全文获取类型
收费全文 | 3036篇 |
免费 | 241篇 |
国内免费 | 196篇 |
专业分类
化学 | 1810篇 |
晶体学 | 64篇 |
力学 | 90篇 |
综合类 | 26篇 |
数学 | 465篇 |
物理学 | 1018篇 |
出版年
2023年 | 48篇 |
2022年 | 63篇 |
2021年 | 68篇 |
2020年 | 72篇 |
2019年 | 77篇 |
2018年 | 83篇 |
2017年 | 81篇 |
2016年 | 110篇 |
2015年 | 89篇 |
2014年 | 112篇 |
2013年 | 164篇 |
2012年 | 204篇 |
2011年 | 189篇 |
2010年 | 141篇 |
2009年 | 174篇 |
2008年 | 160篇 |
2007年 | 141篇 |
2006年 | 115篇 |
2005年 | 113篇 |
2004年 | 80篇 |
2003年 | 88篇 |
2002年 | 86篇 |
2001年 | 56篇 |
2000年 | 34篇 |
1999年 | 41篇 |
1998年 | 30篇 |
1997年 | 28篇 |
1996年 | 36篇 |
1995年 | 39篇 |
1994年 | 28篇 |
1993年 | 36篇 |
1992年 | 42篇 |
1991年 | 27篇 |
1990年 | 31篇 |
1989年 | 32篇 |
1988年 | 21篇 |
1987年 | 23篇 |
1986年 | 28篇 |
1985年 | 37篇 |
1984年 | 37篇 |
1983年 | 27篇 |
1982年 | 19篇 |
1980年 | 18篇 |
1979年 | 20篇 |
1978年 | 18篇 |
1977年 | 17篇 |
1976年 | 21篇 |
1974年 | 17篇 |
1973年 | 31篇 |
1942年 | 16篇 |
排序方式: 共有3473条查询结果,搜索用时 15 毫秒
131.
In this paper, 1,2-bis(2-acetamido-6-pyridyl)ethane, receptor 1, having an ethylene spacer is reported to recognise dicarboxylic acids. The binding study in the solution phase is carried out using 1H NMR (1:1) and UV–vis experiments and in the solid phase by single-crystal X-ray analysis. In 1H NMR, the downfield shifts of specific amide protons of receptor 1 in 1:1 complexes of receptor and guest diacids, and in the UV–vis experiment, the appearance of an isosbestic point as well as significant binding constants are observed, which thus unambiguously support the complexation of receptor 1 with dicarboxylic acids in solution. Receptor 2, simple 2-acetamido-6-methylpyridine, has lower binding constants than receptor 1 due to cooperative binding of two pyridine amide groups with two acid groups of diacids. In the solid phase, the ditopic receptor 1 shows a grid-like polymeric hydrogen-bonded network that changes to a polymeric wave-like 1:1 anti-perpendicular network instead of the syn–syn polymeric 1:1 (Goswami, S.; Dey, S.; Fun, H.-K.; Anjum, S.; Rahman, A.-U. Tetrahedron Lett. 2005, 46, 7187–7191), anti–anti polymeric 1:1 (Goswami, S.; Jana, S.; Dey, S.; Razak, I.A.; Fun, H.-K. Supramol. Chem. 2006 , 18, 571–574; Goswami, S.; Jana, S.; Fun, H.-K. Cryst. Eng. Comm. 2008, 10, 507–517; Goswami, S.; Jana, S.; Dey, S.; Sen, D.; Fun, H.-K.; Chantrapromma, S. Tetrahedron 2008, 64, 6426–6433), syn–syn 2:2 (Karle, I.L.; Ranganathan, D.; Haridas, V. J. Am. Chem. Soc. 1997 , 119, 2777–2783) or top–bottom-bound 1:1 (Garcia-Tellado, F.; Goswami, S.; Chang, S.K.; Geib, S.J.; Hamilton, A.D. J. Am. Chem. Soc. 1990 , 112, 7393–7394) co-crystals. 相似文献
132.
