全文获取类型
收费全文 | 3117篇 |
免费 | 195篇 |
国内免费 | 79篇 |
专业分类
化学 | 825篇 |
晶体学 | 18篇 |
力学 | 110篇 |
综合类 | 18篇 |
数学 | 298篇 |
物理学 | 991篇 |
无线电 | 1131篇 |
出版年
2024年 | 6篇 |
2023年 | 35篇 |
2022年 | 78篇 |
2021年 | 81篇 |
2020年 | 96篇 |
2019年 | 78篇 |
2018年 | 73篇 |
2017年 | 92篇 |
2016年 | 105篇 |
2015年 | 99篇 |
2014年 | 151篇 |
2013年 | 442篇 |
2012年 | 129篇 |
2011年 | 125篇 |
2010年 | 102篇 |
2009年 | 139篇 |
2008年 | 137篇 |
2007年 | 188篇 |
2006年 | 164篇 |
2005年 | 139篇 |
2004年 | 129篇 |
2003年 | 112篇 |
2002年 | 80篇 |
2001年 | 63篇 |
2000年 | 63篇 |
1999年 | 69篇 |
1998年 | 49篇 |
1997年 | 28篇 |
1996年 | 36篇 |
1995年 | 33篇 |
1994年 | 35篇 |
1993年 | 27篇 |
1992年 | 28篇 |
1991年 | 21篇 |
1990年 | 21篇 |
1989年 | 18篇 |
1988年 | 21篇 |
1987年 | 18篇 |
1986年 | 17篇 |
1985年 | 12篇 |
1984年 | 11篇 |
1983年 | 4篇 |
1982年 | 9篇 |
1981年 | 2篇 |
1980年 | 3篇 |
1979年 | 7篇 |
1978年 | 4篇 |
1977年 | 3篇 |
1972年 | 4篇 |
1970年 | 1篇 |
排序方式: 共有3391条查询结果,搜索用时 0 毫秒
21.
Elisa Brivio Alessandro Ceriotti Roberto Della Pergola Luigi Garlaschelli Mario Manassero Mirella Sansoni 《Journal of Cluster Science》1995,6(2):271-287
Redox condensation of [Ru3H(CO)11]- with Ni(CO)4, in tetrahydrofuran solution, under a nitrogen atmosphere, yields the tetranuclear anion [NiRuH(CO)11)-. Subsequent deprotonation with Bu'OK in acetonitrile solution leads to the formation of the related dianion. Both anions have been characterized by spectroscopic techniques, elemental analysis and single crystal X-ray diffraction. [PPh4][NiRu3H(CO)12] crystallizes in the triclinic space group PI with unit cell dimensionsof a = 11.842(2) Å,b = 12.335(3) Å, c = 13.3080) Å,a = 91.89(2)°, = 93.35(1)°,y = 96.41(2)°, Z = 2, V= 1926.9(7) Å'. The NiRu3, metal core of the molecule defines a distorted tetrahedron with nine terminal and three edge bridging carbonyl groups. The hydrido ligand was located by difference Fourier techniques and was found to bridge the NiRu2 basal triangle at a distance of 0.88(6) A from this plane. Selected average distances and angles are: Ru-Ru = 2.839 Å, Ru-Ni = 2.640 Å, Ru-C, = 1.910 A,Ru-C
b
= 2.084 Å, Ni-C
b
= 2.022 Å, Ru-H = 1.77 Å, C-0, = 1.135 Å, C-O
b
= 1.159 Å, M-C-O, = 176.3°,M-C--O
b
= 139.3°;other distances are: Ni-C1 = l.758(7) Å, Ni-H= 1.85(7) Å. [NEt4]2[NiRu3(CO)12] crystallizes in the orthorhombic space group Pnma (no. 62) with unit cell dimensions ofa=20.247(5) Å,b = 15.038(4)Å,c = 12.079(3) Å, Z=4, V=3678(2) A'. The molecule contains a tetrahedral NiRu3 core with eight terminal and four edge bridging carbon monoxide groups which bridge the three Ni-Ru and one Ru-Ru bond. Average distances and angles are: Ru -Ru =2.3050A Ru-Ni 2.648 Å, Ru-C
t
= 1.878 Å, Ru-C
b
2.045 Å, Ni-C
b
= 2.055 Å, C-O
t
= 1.145 Å, C-01,=1.157 Å, M-C-O,= 176.9°, M-C-O
b
= 138.6°; other distance is: Ni-C
t
= 1.754(10) Å,t = terminal,b = bridging. 相似文献
22.
