全文获取类型
收费全文 | 1062篇 |
免费 | 51篇 |
国内免费 | 5篇 |
专业分类
化学 | 872篇 |
晶体学 | 8篇 |
力学 | 13篇 |
数学 | 134篇 |
物理学 | 91篇 |
出版年
2024年 | 2篇 |
2023年 | 11篇 |
2022年 | 21篇 |
2021年 | 20篇 |
2020年 | 21篇 |
2019年 | 26篇 |
2018年 | 16篇 |
2017年 | 9篇 |
2016年 | 31篇 |
2015年 | 34篇 |
2014年 | 36篇 |
2013年 | 69篇 |
2012年 | 58篇 |
2011年 | 103篇 |
2010年 | 47篇 |
2009年 | 51篇 |
2008年 | 73篇 |
2007年 | 97篇 |
2006年 | 75篇 |
2005年 | 73篇 |
2004年 | 61篇 |
2003年 | 35篇 |
2002年 | 33篇 |
2001年 | 11篇 |
2000年 | 9篇 |
1999年 | 12篇 |
1998年 | 11篇 |
1997年 | 11篇 |
1996年 | 7篇 |
1995年 | 7篇 |
1994年 | 8篇 |
1993年 | 6篇 |
1992年 | 5篇 |
1991年 | 3篇 |
1990年 | 3篇 |
1988年 | 1篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1984年 | 3篇 |
1983年 | 3篇 |
1982年 | 6篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1978年 | 3篇 |
1977年 | 1篇 |
1974年 | 1篇 |
排序方式: 共有1118条查询结果,搜索用时 15 毫秒
21.
Lynch CL Hale JJ Budhu RJ Gentry AL Finke PE Caldwell CG Mills SG MacCoss M Shen DM Chapman KT Malkowitz L Springer MS Gould SL DeMartino JA Siciliano SJ Cascieri MA Carella A Carver G Holmes K Schleif WA Danzeisen R Hazuda D Kessler J Lineberger J Miller M Emini E 《Organic letters》2003,5(14):2473-2475
[reaction: see text] A novel approach to alpha,alpha-disubstituted-beta-amino acids (beta(2,2)-amino acids) was employed in the synthesis of a series of 3-(pyrrolidin-1-yl)propionic acids possessing high affinity for the CCR5 receptor and potent anti-HIV activity. The rat pharmacokinetics for these new analogues featured higher bioavailabilities and lower rates of clearance as compared to cyclopentane 1. 相似文献
22.
Companion animal diets may contain up to 50% starch, derived from cereal grains. The amount of resistant starch (RS) in an ingredient depends on the origin and form of the ingredient and on the processing conditions to which the ingredient has been exposed. Extrusion has proven to be a means of optimizing utilization of starch by companion animals. Although the RS fraction of starch typically decreases by extrusion, retrogradation can result in increased concentrations of this fraction. Limited research exists regarding the effects of RS in companion animal nutrition and gastrointestinal health. Existing in vitro and in vivo research indicates that certain RS sources are readily fermented in the large bowel, producing short-chain fatty acids, whereas others are less fermentable, resulting in excellent laxation properties. Feeding dogs a diet high in RS may result in an increase in fecal bulk due to an increased excretion of microbial matter in those cases where RS is highly fermentable, or to indigestibility of the RS source in other cases. RS has a role to play as a potential proxy for dietary fiber, especially for those companion animals fed diets high in protein and fat and devoid of traditional dietary fiber. 相似文献
23.
