全文获取类型
收费全文 | 2773篇 |
免费 | 157篇 |
国内免费 | 13篇 |
专业分类
化学 | 1928篇 |
晶体学 | 24篇 |
力学 | 68篇 |
数学 | 295篇 |
物理学 | 350篇 |
无线电 | 278篇 |
出版年
2024年 | 4篇 |
2023年 | 33篇 |
2022年 | 77篇 |
2021年 | 73篇 |
2020年 | 61篇 |
2019年 | 69篇 |
2018年 | 65篇 |
2017年 | 33篇 |
2016年 | 111篇 |
2015年 | 91篇 |
2014年 | 103篇 |
2013年 | 202篇 |
2012年 | 216篇 |
2011年 | 194篇 |
2010年 | 105篇 |
2009年 | 110篇 |
2008年 | 155篇 |
2007年 | 170篇 |
2006年 | 129篇 |
2005年 | 140篇 |
2004年 | 134篇 |
2003年 | 87篇 |
2002年 | 136篇 |
2001年 | 30篇 |
2000年 | 32篇 |
1999年 | 27篇 |
1998年 | 23篇 |
1997年 | 34篇 |
1996年 | 25篇 |
1995年 | 24篇 |
1994年 | 21篇 |
1993年 | 20篇 |
1992年 | 8篇 |
1991年 | 18篇 |
1990年 | 14篇 |
1989年 | 21篇 |
1988年 | 7篇 |
1987年 | 13篇 |
1986年 | 17篇 |
1985年 | 15篇 |
1984年 | 17篇 |
1983年 | 9篇 |
1982年 | 9篇 |
1981年 | 11篇 |
1980年 | 8篇 |
1979年 | 8篇 |
1978年 | 13篇 |
1977年 | 8篇 |
1976年 | 4篇 |
1973年 | 4篇 |
排序方式: 共有2943条查询结果,搜索用时 15 毫秒
61.
Yin J Aviles P Lee W Ly C Guillen MJ Munt S Cuevas C Faircloth G 《Rapid communications in mass spectrometry : RCM》2005,19(5):689-695
A rapid and sensitive liquid chromatography/tandem mass spectrometry (LC/MS/MS) assay was developed and validated to quantify a novel antineoplastic agent, PM00104, in mouse, rat, dog, and human plasma. The method was validated to demonstrate the specificity, limit of quantification (LOQ), accuracy, and precision of measurements. The calibration range for PM00104 was established using PM00104 standards from 0.01-5.0 ng/mL in blank plasma. The selected reaction monitoring (SRM), based on the m/z 692.2 --> 218.2 transition, was specific for PM00104, and that based on the m/z 697.2 --> 218.2 transition was specific for PM00104 ((13)C(2),(2)H(3)) (the internal standard, IS); no endogenous materials interfered with the analysis of PM00104 and IS from blank plasma. The assay was linear over the concentration range 0.01-5.0 ng/mL. The correlation coefficients for the calibration curves ranged from 0.9981-0.9999. The mean intra-day and inter-day accuracies for all calibration standards (n = 8) ranged from 97-105% (< or =5% bias) in human plasma, and the mean inter-day precision for all calibration standards was less than 8.5%. The mean intra- and inter-day assay accuracy for all quality control (QC) replicates in human plasma (n = 9), determined at each QC level throughout the validated runs, ranged from 96-112% (< or =12% bias) and from 102-105% (< or =5% bias), respectively. The mean intra- and inter-day assay precision was less than 15.0 and 11.8% for all QC levels, respectively. For the QC samples prepared in animal species plasma, the %CV values of the assays ranged from 1.8-8.8% in mouse plasma, from 3.7-13.8% in rat plasma, and from 3.0-7.2% in dog plasma. The assay accuracies ranged from 92-102% (< or =8% bias) for all QC levels prepared in mouse plasma; ranged from 93-106% (< or =7% bias) in rat plasma; and ranged from 95-114% (< or =14% bias) in dog plasma. The assay has been used to support preclinical pharmacokinetic and toxicokinetic studies and is currently used to measure PM00104 plasma concentrations to support clinical trials. 相似文献
62.