In this paper we have reviewed the theoretical framework of the coupled-cluster (cc) based linear response model as a tool
for directly calculating energy differences of spectroscopic interest like excitation energy (ee), ionisation potential (ip)
or electron affinity (ea). In this model, the ground state of a many-electron system is described as in a coupled cluster
theory for closed shells. The electronic ground state is supposed to interact with an external photon field of frequencyw, and the poles of the linear response function as a function ofw furnish with the elementary excitations of the system. Depending on the general form of the coupling term chosen, appropriate
difference energies like ee, ip or EA may be generated. Pertinent derivations of the general working equations are reviewed,
and specific details as well as approximations for ee, ip or ea are indicated. It is shown that the theory bears a close resemblance
to the equation of motion (eom) method but is superior to the latter in that the ground state correlation is taken to all orders and may be looked upon
as essentially a variant of renormalisedtda. A perturbative analysis elucidating the underlying perturbative structure of the formulation is also given which reveals
that the theory has a hybrid structure: the correlation terms are treated akin to an open shellmbpt, while the relaxation terms are treated akin to a Green function theory. A critique of the methodvis-a-vis other cc-based approaches for difference energies forms the concluding part of our review. 相似文献
23.
Effect of Enzyme Modification of Corn Grits on their Properties as an Adsorbent in a Skarstrom Pressure Swing Cycle Dryer 总被引:1,自引:0,他引:1
Corn grits have been tested as a desiccant in a pressure swing adsorption (PSA) system to produce dry air. Two sizes of unmodified corn grits were tested in the PSA system: 2.16 and 0.978 mm in diameter, which dried moist air to dew points of –42°C and –69°C, respectively. A modification technology has been developed for the corn grits that gives an increase in the operational adsorptive capacity in a pressure swing adsorption system, so that they remove as much moisture from air as molecular sieves at the same conditions. After modification, 2.16 mm corn grits dry moist air to a –56°C dew point and the 0.978 mm corn grits dry air to a –80°C dew point. The modification process creates surface modifications on the corn grits apparently making more adsorption sites easily available. The modification procedure increases the specific surface area of the grits and possibly decreases the crystallinity, which would make more hydroxyl groups available for adsorption of water. Possible applications of using corn grits in the pressure swing adsorption system include industrial gas dryers, sorptive cooling air conditioners, and recycling equipment for industrial solvents. 相似文献
24.
Jörg Kärger 《Adsorption》2003,9(1):29-35
A review is given on the main problems associated with the determination and interpretation of molecular diffusion in zeolites. It is shown that the diffusivities may most decisively depend on the relevant space and time scales of observation, as well as on the physical state under which the measurements are carried out. Special emphasis is given to the microscopic techniques and their most recent evidence on the existence of transport resistances distributed over the intracrystalline space. 相似文献
25.
Molecular and nanoscale materials and devices in electronics 总被引:2,自引:0,他引:2
Over the past several years, there have been many significant advances toward the realization of electronic computers integrated on the molecular scale and a much greater understanding of the types of materials that will be useful in molecular devices and their properties. It was demonstrated that individual molecules could serve as incomprehensibly tiny switch and wire one million times smaller than those on conventional silicon microchip. This has resulted very recently in the assembly and demonstration of tiny computer logic circuits built from such molecular scale devices. The purpose of this review is to provide a general introduction to molecular and nanoscale materials and devices in electronics. 相似文献
26.
Karen L. Kindle 《Applied biochemistry and biotechnology》1983,8(2):153-170
Thermostable α-amylases have application in a variety of industrial processes and enzymes from a substantial number of thermophilic
bacteria and fungi have been screened and characterized to varying degrees. The characteristics of these enzymes are summarized
in this review. The genetics of α-amylase production inBacillus subtilis is reviewed and classical and recombinant DNA approaches to increasing α-amylase production are discussed. 相似文献
27.
