全文获取类型
收费全文 | 1702篇 |
免费 | 63篇 |
国内免费 | 26篇 |
专业分类
化学 | 1068篇 |
晶体学 | 7篇 |
力学 | 61篇 |
数学 | 256篇 |
物理学 | 399篇 |
出版年
2023年 | 14篇 |
2022年 | 20篇 |
2021年 | 25篇 |
2020年 | 45篇 |
2019年 | 30篇 |
2018年 | 22篇 |
2017年 | 15篇 |
2016年 | 36篇 |
2015年 | 29篇 |
2014年 | 47篇 |
2013年 | 72篇 |
2012年 | 115篇 |
2011年 | 118篇 |
2010年 | 69篇 |
2009年 | 59篇 |
2008年 | 118篇 |
2007年 | 78篇 |
2006年 | 91篇 |
2005年 | 96篇 |
2004年 | 71篇 |
2003年 | 60篇 |
2002年 | 60篇 |
2001年 | 43篇 |
2000年 | 40篇 |
1999年 | 20篇 |
1998年 | 17篇 |
1997年 | 9篇 |
1996年 | 23篇 |
1995年 | 14篇 |
1994年 | 24篇 |
1993年 | 26篇 |
1992年 | 19篇 |
1991年 | 23篇 |
1990年 | 19篇 |
1989年 | 15篇 |
1988年 | 9篇 |
1987年 | 10篇 |
1986年 | 17篇 |
1985年 | 13篇 |
1984年 | 26篇 |
1983年 | 12篇 |
1982年 | 14篇 |
1981年 | 8篇 |
1980年 | 10篇 |
1979年 | 11篇 |
1978年 | 8篇 |
1977年 | 19篇 |
1976年 | 12篇 |
1974年 | 12篇 |
1973年 | 10篇 |
排序方式: 共有1791条查询结果,搜索用时 203 毫秒
201.
Qian Tang Chengbin Gong Michael Hon-Wah Lam Xiangkai Fu 《Journal of Sol-Gel Science and Technology》2011,59(3):495-504
A photo-responsive molecularly imprinted sol–gel organic-inorganic hybrid material prepared by covalent imprinting of the
template-functional monomer complex formed between 4,4′-dihydroxylazobenzene and ibuprofen was developed to explore the photo-regulated
uptake and release of drug by a silicate-based smart molecularly imprinted materials. After imprinting, the template molecules
(ibuprofen) were removed via hydrolysis in acid, and accurate cavities were left, which could be used as the receptor recognition
sites for ibuprofen. The new organic–inorganic hybrid material shows specific affinity to ibuprofen and reversible uptake
and release of ibuprofen upon alternate irradiation at 365 and 440 nm, respectively. The favorable binding strength of the
imprinted receptor sites in the molecularly imprinted polymer (MIP) for ibuprofen is found to be 2.28 × 103 M−1. Density of receptor sites in the MIP material was 4.0 μmol/g—MIP. 相似文献
202.
In this study, polyaniline-multiwalled carbon nanotube film (PANi-MWCNT) has been polymerized on interdigitated platinum electrode arrays (IDA), fabricated by MEMS technology for the detection of human papillomavirus (HPV) infection, using immobilized peptide aptamers as affinity capture reagent. Label-free, electrochemical detection of the specific immune reaction between antigen peptide aptamer HPV-16-L1 (with a molecular weight of 1825 Da), the most common genotype in cytological normal women worldwide, and its specific antibody of HPV-16 (which is much bigger with molecular weight of ca. 150 kDa) on multifunctional PANi-MWCNT based arrays was reported. The most significant advantage of this technique consists of reagentless and multiple detection of antigen-antibody complex formation on well conducting IDA interface of PANi-MWCNT, without intermediate steps or any labeling reagents, as normally required in the previous works. 相似文献
203.