Wilmer H. Perera Siddanagouda R. Shivanagoudra Jose L. Prez Da Mi Kim Yuxiang Sun Guddadarangavvanahally K. Jayaprakasha Bhimanagouda S. Patil 《Molecules (Basel, Switzerland)》2021,26(4)
Diabetes mellitus is a chronic disease and one of the fastest-growing health challenges of the last decades. Studies have shown that chronic low-grade inflammation and activation of the innate immune system are intimately involved in type 2 diabetes pathogenesis. Momordica charantia L. fruits are used in traditional medicine to manage diabetes. Herein, we report the purification of a new 23-O-β-d-allopyranosyl-5β,19-epoxycucurbitane-6,24-diene triterpene (charantoside XV, 6) along with 25ξ-isopropenylchole-5(6)-ene-3-O-β-d-glucopyranoside (1), karaviloside VI (2), karaviloside VIII (3), momordicoside L (4), momordicoside A (5) and kuguaglycoside C (7) from an Indian cultivar of Momordica charantia. At 50 µM compounds, 2–6 differentially affected the expression of pro-inflammatory markers IL-6, TNF-α, and iNOS, and mitochondrial marker COX-2. Compounds tested for the inhibition of α-amylase and α-glucosidase enzymes at 0.87 mM and 1.33 mM, respectively. Compounds showed similar α-amylase inhibitory activity than acarbose (0.13 mM) of control (68.0–76.6%). Karaviloside VIII (56.5%) was the most active compound in the α-glucosidase assay, followed by karaviloside VI (40.3%), while momordicoside L (23.7%), A (33.5%), and charantoside XV (23.9%) were the least active compounds. To better understand the mode of binding of cucurbitane-triterpenes to these enzymes, in silico docking of the isolated compounds was evaluated with α-amylase and α-glucosidase. 相似文献
63.
Wang Jenn-Henn Chen Xiaolan Chen Jin-Jian Calderon Jose G. Timmons Richard B. 《Plasmas and Polymers》1997,2(4):245-260
The use of a variable duty cycle pulsed RF plasma is shown to provide film chemistry control during polymerization of saturated (CH2Br2) and unsaturated (CH2=CHCH2Br) bromine containing monomers. With both monomers, the degree of bromine atom retention in the films is observed to increase in a progressive fashion as the RF duty cycle employed during plasma polymerization is decreased. The film deposition rates, when expressed in terms of thickness per Joule of RF energy input, increase rapidly as the RF duty cycles are reduced. Additionally, the film morphology is observed to become increasingly smooth with decreasing RF duty cycles during deposition, as illustrated with the allyl bromide monomer. The film chemistry controllability of this study is demonstrated with monomers possessing the relatively weak C-Br bond. As such, the present work represents an important extension of the pulsed plasma polymerization approach to include retention of a labile bond during film formation. The introduction of reactive surface functional groups, at controlled densities, provides additional molecular tailoring possibilities via subsequent chemical derivatization processes. 相似文献
64.
Orte A Bermejo R Talavera EM Crovetto L Alvarez-Pez JM 《The journal of physical chemistry. A》2005,109(12):2840-2846
The presence of excited-state buffer-mediated proton exchange reactions influences the steady-state fluorescence signals from dyes in solution. Since biomolecules in general have some chemical groups that can act as proton acceptors/donors and are usually dissolved in buffer solutions which can also behave as appropriate proton acceptors/donors, the excited-state proton exchange reactions may result in distorted steady-state fluorescence signals. In a previous paper (J. Phys. Chem. A 2005, 109, 734-747), we evaluated kinetic and other pertinent parameters for the excited-state proton reactions of the prototropic forms of 2',7'-difluorofluorescein (Oregon Green 488, OG488), recording a fluorescence decay surface at different pH values and acetate buffer concentrations, analyzed by means of global compartmental analysis. In this article we use the rate constants and the corrected pre-exponential factors from the previously recorded fluorescence decay traces to simulate the decay times and associated pre-exponentials at different acetate buffer concentrations and constant pH and compare these theoretically calculated values with new experimental data. We also calculate the steady-state fluorescence intensity vs pH and vs acetate buffer concentration (at constant pH) and compare these calculated emission values with the experimental data previously published. The agreement between the experimental and simulated data is excellent. 相似文献
65.
