全文获取类型
收费全文 | 2430篇 |
免费 | 69篇 |
国内免费 | 5篇 |
专业分类
化学 | 1581篇 |
晶体学 | 23篇 |
力学 | 67篇 |
数学 | 309篇 |
物理学 | 524篇 |
出版年
2023年 | 40篇 |
2022年 | 77篇 |
2021年 | 78篇 |
2020年 | 66篇 |
2019年 | 66篇 |
2018年 | 56篇 |
2017年 | 36篇 |
2016年 | 74篇 |
2015年 | 71篇 |
2014年 | 62篇 |
2013年 | 135篇 |
2012年 | 127篇 |
2011年 | 190篇 |
2010年 | 99篇 |
2009年 | 102篇 |
2008年 | 143篇 |
2007年 | 123篇 |
2006年 | 107篇 |
2005年 | 103篇 |
2004年 | 98篇 |
2003年 | 47篇 |
2002年 | 48篇 |
2001年 | 40篇 |
2000年 | 43篇 |
1999年 | 26篇 |
1998年 | 14篇 |
1997年 | 26篇 |
1996年 | 28篇 |
1995年 | 15篇 |
1994年 | 19篇 |
1993年 | 25篇 |
1992年 | 11篇 |
1991年 | 16篇 |
1990年 | 19篇 |
1989年 | 11篇 |
1988年 | 13篇 |
1987年 | 15篇 |
1986年 | 12篇 |
1985年 | 15篇 |
1984年 | 16篇 |
1983年 | 14篇 |
1982年 | 12篇 |
1981年 | 18篇 |
1980年 | 12篇 |
1979年 | 16篇 |
1978年 | 14篇 |
1977年 | 10篇 |
1976年 | 13篇 |
1973年 | 12篇 |
1972年 | 7篇 |
排序方式: 共有2504条查询结果,搜索用时 0 毫秒
31.
Hood BL Lucas DA Kim G Chan KC Blonder J Issaq HJ Veenstra TD Conrads TP Pollet I Karsan A 《Journal of the American Society for Mass Spectrometry》2005,16(8):1221-1230
With advancements in the analytical technologies and methodologies in proteomics, there is great interest in biomarker discovery in biofluids such as serum and plasma. Current hypotheses suggest that the low molecular weight (LMW) serum proteome possesses an archive of clipped and cleaved protein fragments that may provide insight into disease development. Though these biofluids represent attractive samples from which new and more accurate disease biomarkers may be found, the intrinsic person-to-person variability in these samples complicates their discovery. Mice are one of the most extensively used animal models for studying human disease because they represent a highly controllable experimental model system. In this study, the LMW serum proteome was compared between xenografted tumor-bearing mice and control mice by differential labeling utilizing trypsin-mediated incorporation of the stable isotope of oxygen, 18O. The digestates were combined, fractionated by strong cation exchange chromatography, and analyzed by nanoflow reversed-phase liquid chromatography coupled online with tandem mass spectrometry, resulting in the identification of 6003 proteins identified by at least a single, fully tryptic peptide. Almost 1650 proteins were identified and quantitated by two or more fully tryptic peptides. The methodology adopted in this work provides the means for future quantitative measurements in comparative animal models of disease and in human disease cohorts. 相似文献
32.
Seghezzo L Trupiano AP Liberal V Todd PG Figueroa ME Gutiérrez MA Da Silva Wilches AC Iribarnegaray M Guerra RG Arena A Cuevas CM Zeeman G Lettinga G 《Applied biochemistry and biotechnology》2003,109(1-3):167-180
A pilot-scale sewage treatment system consisting of two upflow anaerobic sludge bed (UASB) reactors followed by five waste stabilization ponds (WSPs) in series was studied under subtropical conditions. The first UASB reactor started up in only 1 mo (stable operation, high chemical oxygen demand [COD] removal efficiency, low volatile fatty acids concentration in the effluent, alkalinity ratio above 0.7, biogas production above 0.1 Nm3/kg of CODremoved). Removal efficiencies up to 90% were obtained in the anaerobic steps at a hydraulic retention time of 6 + 4 h (80% removal in the first step). Fecal coliform removal in the whole system was 99.9999% (99.94% in anaerobic steps and 99.98% in WSPs). COD balances over UASB reactors are provided. A minimum set of data necessary to build COD balances is proposed. Intermittent sludge washout was detected in the reactors with the COD balances. Sludge washout from single-step UASB reactors should be monitored and minimized in order to ensure constant compliance with discharge standards, especially when no posttreatment is provided. The system combined high COD and fecal coliform removal efficiency with an extremely low effluent concentration, complying with discharge standards, and making it an attractive option for sewage treatment in subtropical regions. 相似文献
33.