One-electron oxidation of bis(4-tert-butylphenyl)aminoxyl with antimony pentachloride and bromine leads to the formation of oxoammonium salts with anions SbCl 6 ? and Br 3 ? respectively. The salt with the Br 3 ? anion converted at heating into a mixture of bromodiphenylamines which formed also from the aminoxyl as a result of previously unknown reaction of three-electron reductive bromination. The mechanisms of these reactions were assumed. 相似文献
133.
Kaushik Sen Bhaskar Mondal Srimanta Pakhira Chandan Sahu Deepanwita Ghosh Abhijit K. Das 《Theoretical chemistry accounts》2013,132(8):1-17
The association reaction between silyl radical (SiH3) and H2O2 has been studied in detail using high-level composite ab initio CBS-QB3 and G4MP2 methods. The global hybrid meta-GGA M06 and M06-2X density functionals in conjunction with 6-311++G(d,p) basis set have also been applied. To understand the kinetics, variational transition-state theory calculation is performed on the first association step, and successive unimolecular reactions are subjected to Rice–Ramsperger–Kassel–Marcus calculations to predict the reaction rate constants and product branching ratios. The bimolecular rate constant for SiH3–H2O2 association in the temperature range 250–600 K, k(T) = 6.89 × 10?13 T ?0.163exp(?0.22/RT) cm3 molecule?1 s?1 agrees well with the current literature. The OH production channel, which was experimentally found to be a minor one, is confirmed by the rate constants and branching ratios. Also, the correlation between our theoretical work and experimental literature is established. The production of SiO via secondary reactions is calculated to be one of the major reaction channels from highly stabilized adducts. The H-loss pathway, i.e., SiH2(OH)2 + H, is the major decomposition channel followed by secondary dissociation leading to SiO. 相似文献
134.
Dr. Shaojun Guo Sen Zhang Prof. Shouheng Sun 《Angewandte Chemie (International ed. in English)》2013,52(33):8526-8544
Advances in chemical syntheses have led to the formation of various kinds of nanoparticles (NPs) with more rational control of size, shape, composition, structure and catalysis. This review highlights recent efforts in the development of Pt and non‐Pt based NPs into advanced nanocatalysts for efficient oxygen reduction reaction (ORR) under fuel‐cell reaction conditions. It first outlines the shape controlled synthesis of Pt NPs and their shape‐dependent ORR. Then it summarizes the studies of alloy and core–shell NPs with controlled electronic (alloying) and strain (geometric) effects for tuning ORR catalysis. It further provides a brief overview of ORR catalytic enhancement with Pt‐based NPs supported on graphene and coated with an ionic liquid. The review finally introduces some non‐Pt NPs as a new generation of catalysts for ORR. The reported new syntheses with NP parameter‐tuning capability should pave the way for future development of highly efficient catalysts for applications in fuel cells, metal‐air batteries, and even in other important chemical reactions. 相似文献
135.
Ramu Surakanti Sumalatha Sanivarapu Chiranjeevi Thulluri Pravin S. Iyer Raghuram S. Tangirala Rambabu Gundla Dr. Uma Addepally Y. L. N. Murthy Lakshmi Velide Dr. Subhabrata Sen 《化学:亚洲杂志》2013,8(6):1168-1176
An elegant reagent‐controlled strategy has been developed for the generation of a diverse range of biologically active scaffolds from a chiral bicyclic lactam. Reduction of the chiral lactam with LAH or alkylation with LHMDS to trigger different cyclization reactions have been shown to generate privileged scaffolds, such as pyrrolidines, indolines, and cyclotryptamines. Their amenability to substitution allows us to create various compound libraries by using these scaffolds. In silico studies were used to estimate the drug‐like properties of these compounds. Selected compounds were subjected to anticancer screening by using three different cell lines. In addition, all these compounds were subjected to antibacterial screening to gauge the spectrum of biological activity that was conferred by our DOS methodology. Gratifyingly, with no additional iterative cycles, our method directly generated anticancer compounds with potency at low nanomolar concentrations, as represented by spiroindoline 14 . 相似文献
136.