Frutos LM Castano O Andres JL Merchan M Acuna AU 《The Journal of chemical physics》2004,120(3):1208-1216
Triplet energy transfer (TET) from aromatic donors to 1,3,5,7-cyclooctatetraene (COT) is an extreme case of "nonvertical" behavior, where the transfer rate for low-energy donors is considerably faster than that predicted for a thermally activated (Arrhenius) process. To explain the anomalous TET of COT and other molecules, a new theoretical model based on transition state theory for nonadiabatic processes is proposed here, which makes use of the adiabatic potential energy surfaces (PES) of reactants and products, as computed from high-level quantum mechanical methods, and a nonadiabatic transfer rate constant. It is shown that the rate of transfer depends on a geometrical distortion parameter gamma=(2g(2)/kappa(1))(1/2) in which g stands for the norm of the energy gradient in the PES of the acceptor triplet state and kappa(1) is a combination of vibrational force constants of the ground-state acceptor in the gradient direction. The application of the model to existing experimental data for the triplet energy transfer reaction to COT from a series of pi,pi(*) triplet donors, provides a detailed interpretation of the parameters that determine the transfer rate constant. In addition, the model shows that the observed decrease of the acceptor electronic excitation energy is due to thermal activation of C=C bond stretchings and C-C bond torsions, which collectively change the ground-state COT bent conformation (D(2d)) toward a planar triplet state (D(8h)). 相似文献
66.
Roberto del Río-Rodríguez Lorena Fragoso-Jarillo Alberto F. Garrido-Castro M. Carmen Maestro Jose A. Fernndez-Salas Jos Alemn 《Chemical science》2022,13(22):6512
Herein, we report, a general, facile and environmentally friendly Minisci-type alkylation of N-heteroarenes under simple and straightforward electrochemical conditions using widely available alkyl halides as radical precursors. Primary, secondary and tertiary alkyl radicals have been shown to be efficiently generated and coupled with a large variety of N-heteroarenes. The method presents a very high functional group tolerance, including various heterocyclic-based natural products, which highlights the robustness of the methodology. This applicability has been further proved in the synthesis of various interesting biologically valuable building blocks. In addition, we have proposed a mechanism based on different proofs and pieces of electrochemical evidence.Herein, we report, a general, facile and environmentally friendly Minisci-type alkylation of N-heteroarenes under simple and straightforward electrochemical conditions using widely available alkyl halides as radical precursors. 相似文献
67.
Learning from Examples with Information Theoretic Criteria 总被引:3,自引:0,他引:3
Jose C. Principe Dongxin Xu Qun Zhao John W. Fisher III 《The Journal of VLSI Signal Processing》2000,26(1-2):61-77
This paper discusses a framework for learning based on information theoretic criteria. A novel algorithm based on Renyi's quadratic entropy is used to train, directly from a data set, linear or nonlinear mappers for entropy maximization or minimization. We provide an intriguing analogy between the computation and an information potential measuring the interactions among the data samples. We also propose two approximations to the Kulback-Leibler divergence based on quadratic distances (Cauchy-Schwartz inequality and Euclidean distance). These distances can still be computed using the information potential. We test the newly proposed distances in blind source separation (unsupervised learning) and in feature extraction for classification (supervised learning). In blind source separation our algorithm is capable of separating instantaneously mixed sources, and for classification the performance of our classifier is comparable to the support vector machines (SVMs). 相似文献
68.
69.
70.