全文获取类型
收费全文 | 1511篇 |
免费 | 34篇 |
国内免费 | 5篇 |
专业分类
化学 | 1117篇 |
晶体学 | 9篇 |
力学 | 34篇 |
综合类 | 1篇 |
数学 | 197篇 |
物理学 | 192篇 |
出版年
2023年 | 13篇 |
2022年 | 30篇 |
2021年 | 49篇 |
2020年 | 42篇 |
2019年 | 33篇 |
2018年 | 30篇 |
2017年 | 34篇 |
2016年 | 47篇 |
2015年 | 35篇 |
2014年 | 51篇 |
2013年 | 84篇 |
2012年 | 91篇 |
2011年 | 101篇 |
2010年 | 67篇 |
2009年 | 60篇 |
2008年 | 86篇 |
2007年 | 89篇 |
2006年 | 68篇 |
2005年 | 74篇 |
2004年 | 66篇 |
2003年 | 41篇 |
2002年 | 51篇 |
2001年 | 14篇 |
2000年 | 15篇 |
1999年 | 10篇 |
1998年 | 10篇 |
1997年 | 13篇 |
1996年 | 14篇 |
1995年 | 17篇 |
1994年 | 12篇 |
1993年 | 16篇 |
1992年 | 14篇 |
1991年 | 9篇 |
1990年 | 10篇 |
1989年 | 8篇 |
1988年 | 11篇 |
1987年 | 13篇 |
1985年 | 4篇 |
1983年 | 12篇 |
1982年 | 11篇 |
1981年 | 9篇 |
1980年 | 8篇 |
1979年 | 4篇 |
1978年 | 10篇 |
1977年 | 5篇 |
1976年 | 10篇 |
1975年 | 5篇 |
1974年 | 8篇 |
1970年 | 4篇 |
1955年 | 3篇 |
排序方式: 共有1550条查询结果,搜索用时 0 毫秒
81.
Marcel Špulák Zdeněk Novák Karel Palát Jiří Kuneš Jana Pourová Milan Pour 《Tetrahedron》2013,69(6):1705-1711
Contrary to a number of reports, alkylations of the privileged 3,4-dihydroquinazoline scaffold provide N3-alkylated products, and not 4-alkoxyquinazolines. To correctly assign the structure, 13C NMR shifts of the –Z–CHn– (Z=O, N) fragment are necessary; resonances in the 45–55 ppm range are indicative of N3-alkylation. Treatment of 3,4-dihydroquinazoline-4-one with p-TsCl afforded the N3-tosylated compound, whose reaction with an amine yielded the corresponding N3-alkyl derivative. A mechanism corroborated by 15N-labeling involving pyrimidine ring opening and recyclisation is proposed. Finally, the unambiguous preparation of 4-alkoxyquinazolines is described via treatment of 3,4-dihydroquinazoline-4-ones with PCl5 followed by an alkoxide. 相似文献
82.
This report describes a new type of intra-intermolecular criss-cross cycloadditions. Thermal reactions of unsymmetrical allenylazines in the presence of alkynes led to three fused five-membered heterocycles in some cases. In the case of unsymmetrical substituted alkynes, a regioselectivity was observed. The molecular structures of all products are discussed. One X-ray crystal structure is also reported. 相似文献
83.
