全文获取类型
收费全文 | 71020篇 |
免费 | 11871篇 |
国内免费 | 2818篇 |
专业分类
化学 | 72411篇 |
晶体学 | 986篇 |
力学 | 1713篇 |
综合类 | 34篇 |
数学 | 5567篇 |
物理学 | 4998篇 |
出版年
2023年 | 97篇 |
2022年 | 261篇 |
2021年 | 523篇 |
2020年 | 998篇 |
2019年 | 2669篇 |
2018年 | 2502篇 |
2017年 | 2923篇 |
2016年 | 3322篇 |
2015年 | 5480篇 |
2014年 | 5207篇 |
2013年 | 7452篇 |
2012年 | 6695篇 |
2011年 | 5526篇 |
2010年 | 4539篇 |
2009年 | 4486篇 |
2008年 | 4899篇 |
2007年 | 4381篇 |
2006年 | 3927篇 |
2005年 | 3709篇 |
2004年 | 3164篇 |
2003年 | 2805篇 |
2002年 | 3391篇 |
2001年 | 1839篇 |
2000年 | 1693篇 |
1999年 | 875篇 |
1998年 | 298篇 |
1997年 | 297篇 |
1996年 | 311篇 |
1995年 | 316篇 |
1994年 | 222篇 |
1993年 | 187篇 |
1992年 | 159篇 |
1991年 | 105篇 |
1990年 | 69篇 |
1989年 | 53篇 |
1988年 | 52篇 |
1987年 | 44篇 |
1986年 | 42篇 |
1985年 | 31篇 |
1984年 | 33篇 |
1983年 | 12篇 |
1982年 | 27篇 |
1981年 | 14篇 |
1980年 | 18篇 |
1979年 | 15篇 |
1978年 | 7篇 |
1977年 | 8篇 |
1975年 | 4篇 |
1974年 | 3篇 |
1973年 | 6篇 |
排序方式: 共有10000条查询结果,搜索用时 218 毫秒
991.
The conversion and residence time were investigated during the bulk polymerization of styrene in a twin screw extruder. It was found that polymerization mainly occurred in the zone between 400 and 1000 mm along the screw axis in the extruder, corresponding to the residence time of the reactants ranging from 1 to 4 min in the extruder. Furthermore, the processing conditions (feed rate, screw rotation rate) and average molecular weight of the polymer have a great effect on the residence time. Based on dimensionless analysis, a model of the residence time has been built‐up, which has been confirmed by the results of realistic measurements. A kinetic model of the polymerization has also been established under the assumption that the screw extruder can be regarded as an ideal plug flow reactor. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
992.
The bi(anthracene‐9,10‐dimethylene) photoisomer has remarkably long C–C single bonds. To examine the lengthening of the C–C bond, we propose a novel procedure for quantitatively analyzing orbital interactions in a molecule at the level of the ab initio molecular orbital method. In this procedure, we can cut off the specific through‐space/bond interactions in a molecule by artificially increasing the absolute magnitude of the exponents in a Gaussian function. Then, the spatial orbital interactions were perfectly cut off, and, each term that makes up the total energy, that is, the nuclear–electron attractions, the electron–electron repulsions, and the nuclear–nuclear repulsions cancel each other. Several model molecules of the photoisomer were analyzed by this procedure. It was found that the orbital interaction between the p orbital on the benzene ring and the σ* orbital on the C–C bond in question, σ→σ* electron transfer through π orbital, weakens the C–C bond efficiently when these orbitals were located in the “periplanar” conformation. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001 相似文献
993.