Ryu I 《Chemical record (New York, N.Y.)》2002,2(4):249-258
New approaches in radical carbonylation chemistry are described. We have successfully integrated tin mediated radical carbonylation chemistry into modern fluorous applications and separation techniques. We revealed that radical carbonylation reactions can be performed using fluorous tin mediators, such as fluorous tin hydride and fluorous allyltin reagents. Fine tuning of the reaction conditions resulted in a good efficiency equivalent to conventional tin mediators. The tedious procedure of removing organotin byproducts can be circumvented through the use of fluorous/organic liquid-liquid extraction or fluorous liquid-solid phase extraction with fluorous reverse phase silica (FRPS). Also described are newly developed tandem carbonylation reactions that are based on species hybridization approaches. Using a radical/anionic hybrid system based on zinc-induced one-electron reduction, we achieved a three-component coupling reaction consisting of 4-alkenyl iodides, carbon monoxide, and electron-deficient alkenes. We observed two types of annulations processes, namely [4 + 1](radical)/[3 + 2](anionic) and [5 + 1](radical)/[3 + 2](anionic), which lead to the production of bicyclo[3.3.0]octanols and bicyclo[3.2.1]octanols, respectively. We found a radical/palladium hybrid system to be useful in the construction of new cyclic systems that incorporate two or three molecules of carbon monoxide. 相似文献
28.
M. F. Gonnord I. Ignatiadis A. Jaulmes C. Vidal-Madjar 《Journal of separation science》1987,10(7):392-397
The performances of some numerical methods to improve the signal to noise ratio are compared and applied to enhance noisy signals obtained in gas chromatography with capillary columns and a flame Ionization detector. Several methods have been considered: cutoffs In the Fourier transform of the recorded signal; real time numerical filtering; theoretical model curve fitting; and the correlation of a chromatogram recorded from a pseudorandomly injected sample with the pseudorandom injection function. Numerical real time filtering is shown to be the most convenient method when the main periodic component of the noise has been determined by Fourier analysis. 相似文献
29.
Barontini F. Marsanich K. Cozzani V. 《Journal of Thermal Analysis and Calorimetry》2004,78(2):599-619
The TG-FTIR technique was used in the present study to investigate the thermal degradation behaviour of materials containing
brominated flame retardants under fire conditions. Time-temperature profiles and oxygen concentrations typical of selected
fire scenarios were reproduced in the thermogravimetric analyzer, while the characterization of the gaseous products generated
was performed by the simultaneous FTIR analysis. FTIR analysis combined with the use of specific calibration procedures allowed
the quantitative estimation of the gaseous products evolved as a function of experimental conditions. The results obtained
allowed the straightforward assessment and the comparison of the quantities of hydrogen bromide formed in the oxidation and
thermal degradation of pure brominated flame retardants and of flame retarded materials of industrial interest. Hydrogen bromide
yields resulted dependent on the experimental conditions used, such as oxygen concentration and heating rate. Although TG-FTIR
experiments only provide a representation of the actual heterogeneous combustion products in real fire conditions, the coupled
TG-FTIR technique proved to be a straightforward experimental methodology allowing one to obtain reference data on the nature
and quantities of the macropollutants generated in a fire.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
30.
Methods for metal preconcentration are often described in the literature. However, purposes are often different, depending
on whether the methods are applied in environmental, clinical or technological fields. The respective method needs to be efficient,
give high sensitivity, and ideally also is selective which is useful when used in combination with atomic spectroscopy. This
review presents the actual tendencies in metal preconcentration using techniques such as Flame Atomic Absorption Spectrometry
(FAAS), Electrothermal Atomic Absorption Spectrometry (ETAAS), Hydride Generation Atomic Absorption Spectrometry (HGAAS),
Inductively Coupled Plasma Optical Emission Spectrometry (ICP OES) and Inductively Coupled Plasma Mass Spectrometry (ICP-MS).
Procedures based on related to electrochemical, coprecipitation/precipitation, liquid–liquid and solid–liquid extraction and
atom trapping mechanisms are presented.
Correspondence: Department of Analytical Chemistry, Universidade Estadual de Campinas – UNICAMP, P.O. Box 6154, 13083-970
Campinas, Brazil. e-mail: zezzi@iqm.unicamp.br
Received December 20, 2001; accepted October 11, 2002 相似文献