Zuzana Vasková Jan Moncol Maria Korabik Dušan Valigura Jozef Švorec Tadeusz Lis Marian Valko Milan Melník 《Polyhedron》2010
A new complex of unusual composition [Cu(3-O2Nbz)2(nia)(H2O)2] (1) (nia = nicotinamide, 3-O2Nbz = 3-nitrobenzoate) has been prepared and studied together with two other complexes of composition [Cu(4-O2Nbz)2(nia)2(H2O)2] (2) and [Cu(4-O2Nbz)2(nia)2]?(4-O2NbzH)2 (3) (4-O2Nbz = 4-nitrobenzoate). The composition of all complexes has been determined by elemental analysis, the complexes have been studied by electronic, infrared and EPR spectroscopy, as well as by magnetization measurements over the temperature range 1.8–300 K, and their structures have been solved. The structure of complex (1) consists of molecules, where Cu(II) atom is monodentately coordinated by the pair of 3-nitrobenzoato anions in trans -positions together with water and nicotinamide molecules, forming nearly tetragonal basal plane, and by another water molecule in axial position of tetragonal-pyramidal coordination polyhedron. The neighboring molecule coordination polyhedron basal planes are coplanar and allow formation of supramolecular dimers with strong H-bonds between hydrogen atoms from equatorially coordinated water molecules and uncoordinated carboxylate oxygen atoms thus giving the nearest Cu?Cu distance of 4.886(2) Å. Magnetization measurements showed that complex (1) exhibits maximum of magnetic susceptibility at 6.5 K and a fit to Bleaney-Bowers equation gave singlet–triplet energy gap 2J = −6.25 cm−1, and zJ′ = −0.03 cm−1. This might be an experimental proof that the carboxylate bridges extended with hydrogen bonds are the pathway of the spin–spin interactions. The temperature dependence of changes in EPR spectra of (1) and the spectrum at 4.2 K have confirmed its hydrogen bonded dimeric structure. The calculated Cu?Cu distance 4.8 Å is in very good agreement with the value obtained from crystal structure. The complexes (2) and (3) at 300 K exhibit magnetic moment μeff = 1.98 B.M. and μeff = 1.84 B.M., respectively. These values practically do not change with lowering the temperature up to 5 K and only small drops to μeff = 1.87 B.M. (for (2)) and μeff = 1.79 B.M. (for (3)) at 1.8 K have been observed. The EPR spectra of complex (2) at room temperature as well as at 77 K are of axial type with g⊥ = 2.062 and g|| = 2.285 and exhibit resolved parallel hyperfine splitting with A|| = 160 Gauss. The EPR spectra of complex (3) at room temperature as well as at 77 K are of axial type with g⊥ = 2.065 and g|| = 2.235 and exhibit unresolved parallel hyperfine splitting. EPR spectra of (2) and (3) are consistent with the X-ray structure. 相似文献
84.
Alexander Popkov Jiří Hanusek Jiří Čermák Vratislav Langer Robert Jirásko Michal Holčapek Milan Nádvorník 《Journal of Radioanalytical and Nuclear Chemistry》2010,285(3):621-626
In this communication the evaluation of eleven new metallocomplex alanine synthons bearing C2-symmetric benzyl groups with electron-donating and electron-withdrawing substituents is described. α-Methylated glycine synthons (alanine complexes) were evaluated alongside alanine synthons in order to obtain a deeper understanding of the relationship between their structures and stereochemistry of monoalkylated products and to choose several candidates for their further tests for stereospecific preparation of 6-[18F]FDOPA. Glycine-derived analogues of the complexes 3–5 are the best candidates for the development of a 6-[18F]FDOPA preparation procedure. In the model epimerisation reaction they demonstrated the best performance, much better compared to the previously described compound 2. Complexes 3, 5 and 8 are the best in asymmetric preparation of β-13C monolabelled α-aminoisobutyric acid. They have to be tested in the preparation of α-methyl amino acids like 6-[18F]-α-methylDOPA and 2-[18F]-α-methyltyrosine. 相似文献
85.
A rapid micro‐analytical multiresidue method was developed for analysis of pyrethroids (kadethrin K, cypermethrin C and permethrin P) in soil micro‐sample (200 mg). It uses on‐line flow‐through extraction of soil micro‐samples (packed into a short glass column) with a methanol‐aqueous citric acid buffer mixture, successive on‐line SPE preconcentration of analytes from the extract and on‐line RP‐HPLC analysis with UV photometric detection. The separation of pyrethroids is performed on a Purospher RP‐18e column with methanol/water as mobile phase. Effects of sorbent placed at the bottom of a short column holding the soil sample and different kinds of on‐line SPE columns were tested. Besides, the influence of volume of the effluent on the pyrethroids recovery was also studied. Calibration curves were linear over the range assayed from 0.01 to 0.2 μg/mL with correlation coefficients of linear regression (least‐squares method) in the range 0.998–0.999. Recovery studies were carried out at 0.25–1.00 μg/g dry soil fortification level and obtained recoveries were for K 81–84%, C 56–59% and for P 58–63%. Achieved LOD (confidence band) of studied pyrethroids were for large‐volume injection (1 mL) 4.5 ng K, 3.7 ng C, 3.6 ng P or 27 ng/g K, 32 ng/g C and 29 ng/g P in dry soil “solid sampling HPLC”. 相似文献
86.