Green Bis-(2-iminoisopropyl-thiophenolato)nickel(II) and other Similar NiII Complexes The compounds [NiII(iitp)2] 1 (iitp = 2-iminoisopropyl-thiophenolate), [Ni(imptp)2] · 2 CH3OH 2 , a dinuclear compound with an Ni? Ni distance of 276 pm, and [PPh4] · [NiII(imptp)(SCN)] 3 (imptp = 2-(2-iminopentane-4-on)-thiophenolate) have been prepared by the reaction of nickel(II)-acetate-tetrahydrate with 2-iminoisopropyl-thiophenole and 2-(2-iminopentane-4-on)-thiophenole in methanol, respectively. They have been characterized by single-crystal X-ray structure analysis and other physical methods. The redox behaviour of 1–3 has been studied in detail (chemically as well as by cyclovoltammetry and ESR spectroscopy). Particularly interesting are the electronic properties of 1 and its reduction with NaBH4 and the following reaction of the product with O2. The complexes are model compounds for some Ni-containing enzymes. For details of the crystal structure determination see “Inhaltsübersicht”. 相似文献
994.
For use in routine prenatal diagnostics, we developed software and methods for automatic aneuploidy detection based on a commercial multiplex ligation-dependent probe amplification (MLPA) kit. Software and methods ensure a reliable, objective, and fast workflow, and may be applied to other types of MLPA kits. Following CE of MLPA amplification products, the software automatically identified the peak area for each probe, normalized it in relation to the neighboring peak areas of the test sample, computed the ratio relative to a reference created from normal samples, and compensated the ratio for a side effect of the normalization procedure that scaled all chromosomally normal DNA peak areas slightly up or down depending on the kind of aneuploidy present. For the chromosomes 13, 18, 21, X, and Y, probe reliability weighted mean ratio values and corresponding SDs were calculated, and the significance for being outside a reference interval around ratio 1.0 was tested. p < or = 1% suggested aneuploidy and 1 < p < or = 5% suggested potential aneuploidy. Individual peaks, where the normalized area was situated more than 4 SD from the corresponding reference, suggested possible partial deletion or gain. Sample quality was automatically assessed. Control probes were not required. Having used the software and methods for two years, we conclude that a reliable, objective, and fast workflow is obtained. 相似文献
995.
The proton affinity on each of the possible sites in the antitumor 2‐(4‐aminophenyl)benzazoles has been calculated at the B3LYP/6‐311G** level of theory in the gas phase and in solution. The N3‐site of protonation is found to be strongly favored over the NH2‐site for the studied compounds both in gas phase and in solution. The stability of N3‐protonated species is explained by the resonance interaction of the NH2‐group with the heterocyclic ring. The potential energy surface (PES) for the protonation process was studied at the density functional theory (DFT)/B3LYP/6‐311++G** level of theory. Solvent effects on the PES were also examined using two models: Onsager self‐consistent field and polarizable continuum model (PCM). © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 相似文献
996.
The cyclic voltammetric behavior of carbon paste electrodes modified by direct admixing with the products of the reactions between ethanedial (glyoxal) and 5-amino-1,10-phenanthroline at 100°C and that of their iron(II) complexes is reported. The ligand(s) produced in absence of iron(II) are able to complex iron(II) and copper(II) ions reversibly, but other ions such as nickel(II), cobalt(II), cadmium(II) and manganese(II), if complexed, show no electrochemical activity. Admixing with the products of the reaction in the presence of excess of iron(II) ion, because of high insolubility and fast electron exchange, produces surfaces useful for amperometric detection in continuous-flow systems. The voltammetric and amperometric behavior in the presence of HSO?3 ions is reported in order to illustrate this application. 相似文献
997.
Ramin Ghorbani‐Vaghei Mohammad Ali Zolfigol Nasrin Moshfeghifar Nadiya Koukabi Gholamabbas Chehardoli 《中国化学会会志》2007,54(3):791-794
An efficient method for the oxidative coupling of thiols to their corresponding disulfides by new reagents poly(N‐bromobenzene‐1,3‐disulfonylamide) PBBS , N,N,N′,N′‐tetrabromobenzene‐1,3‐disulfonylamide TBBDA and DABCO‐bromine complex is described. The reaction was applicable to a variety of thiols with high chemoselectivity. 相似文献
998.