Single crystals of two liquid crystal compounds, 5‐{[4′‐(((pentyl)oxy)‐4‐biphenylyl)carbonyl]oxy}‐1‐pentyne (A3EO5) and 5‐{[(4′‐nonyloxy‐4‐biphenylyl)carbonyl]oxy}‐1‐pentyne (A3EO9), have been prepared by solution growth technique. The morphologies and structures of A3EO5 and A3EO9 crystals were investigated by wide angle X‐ray diffraction (WXRD), atom force microscope (AFM) and transmission electron microscope (TEM). In contrast to the same series of compounds which have a longer alkyl tail, 5‐{[(4′‐heptoxy‐4‐biphenylyl)carbonyl]oxy}‐1‐pentyne (A3EO7), 5‐{[(4′‐heptoxy‐4‐biphenylyl)oxy]carbonyl}‐1‐pentyne (A3E′O7) and A3EO9, A3EO5 shows strikingly different crystalline behavior. The former three compounds have only one crystal form, whereas A3EO5 exhibits polymorphism. Specifically, A3EO5 crystals grown from toluene solution show two crystal forms. The first one is crystal I which adopts a monoclinic P112/m space group with unit cell parameters of a?5.79 Å, b?8.34 Å, c?43.92 Å, γ?96°, and the other one is crystal II which adopts a monoclinic P112 space group with unit cell parameters of a?5.55 Å, b?7.38 Å, c?31.75 Å, γ?94°. When using dioxane as the solvent to grow A3EO5 crystal, we can selectively obtain crystal I. A3EO5 melt‐grown crystals also have two crystal forms which derive from crystal I and crystal II, respectively. The different crystalline behavior of the compounds should correlate with their different electron dipole moment resulting from the different length of alkyl tail. 相似文献
204.
Anthony J. Veloso Tiffiny Chan Vinci Wing Sze Hung Leayen Lam Kagan Kerman 《Electroanalysis》2011,23(12):2753-2756
The amyloid‐β (Aβ) aggregation pathway is an important target for the discovery of drugs that can prevent or delay the onset of Alzheimer’s disease (AD). The electrochemistry of Congo Red (CR) represents a particularly promising tool for screening of Aβ‐binding therapeutics in a rapid and cost‐effective format. The results of the differential pulse voltammetry (DPV) measurements were confirmed using simultaneous UV‐vis analysis of the same incubated Aβ samples. The early changes in the electrochemical signals were attributed to the interaction of the Aβ oligomers with CR. The electrochemical approach, in principle, allowed monitoring small molecule‐Aβ interactions on the time scale of aggregation. 相似文献
205.
Vasu SS Huynh LK Davidson DF Hanson RK Golden DM 《The journal of physical chemistry. A》2011,115(12):2549-2556
Reactions of hydroxyl (OH) radicals with 1-butene (k(1)), trans-2-butene (k(2)), and cis-2-butene (k(3)) were studied behind reflected shock waves over the temperature range 880-1341 K and at pressures near 2.2 atm. OH radicals were produced by shock-heating tert-butyl hydroperoxide, (CH(3))(3)-CO-OH, and monitored by narrow-line width ring dye laser absorption of the well-characterized R(1)(5) line of the OH A-X (0, 0) band near 306.7 nm. OH time histories were modeled using a comprehensive C(5) oxidation mechanism, and rate constants for the reaction of OH with butene isomers were extracted by matching modeled and measured OH concentration time histories. We present the first high-temperature measurement of OH + cis-2-butene and extend the temperature range of the only previous high-temperature study for both 1-butene and trans-2-butene. With the potential energy surface calculated using CCSD(T)/6-311++G(d,p)//QCISD/6-31G(d), the rate constants and branching fractions for the H-abstraction channels of the reaction of OH with 1-butene were calculated in the temperature range 300-1500 K. Corrections for variational and tunneling effects as well as hindered-rotation treatments were included. The calculations are in good agreement with current and previous experimental data and with a recent theoretical study. 相似文献
206.