Rui Feng Yong Zhang He Li Dan Wu Xiaodong Xin Sen Zhang Haiqin Yu Qin Wei Bin Du 《Analytica chimica acta》2013
Nano-montmorillonites belong to aluminosilicate clay minerals with innocuity, high specific surface area, ion exchange, and favorable adsorption property. Due to the excellent properties, montmorillonites can be used as labels for the electrochemical immunosensors. In this study, nano-montmorillonites were converted to sodium montmorillonites (Na-Mont) and further utilized for the immobilization of thionine (TH), horseradish peroxidase (HRP) and the secondary anti-zeranol antibody (Ab2). The modified particles, Na-Mont-TH-HRP-Ab2 were used as labels for immunosensors to detect zeranol. This protocol was used to prepare the immunosensor with the primary antibody (Ab1) immobilized onto the nanoporous gold films (NPG) modified glassy carbon electrode (GCE) surface. Within zeranol concentration range (0.01–12 ng mL−1), a linear calibration plot (Y = 0.4326 + 8.713 X, r = 0.9996) was obtained with a detection limit of 3 pg mL−1 under optimal conditions. The proposed immunosensor showed good reproducibility, selectivity, and stability. This new type of immunosensors with montmorillonites and NPG as labels may provide potential applications for the detection of zeranol. 相似文献
137.
One‐pot protocol for the synthesis of novel class of triazole linked 2‐sugar and 2‐aryl substituted benzimidazoles has been developed. The rapid and simple method involves copper (I) catalyzed simultaneous formation of benzimidazole and triazole rings at room temperature and in high yield. 相似文献
138.
139.
The mixed-metal cluster Yb4O4(OiPr)16Na12 has been synthesized and structurally determined by IR, elemental analysis, and single-crystal X-ray diffraction. The crystal belongs to the cubic system, space group P23 with a = b = c = 13.9788(3), V = 2731.55(10)3 , Z = 1, Dc = 1.202 g/cm 3 , Mr = 1977.42, = 3.480 mm-1 , F(000) = 972, the final R = 0.0288 and wR = 0.1511 for 1677 observed reflections with Ⅰ > 2σ(Ⅰ). X-ray analysis reveals that Yb4O4 (OiPr)16Na12 is centrosym-metric and the structure contains four ytterbium metals and twelve sodium metals, and each ytterbium atom is coordinated by six oxygen atoms. In addition, an ancillary computational analysis of the optimized molecular unit was provided. The large energy gap (3.31 eV) between HOMO and LUMO indicates that the structure framework is particularly stable. 相似文献
140.
Nguyen Huy Thuan Ramesh Prasad Pandey Ta Thi Thu Thuy Je Won Park Jae Kyung Sohng 《Applied biochemistry and biotechnology》2013,171(8):1956-1967
Myricetin is an important flavonol whose medically important properties include activities as an antioxidant, anticarcinogen, and antimutagen. The solubility, stability, and other biological properties of the compounds can be enhanced by conjugating aglycon with sugar moieties. The type of sugar moiety also plays a significant role in the biological and physical properties of the natural product glycosides. Reconstructed Escherichia coli containing thymidine diphosphate-α-l-rhamnose sugar gene cassette and Arabidopsis-derived glycosyltransferase were used for rhamnosylation of myricetin. Myricetin (100 μM) was exogenously supplemented to induced cultures of engineered E. coli. The formation of target product—myricetin-3-O-α-l-rhamnoside—was confirmed by chromatographic and NMR analyses. The yield of product was improved by using various mutants and methylated cyclodextrin as a molecular carrier for myricetin in combination with E. coli M3G3. The maximal yield of product is 55.6 μM (3.31-fold higher than the control E. coli MG3) and shows 55.6 % bioconversion of substrate under optimized conditions. 相似文献