N.V. Loginova T.V. Kovalchuk R.A. Zheldakova A.A. Chernyavskaya N.P. Osipovich G.K. Glushonok G.I. Polozov V.N. Povalishev V.L. Sorokin O.I. Shadyro 《Polyhedron》2006,25(18):3603-3610
Cu (II) complexes with 3,5-di(tert-butyl)-1,2-benzenediol (I), 4,6-di(tert-butyl)-1,2,3-benzentriol (II) and sulfur-containing sterically hindered o-diphenol derivatives such as 4,6-di(tert-butyl)-3-(2-hydroxyethylsulfanyl)-1,2-benzenediol (III) and 2-[4,6-di(tert-butyl)-2,3-dihydroxyphenylsulfanyl]acetic acid (IV) have been synthesized and characterized by means of elemental analysis, TG/DTA, FT-IR, ESR, XPS, XPD and conductivity measurements. Antifungal activities of these ligands and their respective Cu (II) complexes have been determined against Aspergillus niger, Fusarium sp., Penicillium lividum, Mucor sp. and Botrytis cinerea. Most of the compounds (both the free ligands and the complexes) exert pronounced antifungal activities (RI 70%), and virtually all of them (apart from the Cu(LII)2 complex) have the highest inhibitory properties (RI = 100%) against B. cinerea. 相似文献
999.
Gabelica V Galic N Rosu F Houssier C De Pauw E 《Journal of mass spectrometry : JMS》2003,38(5):491-501
A method for determining the equilibrium association constant of a complexation reaction A + B left harpoon over right harpoon AB by electrospray ionization mass spectrometry is described. The method consists in measuring the relative intensities of the peaks corresponding to A and to AB in equimolar A-B solutions at different concentrations C(0). The results are fitted by a non-linear least-squares procedure, with the two variable parameters being the equilibrium association constant K(a) and a factor R, defined by I(AB)/I(A) = R x [AB]/[A]. The factor R is the ratio between the response factors of AB and A, and corrects for the relative electrospray responses of the complex and the free substrate A, mass discrimination of instrumental origin and/or moderate in-source dissociation. The method is illustrated with the following two systems: complexes between a double-stranded 12-base pair oligonucleotide and minor groove binders, and cyclodextrin complexes with alpha,omega-dicarboxylic acids. For the oligonucleotide complexes, it is found that the response of the complex is not dramatically different to the response of the free oligonucleotide duplex, as the double helix conformation is disturbed by the drug only to a minor extent. In the case of cyclodextrin complexes, these complexes were found to have a much higher response than free cyclodextrin. This may be due to the fact that cyclodextrin is neutral in solution, whereas the complex is charged, but it can also stem from the fact that a significant proportion of the complex is in a non-inclusion geometry. The present method requires the exact determination of the concentrations of the reactants and is applicable to 1 : 1 complexes. 相似文献
1000.
The mass resolution of a time-of-flight (TOF) mass spectrometer is directly proportional to its total flight pathlength. Multi-turn or multi-passage ion optical geometries are necessary to obtain fight distances of sufficient length within reasonable size limitations. We have investigated ion optics for a multi-turn TOF mass spectrometer with electrostatic sectors. The concept of 'perfect' focusing conditions is introduced. Furthermore, a new type of multi-turn TOF mass spectrometer, the MULTUM Linear plus, was developed. It consists of four cylindrical electric sectors and 28 electric quadrupole lenses. It has a vacuum chamber 60 x 70 x 20 cm in size. Mass resolution is demonstrated to increase according to the number of ion cycles. A mass resolution of 350 000 (m/z = 28, FWHM) was achieved after 501.5 cycles. The MULTUM Linear plus analyzer is not simple, however; 28 electric quadrupole lenses are used. In order to reduce the number of ion optical parts, an improved multi-turn TOF mass spectrometer, the MULTUM II, consisting of only four toroidal electric sectors, was also developed. The possibility of tandem mass spectrometric applications using multi-turn TOF mass spectrometers is also discussed. 相似文献