Barragán P Errea LF Macías A Méndez L Rabadán I Riera A Lucas JM Aguilar A 《The Journal of chemical physics》2004,121(23):11629-11638
The lowest two ab initio potential energy surfaces (PES), and the corresponding nonadiabatic couplings between them, have been obtained for the H3+ system; the molecular data are compared to those calculated with the diatomic in molecules (DIM) method. The form of the couplings is discussed in terms of the topology of the molecular structure of the triatomic. The method of Baer is employed to generate "diabatic" states and the residual nonadiabatic couplings are calculated. The ab initio results for these are markedly different from the corresponding DIM data, and show the need to consider the third PES. 相似文献
34.
Optical detection of triggered atherosclerotic plaque disruption by fluorescence emission analysis 总被引:2,自引:0,他引:2
Christov A Dai E Drangova M Liu L Abela GS Nash P McFadden G Lucas A 《Photochemistry and photobiology》2000,72(2):242-252
Fluorescence emission analysis (FEA) has proven to be very sensitive for the detection of elastin, collagen and lipids, which are recognized as the major sources of autofluorescence in vascular tissues. FEA has also been reported to detect venous thromboemboli. In this paper we have tested the hypothesis that FEA can reproducibly detect in vivo and in vitro triggered plaque disruption and thrombosis in a rabbit model. Fluorescence emission (FE) spectra, recorded in vivo, detected Russell's viper venom (RVV)-induced transformation of atherosclerotic plaque. FE intensity at 410-490 nm 4 weeks after angioplasty was significantly lower (P < 0.0033 by analysis of variance) in RVV-treated rabbits when compared to control animals with stable plaque. FE spectral profile analyses also demonstrated a significant change in curve shape as demonstrated by polynomial regression analysis (R2 from 0.980 to 0.997). We have also demonstrated an excellent correlation between changes in FE intensity and the structural characteristics detected at different stages of "unstable atherosclerotic plaque" development using multiple regression analysis (R2 = 0.989). Thus, FEA applied in vivo is a sensitive and highly informative diagnostic technique for detection of triggered atherosclerotic plaque disruption and related structural changes, associated with plaque transformation, in a rabbit model. 相似文献
35.
Analogy and deuterium labeling demonstrate that considerable remote group interaction occurs between functional groups at positions 7 and 16 in 16, 17-secosteroids. It is proposed that ion-dipole interact?ions separations of distances of 10 to 2 Å will involve energies of 1–30 kcal mol?1 and can play a significant role in fragmentation processes. Successive loss of one, two and three HOAc molecules from a milecular or daughter ion increase progressively in relative intensity; irregularity in this pattern indicates the operation of special factors or multiple genesis of daughter ions having the same m/e. Evidence is presented which suggests that facile ketene ejection from the acetate functional group only occurs from a radical ion and must be preceded by transfer of a hydrogen radical from the acetate group to the site of charge localization. 相似文献
36.
Maria Merces Marques C. Costa F. Lemos F. Ram?a Ribeiro A. R. Dias 《Reaction Kinetics and Catalysis Letters》1997,62(1):9-15
In this paper we present a kinetic approach to the analysis of steady-state homogeneous Ziegler-Natta polymerization activity
data. The influence of the number of monomeric species that are coordinated to the active site on the apparent rate law is
discussed and the equations are fitted to the experimental results. 相似文献
37.
