5 tricyclic adducts 5a, 5b, and 5c, respectively. The sensitized photocycloaddition of the diene 14 also gave the cis-syn-cis adduct 15 showing that the copper(I) catalyst does not have any influence on the stereochemical course through coordination with the anomeric ring oxygen of the furano sugar. The identical stereochemical course observed under both catalyzed and sensitized photoaddition reactions have been attributed to be of steric origin. Bis(dienes) 25a and 25b, which gave an intractable mixture on copper(I)-catalyzed irradiation, underwent smooth photocycloaddition in the presence of benzophenone, and the resulting 1,2-divinyl cyclobutanes underwent spontaneous [3.3]-rearrangement at room temperature to produce bicyclo[6.3.0]undecanes 30a and 30b, respectively. This investigation provides an approach for the construction of enantiopure bicyclo[3.2.0]heptanes and -[6.3.0]undecanes. 相似文献
85.
Grace‐Ann M. Lobo Sneha A. Chitre Spandan M. Rathod Robert B. Smith Ray Leslie Callum Livingstone James Davis 《Electroanalysis》2007,19(24):2523-2528
The exploitation of 2‐bromo‐1,4‐naphthoquinone (NQBr) as a selective redox label for the determination of reduced thiol functionalities (RSH) has been investigated. The system is selective for RSH functionality, giving distinct voltammetric signals for glutathione and cysteine but can also be adapted for broad spectrum thiol detection. Ion chromatographic protocols based on conductimetric detection enable total RSH analysis (protein and monomolecular moieties) within human plasma. Bromide released through the reaction can be easily quantified and integrated within normal IC measurements. The efficacy of the approach has been assessed and the response validated through comparison with the standard colorimetric technique. 相似文献
86.
Trace amounts of lead in copper can be determined by differential-pulse anodic-stripping voltammetry after separating it from the matrix. Lead was quantitatively retained on a small Dowex 1-X4 ion-exchange column, without retaining copper when present as a copper-amine complex in solutions containing 0.2 M sodium hydroxide. Subsequent desorption was done with 2 M nitric acid. After deposition for 1 min on a hanging mercury drop electrode and subsequent stripping, the limit of detection was 2 ng ml?1 and the limit of quantification was 6.6 ng ml?1. Recoveries of lead were checked by standard addition to copper solution. 相似文献
87.
[structure: see text] The synthesis and characterization of a series of low-valent organoselenium compounds derived from 1-bromo-4-tert-butyl-2,6-di(formyl)benzene (22) is described. The synthesis of diselenide 25 was achieved by the lithiation route whereas bis(4-tert-butyl-2,6-di(formyl)phenyl) diselenide (26) was synthesized by treating 22 with disodium diselenide. A series of monoselenides (27, 28, and 29) was obtained by facile nucleophilic substitution of bromine in 22, using the corresponding selenolates as nucleophiles. The halogenation reactions of bis(4-tert-butyl-2,6-di(formyl)phenyl) diselenide (26) did not afford the corresponding selenenyl halides but resulted in the isolation of an unexpected cyclic selenenate ester 34 as a product. The selenide 32 was synthesized by the treatment of dimethoxymethyl diselenide with trilithiated 2-bromo-5-tert-butyl-N,N'-di(phenyl)isophthalamide. The existence of potential Se...O intramolecular nonbonding interactions was examined by IR, (1)H, and (77)Se NMR spectroscopy, X-ray crystallography, and computational studies. The X-ray crystal structures of 26 and 27, having two ortho formyl groups, reveal the absence of any Se...O interactions. However, the Se...O interactions were observed in the selenenate ester 34 where one of the formyl groups has been utilized for the selenenate ring formation. The crystal structures of 26 and 27 exhibited intermolecular short-range C-H...Se interactions (hydrogen bonding). Although there are four heteroatoms in carbamoyl moieties ortho to selenium capable of forming a five-membered ring on intramolecular coordination, no such intramolecular Se...X (X = N, O) interaction was observed in the crystal structure of 32. The density functional theory calculations at the B3LYP/6-31G* level predicted that for all the diformyl systems (47a-c, 48a-c), the anti,anti conformer (when both formyl oxygen atoms point away from the selenium) is more stable. This preference was found to be reversed in the monoformyl-substituted systems (50a,b, 51a,b), where the syn conformer (when formyl oxygen is near the selenium) is energetically more favorable than the anti conformer. 相似文献
88.
Frost RL Kristof J Horvath E Martens WN Kloprogge JT 《Journal of colloid and interface science》2002,251(2):350-359
Controlled rate thermal analysis (CRTA) allows the separation of adsorbed and intercalated hydrazine. CRTA displays the presence of three different types of hydrogen-bonded hydrazine in the intercalation complex: (a) The first is adsorbed loosely bonded on the kaolinite structure fully expanded by hydrazine-hydrate and liberated between approx 50 and 70 degrees C (b) The second intercalated hydrazine is lost between approx 70 and 85 degrees C. (c) The third type of intercalated-hydrazine molecule is lost in the 85-130 degrees C range. CRTA at 70 degrees C enables the removal of hydrazine-water and results in the partial collapse of the hydrazine-intercalated kaolinite structure to form a hydrazine-intercalated kaolinite. Removal of the adsorbed hydrazine enables the DRIFT spectra of the hydrazine-intercalated complex without any adsorbed hydrazine to be obtained. A band at 3626 cm(-1) attributed to the inner surface hydroxyls of kaolinite hydrogen bonded to hydrazine is observed. The intercalation of hydrazine-hydrate into kaolinite is complex and results from the different types of surface interactions of the hydrazine with the kaolinite surfaces. 相似文献
89.
J. Lawry A. Ray D. Klimesch P. Thomas J.-P. Guerbois J. Harrison 《Journal of Thermal Analysis and Calorimetry》2005,80(3):637-641
Summary Due to growing environmental concerns and the need to use less energy-intensive building products, alternatives and improvements to Portland cement (PC) are being actively researched worldwide. Use of supplementary materials is now a common practice where PC is the predominant component of inorganic building products. This study aims to investigate the potential of magnesia (MgO), derived from a naturally occurring raw material magnesite, as a supplementary material. Results from mortar samples prepared with 10 and 20% replacements of ordinary Portland cement (OPC) by MgO are presented. DTA-TG was used to study and characterise the hydration behaviour of MgO in OPC environment after 3, 7, 14, 28, 56 and 90 days of moist curing. Microstructural and compressive strength determinations providing additional information on the influence of hydrated phases are also reported. 相似文献
90.
Reaction of Hg(S7N)2 with cis- PtCl2(PR3)2 (PR3 = PPh3, PPh2Me, PPHMe2, PEt3) in the presence of Na[PF6] gives [Pt(S3N)(PR3)2][PF6] in 32–46% yield. The complexes have been characterized by IR, NMR and microanalyses. The X-ray crystal structures of two examples (PR3 = PPh2Me and PEt3) show that the S3N− ligand coordinates in a bidentate fashion via two sulphur atoms. 相似文献