Dong M Si YQ Sun SY Pu XP Yang ZJ Zhang LR Zhang LH Leung FP Lam CM Kwong AK Yue J Zhou Y Kriksunov IA Hao Q Lee HC 《Organic & biomolecular chemistry》2011,9(9):3246-3257
Human CD38 is a novel multi-functional protein that acts not only as an antigen for B-lymphocyte activation, but also as an enzyme catalyzing the synthesis of a Ca(2+) messenger molecule, cyclic ADP-ribose, from NAD(+). It is well established that this novel Ca(2+) signaling enzyme is responsible for regulating a wide range of physiological functions. Based on the crystal structure of the CD38/NAD(+) complex, we synthesized a series of simplified N-substituted nicotinamide derivatives (Compound 1-14). A number of these compounds exhibited moderate inhibition of the NAD(+) utilizing activity of CD38, with Compound 4 showing the highest potency. The crystal structure of CD38/Compound 4 complex and computer simulation of Compound 7 docking to CD38 show a significant role of the nicotinamide moiety and the distal aromatic group of the compounds for substrate recognition by the active site of CD38. Biologically, we showed that both Compounds 4 and 7 effectively relaxed the agonist-induced contraction of muscle preparations from rats and guinea pigs. This study is a rational design of inhibitors for CD38 that exhibit important physiological effects, and can serve as a model for future drug development. 相似文献
207.
The electrochemical reduction of diphenylphosphinate esters leads smoothly and in high yields to the corresponding deoxygenated products. In comparison with the previously developed methodologies, the electrolysis could be performed at lower temperature and with a higher current density, resulting in a shorter reaction time. 相似文献
208.
McCrane MP Weinert EE Lin Y Mazzola EP Lam YF Scholl PF Rokita SE 《Organic letters》2011,13(5):1186-1189
Selective oxidation by bis[(trifluoroacetoxy)iodo]benzene (BTI) provides an effective trap for quenching adducts formed reversibly between dC and an ortho-quinone methide (QM) under physiological conditions. A model adduct generated by 4-methyl-o-QM and 2'-deoxycytidine is rapidly converted by intramolecular cyclization and loss of aromaticity to a characteristic product for quantifying QM alkylation. However, BTI induces a surprising rearrangement driven by overoxidation of a derivative lacking an alkyl substituent at the 4-position of the QM. 相似文献
209.
Hein JE Burés J Lam YH Hughes M Houk KN Armstrong A Blackmond DG 《Organic letters》2011,13(20):5644-5647
Experimental and computational studies probing the nature of intermediates in the α-amination of aldehydes catalyzed by prolinate salts support an enamine carboxylate intermediate in the stereodetermining step. 相似文献
210.
Variance-constrained dissipative observer-based control for a class of nonlinear stochastic systems with degraded measurements 总被引:1,自引:0,他引:1
Zidong Wang James Lam Yuming Bo 《Journal of Mathematical Analysis and Applications》2011,377(2):645-658
This paper is concerned with the variance-constrained dissipative control problem for a class of stochastic nonlinear systems with multiple degraded measurements, where the degraded probability for each sensor is governed by an individual random variable satisfying a certain probabilistic distribution over a given interval. The purpose of the problem is to design an observer-based controller such that, for all possible degraded measurements, the closed-loop system is exponentially mean-square stable and strictly dissipative, while the individual steady-state variance is not more than the pre-specified upper bound constraints. A general framework is established so that the required exponential mean-square stability, dissipativity as well as the variance constraints can be easily enforced. A sufficient condition is given for the solvability of the addressed multiobjective control problem, and the desired observer and controller gains are characterized in terms of the solution to a convex optimization problem that can be easily solved by using the semi-definite programming method. Finally, a numerical example is presented to show the effectiveness and applicability of the proposed algorithm. 相似文献