Superoxide reductases (SORs) belong to a new class of metalloenzymes that degrade superoxide by reducing it to hydrogen peroxide. These enzymes contain a catalytic iron site that cycles between the Fe(II) and Fe(III) states during catalysis. A key step in the reduction of superoxide has been suggested to involve HO(2) binding to Fe(II), followed by innersphere electron transfer to afford an Fe(III)-OO(H) intermediate. In this paper, the mechanism of the superoxide-induced oxidation of a synthetic ferrous SOR model ([Fe(II)(S(Me2)N(4)(tren))](+) (1)) to afford [Fe(III)(S(Me2)N(4)(tren)(solv))](2+) (2-solv) is reported. The XANES spectrum shows that 1 remains five-coordinate in methanolic solution. Upon reaction of 1 with KO(2) in MeOH at -90 degrees C, an intermediate (3) is formed, which is characterized by a LMCT band centered at 452(2780) nm, and a low-spin state (S = 1/2), based on its axial EPR spectrum (g(perpendicular) = 2.14; g(parallel) = 1.97). Hydrogen peroxide is detected in this reaction, using both (1)H NMR spectroscopy and a catalase assay. Intermediate 3 is photolabile, so, in lieu of a Raman spectrum, IR was used to obtain vibrational data for 3. At low temperatures, a nu(O-O) Fermi doublet is observed in the IR at 788(2) and 781(2) cm(-)(1), which collapses into a single peak at 784 cm(-1) upon the addition of D(2)O. This vibrational peak diminishes in intensity over time and essentially disappears after 140 s. When 3 is generated using an (18)O-labeled isotopic mixture of K(18)O(2)/K(16)O(2) (23.28%), the vibration centered at 784 cm(-1) shifts to 753 cm(-1). This new vibrational peak is close to that predicted (740 cm(-1)) for a diatomic (18)O-(18)O stretch. In addition, a nu(O-O) vibrational peak assigned to free hydrogen peroxide is also observed (nu(O-O) = 854 cm(-1)) throughout the course of the reaction between Fe(II)-1 and superoxide and is strongest after 100 s. XAS studies indicate that 3 possesses one sulfur scatterer at 2.33(2) A and four nitrogen scatterers at 2.01(1) A. Addition of two Fe-O shells, each containing one oxygen, one at 1.86(3) A and one at 2.78(3) A, improved the EXAFS fits, suggesting that 3 is an end-on peroxo or hydroperoxo complex, [Fe(III)(S(Me2)N(4)(tren))(OO(H))](+). Upon warming above -50 degrees C, 3 is converted to 2-MeOH. In methanol and methanol:THF (THF = tetrahydrofuran) solvent mixtures, 2-MeOH is characterized by a LMCT band at lambda(max) = 511(1765) nm, an intermediate spin-state (S = 3/2), and, on the basis of EXAFS, a relatively short Fe-O bond (assigned to a coordinated methanol or methoxide) at 1.94(10) A. Kinetic measurements in 9:1 THF:MeOH at 25 degrees C indicate that 3 is formed near the diffusion limit upon addition of HO(2) to 1 and converts to 2-MeOH at a rate of 65(1) s(-1), which is consistent with kinetic studies involving superoxide oxidation of the SOR iron site. 相似文献
24.
Stroh JG Loulakis P Lanzetti AJ Xie J 《Journal of the American Society for Mass Spectrometry》2005,16(1):38-45
Limited proteolysis is an important and widely used method for analyzing the tertiary structure and determining the domain boundaries of proteins. Here we describe a novel method for determining the N- and C-terminal boundary amino acid sequences of products derived from limited proteolysis using semi-specific and/or non-specific enzymes, with mass spectrometry as the only analytical tool. The core of this method is founded on the recognition that cleavage of proteins with non-specific proteases is not random, but patterned. Based on this recognition, we have the ability to determine the sequence of each proteolytic fragment by extracting a common association between data sets containing multiple potential sequences derived from two or more different mass spectral molecular weight measurements. Proteolytic product sequences derived from specific and non-specific enzymes can be accurately determined without resorting to the conventional time-consuming and laborious methods of SDS-PAGE and N-terminal sequencing analysis. Because of the sensitivity of mass spectrometry, multiple transient proteolysis intermediates can also be identified and analyzed by this method, which allows the ability to monitor the progression of proteolysis and thereby gain insight into protein structures. 相似文献
25.
With the release of the human genome sequence, there has been increasing attention given to other genetic analyses, including the detection of genetic variations and fast sequencing of multiple samples for pharmacogenomics studies. Rapid injections of samples in multiplexed separation channels by optically gated sample introduction are shown here for DNA separation. Serial separations of four amino acids are shown in less than four seconds on a microchip with four multiplexed channels. Five short oligonucleotides have also been rapidly separated in 2% LPA with four channels using this technique. In addition, multiple unique samples have been simultaneously separated and five-base resolution has been demonstrated. 相似文献
26.
Julie L. S. Bell David J. Wesolowski Donald A. Palmer 《Journal of solution chemistry》1993,22(2):125-136
The dissociation quotients of formic acid were measured potentiometrically from 25 to 200°C in NaCl solutions at ionic strengths of 0.1, 0.3 1.0, 3.0, and 5.0 mol-kg–1. The experiments were carried out in a concentration cell with hydrogen electrodes. The resulting molal acid dissociation quotients for formic acid, as well as a set of infinite dilution literature values and a calorimetrically-determined enthalpy of reaction, were fitted by an empirical equation involving an extended Debye Hückel term and seven adjustable parameters involving functions of temperature and ionic strength. This regressional analysis yielded the following thermodynamic quantities for 25°C: logK=–3.755±0.002, Ho=–0.09±0.15 kJ-mol–1, So=–72.2±0.5 J-K–1-mol–1, and C
p
o
=–147±4 J-K–1-mol–1. The isocoulombic form of the equilibrium constant is recommended for extrapolation to higher temperatures. 相似文献
27.