Ibrahim Y Alsharaeh E Dias K Meot-Ner Mautner M El-Shall MS 《Journal of the American Chemical Society》2004,126(40):12766-12767
We studied the stepwise hydration and solvent-mediated deprotonation of the benzene*+ cation (Bz*+) and found several unusual features. The solvent binding energies DeltaH on-1,n for the reactions Bz*+(H2O)n-1 + H2O --> Bz*+(H2O)n are nearly constant at 9 +/- 1 kcal mol-1 for n = 1 to 8. We observed a remarkable sudden decrease in the entropy of association accompanying the formation of Bz*+(H2O)7 and Bz*+(H2O)8, indicating strong orientational restraint in the hydration shells of these clusters consistent with the formation of cagelike structures. We observed the size-dependent deprotonation of Bz*+ in a cooperative multibody process, where n H2O molecules (n >/= 4) can remove a proton from Bz*+ to form protonated water clusters. We measured, for the first time, the temperature dependence of such a process and found a negative temperature coefficient of a magnitude unprecedented in any chemical reaction, of the form k = AT-67+/- 4, or in an Arrhenius form having an activation energy of -34 +/- 1 kcal mol-1. The temperature effect may be explained by Bz*+ and four H2O molecules needing to be assembled from gas-phase components to form the reactive species. Such large temperature effects may be therefore general in solvent cluster-mediated reactions. 相似文献
38.
The temperature dependence in the range 23–135°C of hot-drawn HDPE plates maintained free from contraction was investigated by WAXS and DSC. A specially designed cylindrical chamber was used for the WAXS patterns. The results confirm the coexistence of two populations of orthorhombic crystals which have different lattice and thermal behaviour. The crystal lattice parameter a shows expansion, while b exhibits expansion up to 90°C, followed by contraction as the temperature is raised to melting. On the other hand, the c parameter is practically constant. 相似文献
39.
Subhendu?Biswas Kamala?Mitra Bibhutosh?AdhikaryEmail author C.?Robert.?Lucas 《Transition Metal Chemistry》2005,30(5):586-592
Synthesis of six hydroxo-bridged binuclear manganese(III) complexes of formulae [MnL-X-MnL](ClO4) [X = OH (1–6)] along with a mononuclear manganese(III) complex (7) [Mn(L)(L′)(MeOH)2] [HL′ = 2-(2-hydroxy-phen-yl)benzimidazole] and two carboxylate-bridged binuclear manganese(III) complexes (8) and (9) are described. The complexes have been characterized by the combination of i.r., u.v.-vis spectroscopy, magnetic moments and by their redox properties. The electronic spectra of all the complexes exhibit almost identical features consisting of two d–d bands at ca. 550 and 600 nm, one MLCT band at ca.400 nm, together with two π–π* intra-ligand transitions at ca. 250 nm and ca.300 nm. Room temperature magnetic data range from μ = 2.7–3.0 BM indicates some super-exchange between the binuclear metal centers via bridging hydroxo/carboxylato groups. The X-ray crystal structure of the binuclear complex (5) revealed that it has a symmetric MnIIIN2O2 core bridged by a hydroxyl group. The X-ray analysis of the mononuclear complex (7) showed that the manganese-center possesses a distorted octahedral geometry. Electrochemical properties of hydroxo-bridged manganese(III) complexes (1–6) show identical features consisting of an irreversible and a quasi-reversible reduction corresponding to the Mn2III → MnIIMnIII → MnIIMnII couples in the voltammogram. It was found that electron withdrawing substituents on the ligand result in easier reduction. Complex (7) displays an irreversible reduction at 0.08 V and a reversible oxidation at 0.45V assignable to the MnIII → MnII reduction and MnIII → MnIV oxidation, respectively. The carboxylate-bridged compound (8) exhibits two irreversible oxidations at 0.4 and 0.6 V, probably due to Mn2III → MnIIIMnIV → MnIVMnIV oxidations and shows a quasi-reversible reductive wave at −0.85 V, tentatively assigned to Mn2III → MnIIMnIII reduction. 相似文献
40.
A structural study of a nonstoichiometric niobium-zirconium oxyfluoride with the ReO3 type structure
Within the ZrNbOF quaternary system a nonstoichiometric compound of the ReO3 structure is formed with composition limits given by MX2.9MX3.14. Crystals at the lower end of this range with a composition of Nb0.55Zr0.45O1.1F1.8 (MX2.9) have been investigated by optical and electron microscopy and by powder and single crystal X-ray diffraction in order to determine the mode by which the nonstoichiometry has been accommodated in the structure. It was found that the material does not contain crystallographic shear planes or have a perovskite bronze type of structure but contains vacancies in the anion lattice. It seems likely that these defects are associated into clusters with a definite structure rather than being isolated from each other. 相似文献