Hofer M Pospíšil M Hoferová Z Weiterová L Komůrková D 《Molecules (Basel, Switzerland)》2012,17(5):5615-5625
The presented review summarizes experimental data obtained with a mouse model when investigating the relationship between inhibition of prostaglandin production and hematopoiesis. While prostaglandin E2 acts in a negative feedback control of myelopoiesis, inhibition of cyclooxygenases, responsible for its production, shifts the feedback to positive control. Based on these relationships, agents inhibiting cyclo-oxygenases, known as non-steroidal anti-inflammatory drugs (NSAIDs), can activate hematopoiesis and be protective or curative under myelosuppressive states. The effectiveness of therapeutic use of NSAIDs in these situations is expressive especially under the selective inhibition of cyclooxygenase-2 (COX-2), when undesirable side effects of cyclooxygenase-1 inhibition, like gastrointestinal damage, are absent. The effects of the clinically approved selective COX-2 inhibitor, meloxicam, were investigated and demonstrated significant hematopoiesis-stimulating and survival-enhancing actions of this drug in sublethally or lethally γ-irradiated mice. These effects were connected with the ability of meloxicam to increase serum levels of the granulocyte colony-stimulating factor. It can be inferred from these findings that selective COX-2 inhibitors might find their use in the treatment of myelosuppressions of various etiologies. 相似文献
87.
In our laboratory, we have been studying the reductive processes that occur during matrix-assisted laser desorption/ionization (MALDI) experiments. Recently, we have finished an analysis of the DHB matrix effect on the azo group in cyclic peptides. However, deep understanding of disulfide bond behaviour during a mass spectrometry (MS) experiment is much more important in proteomics as its reduction can cause serious errors in protein spectra interpretation. Therefore, we have focused on intra- and intermolecular disulfide bonds as well as disulfide bonds connecting cysteine and 2-thio-5-nitrobenzoic acid (TNB, Ellman's reagent modification) in model peptides during MALDI MS measurements. While the reduction was not observed for intra- and intermolecular cysteine-cysteine disulfide bonds, the disulfide connection between cysteine and TNB was always affected. It was proved that TNB and Ellman's reagent can act as a matrix itself. The results obtained enabled us to propose a reaction mechanism model which is able to describe the phenomena observed during the desorption/ionization process of disulfide-containing molecules. 相似文献
88.
89.
Dr. Mark Feyand Milan Köppen Prof. Dr. Gernot Friedrichs Prof. Dr. Norbert Stock 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(37):12537-12546
A systematic investigation of the systems Bi3+/carboxylic acid/HNO3 for the tri‐ and tetracarboxylic acids pyromellitic acid (H4Pyr), trimellitic acid (H3Tri) and trimesic acid (H3BTC) acid led to the discovery of five new bismuth carboxylates. Structural characterisation allowed the influence of the linker geometry and the Bi3+:linker molar ratio in the starting solution on the crystal structure to be determined. The crystallisation of three selected compounds was investigated by in situ energy‐dispersive X‐ray diffraction. Three new crystalline intermediates were observed within minutes, and two of them could be isolated by quenching of the reaction mixture. Their crystal structures were determined from laboratory and synchrotron X‐ray powder diffraction data and allowed a possible reaction pathway to be established. In depth characterisation of the luminescence properties of the three bismuth pyromellate compounds was carried out. Fluorescence and phosphorescence could be assigned to (mainly) ligand‐ and metal‐based transitions. The polymorphs of Bi(HPyr) exhibit different luminescence properties, although their structures are very similar. Surprisingly, doping of the three host structures with Eu3+ and Tb3+ ions was only successful for one of the polymorphs. 相似文献
90.
By adopting the convention that shared double bonds in polycyclic conjugated hydrocarbons contribute with one -electron and unshared ones with two -electrons, a partition of -electrons in each ring (-electron content, EC) can be obtained by averaging over all Kekulé structures, which are assumed to have equal weights. This affords a simple measure of local aromaticity that is comparable with other such local aromaticity indices in polycyclic benzenoids. 相似文献