28.
Joseph Lau Hwan Lee Julie Rousseau Franois Bnard Kuo-Shyan Lin 《Molecules (Basel, Switzerland)》2022,27(15)
Radioligand therapy (RLT) is an emergent drug class for cancer treatment. The dose administered to cancer patients is constrained by the radiation exposure to normal tissues to maintain an appropriate therapeutic index. When a radiopharmaceutical or its radiometabolite is retained in the kidneys, radiation dose deposition in the kidneys can become a dose-limiting factor. A good exemplar is [177Lu]Lu-DOTATATE, where patients receive a co-infusion of basic amino acids for nephroprotection. Besides peptides, there are other classes of targeting vectors like antibody fragments, antibody mimetics, peptidomimetics, and small molecules that clear through the renal pathway. In this review, we will review established and emerging strategies that can be used to mitigate radiation-induced nephrotoxicity, with a focus on the development and incorporation of cleavable linkers for radiopharmaceutical designs. Finally, we offer our perspectives on cleavable linkers for RLT, highlighting future areas of research that will help advance the technology. 相似文献
29.
Dr. Matthieu Autillo Md. Ashraful Islam Julie Héron Laetitia Guérin Dr. Eleonor Acher Dr. Christelle Tamain Dr. Marie-Claire Illy Dr. Philippe Moisy Dr. Eric Colineau Dr. Jean-Christophe Griveau Dr. Claude Berthon Dr. Hélène Bolvin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(24):7138-7153
Actinide +VI complexes ( = , and ) with dipicolinic acid derivatives were synthesized and characterized by powder XRD, SQUID magnetometry and NMR spectroscopy. In addition, and complexes were described by first principles CAS based and two-component spin-restricted DFT methods. The analysis of the 1H paramagnetic NMR chemical shifts for all protons of the ligands according to the X-rays structures shows that the Fermi contact contribution is negligible in agreement with spin density determined by unrestricted DFT. The magnetic susceptibility tensor is determined by combining SQUID, pNMR shifts and Evans’ method. The SO-RASPT2 results fit well the experimental magnetic susceptibility and pNMR chemical shifts. The role of the counterions in the solid phase is pointed out; their presence impacts the magnetic properties of the complex. The temperature dependence of the pNMR chemical shifts has a strong contribution, contrarily to Bleaney's theory for lanthanide complexes. The fitting of the temperature dependence of the pNMR chemical shifts and SQUID magnetic susceptibility by a two-Kramers-doublet model for the complex and a non-Kramers-doublet model for the complex allows for the experimental evaluation of energy gaps and magnetic moments of the paramagnetic center. 相似文献
30.
Dr. Julie Jung M. Ashraful Islam Dr. Vincent L. Pecoraro Dr. Talal Mallah Dr. Claude Berthon Dr. Hélène Bolvin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(66):15112-15122
Two series of lanthanide complexes have been chosen to analyze trends in the magnetic properties and crystal field parameters (CFPs) along the two series: The highly symmetric LnZn16(picHA)16 series (Ln=Tb, Dy, Ho, Er, Yb; picHA=picolinohydroxamic acid) and the [Ln(dpa)3](C3H5N2)3 ⋅ 3H2O series (Ln=Ce–Yb; dpa=2,6-dipicolinic acid) with approximate three-fold symmetry. The first series presents a compressed coordination sphere of eight oxygen atoms whereas in the second series, the coordination sphere consists of an elongated coordination sphere formed of six oxygen atoms. The CFPs have been deduced from ab initio calculations using two methods: The AILFT (ab initio ligand field theory) method, in which the parameters are determined at the orbital level, and the ITO (irreducible tensor operator) decomposition, in which the problems are treated at the many-electron level. It has been found that the CFPs are transferable from one derivative to another, within a given series, as a first approximation. The sign of the second-order parameter differs in the two series, reflecting the different environments. It has been found that the use of the strength parameter S allows for an easy comparison between complexes. Furthermore, in both series, the parameters have been found to decrease in magnitude along the series, and this decrease is attributed to covalent effects. 相似文献