全文获取类型
收费全文 | 3001篇 |
免费 | 103篇 |
国内免费 | 19篇 |
专业分类
化学 | 2385篇 |
晶体学 | 31篇 |
力学 | 38篇 |
数学 | 299篇 |
物理学 | 370篇 |
出版年
2024年 | 3篇 |
2023年 | 17篇 |
2022年 | 37篇 |
2021年 | 49篇 |
2020年 | 70篇 |
2019年 | 66篇 |
2018年 | 45篇 |
2017年 | 34篇 |
2016年 | 75篇 |
2015年 | 70篇 |
2014年 | 83篇 |
2013年 | 118篇 |
2012年 | 257篇 |
2011年 | 314篇 |
2010年 | 125篇 |
2009年 | 106篇 |
2008年 | 227篇 |
2007年 | 255篇 |
2006年 | 222篇 |
2005年 | 232篇 |
2004年 | 204篇 |
2003年 | 161篇 |
2002年 | 165篇 |
2001年 | 37篇 |
2000年 | 34篇 |
1999年 | 15篇 |
1998年 | 17篇 |
1997年 | 17篇 |
1996年 | 25篇 |
1995年 | 8篇 |
1994年 | 8篇 |
1993年 | 10篇 |
1992年 | 2篇 |
1991年 | 3篇 |
1990年 | 2篇 |
1989年 | 1篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1974年 | 1篇 |
1973年 | 1篇 |
排序方式: 共有3123条查询结果,搜索用时 15 毫秒
81.
Tugarinov V Hwang PM Ollerenshaw JE Kay LE 《Journal of the American Chemical Society》2003,125(34):10420-10428
A comparison of HSQC and HMQC pulse schemes for recording (1)H[bond](13)C correlation maps of protonated methyl groups in highly deuterated proteins is presented. It is shown that HMQC correlation maps can be as much as a factor of 3 more sensitive than their HSQC counterparts and that the sensitivity gains result from a TROSY effect that involves cancellation of intra-methyl dipolar relaxation interactions. (1)H[bond](13)C correlation spectra are recorded on U-[(15)N,(2)H], Ile delta 1-[(13)C,(1)H] samples of (i) malate synthase G, a 723 residue protein, at 37 and 5 degrees C, and of (ii) the protease ClpP, comprising 14 identical subunits, each with 193 residues (305 kDa), at 5 degrees C. The high quality of HMQC spectra obtained in short measuring times strongly suggests that methyl groups will be useful probes of structure and dynamics in supramolecular complexes. 相似文献
82.
Slaughter BD Unruh JR Price ES Huynh JL Bieber Urbauer RJ Johnson CK 《Journal of the American Chemical Society》2005,127(34):12107-12114
We used single-pair fluorescence resonance energy transfer (spFRET) measurements to characterize denatured and partially denatured states of the multidomain calcium signaling protein calmodulin (CaM) in both its apo and Ca(2+)-bound forms. The results demonstrate the existence of an unfolding intermediate. A CaM mutant (CaM-T34C-T110C) was doubly labeled with fluorescent probes AlexaFlour 488 and Texas Red at opposing globular domains. Single-molecule distributions of the distance between fluorophores were obtained by spFRET at varying levels of the denaturant urea. Multiple conformational states of CaM were observed, and the amplitude of each conformation was dependent on urea concentration, with the amplitude of an extended conformation increasing upon denaturation. The distributions at intermediate urea concentrations could not be adequately described as a combination of native and denatured conformations, showing that CaM does not denature via a two-state process and demonstrating that at least one intermediate is present. The intermediate conformations formed upon addition of urea were different for Ca(2+)-CaM and apoCaM. An increase in the amplitude of a compact conformation in CaM was observed for apoCaM but not for Ca(2+)-CAM upon the addition of urea. The changes in the single-molecule distributions of CaM upon denaturation can be described by either a range of intermediate structures or by the presence of a single unfolding intermediate that grows in amplitude upon denaturation. A model for stepwise unfolding of CaM is suggested in which the domains of CaM unfold sequentially. 相似文献
83.
An adjustable low-mass filter has been developed for an electrospray ionization (ESI) source to block ions associated with unwanted background species from entering the mass spectrometer. The low-mass filter is made by using an adjustable potential energy barrier from the conductance-limiting plate of an electrodynamic ion funnel, which prohibits species with higher ion mobilities from exiting the ESI source. We show that this arrangement provides a linear voltage adjustment for low-mass filtering from m/z 0 to 500. Mass filtering above m/z 500 is also performed; however, higher-mass species are attenuated. The mass filter was tested with a liquid chromatography/mass spectrometry (LC/MS) analysis of a bovine serum albumin (BSA) tryptic digest and resulted in the ability to block low-mass, background species, which accounted for 40-70% of the total ion current immediately behind the ESI source during peak elution and detection. 相似文献
84.
In analysis of the thermodynamics of the transfer of a solute from the mobile phase to the stationary phase in reversed-phase liquid chromatography, it is nearly always assumed that the phase ratio is constant. This type of analysis is typically performed by applying a form of the van't Hoff equation, which relates the retention factor to temperature via the enthalpy and entropy of transfer. When non-linear van't Hoff plots are observed, it is often assumed that the enthalpy and entropy of transfer change with temperature. However, when the possibility of a change in the phase ratio is considered, it becomes apparent that non-linear van't Hoff behavior may or may not be due to changes in enthalpy or entropy. In this work, we present mathematical evidence that phase ratio changes, if they occur, can cause deviations from linearity in a van't Hoff plot. We also show that the phase ratio influence can be eliminated by considering the molecular difference between two solutes instead of the solutes themselves. The resulting selectivity van't Hoff plots may be linear, even when the van't Hoff plots of the two solutes are non-linear. In such cases, temperature-dependent phase ratio changes, and not necessarily changes in the transfer enthalpy, may be responsible for the curved van't Hoff plots of the individual solutes. In addition, we present chromatographic evidence that different solutes may "see" different thermodynamic phase ratios. It is clear that the concept of a phase ratio in reversed-phase chromatography is not nearly as well defined as a phase ratio in a bulk system like a liquid-liquid extraction. 相似文献
85.
Chin JW Santoro SW Martin AB King DS Wang L Schultz PG 《Journal of the American Chemical Society》2002,124(31):9026-9027
We report the selection of a new orthogonal aminoacyl tRNA synthetase/tRNA pair for the in vivo incorporation of a photocrosslinker, p-azido-l-phenylalanine, into proteins in response to the amber codon, TAG. The amino acid is incorporated in good yield with high fidelity and can be used to crosslink interacting proteins. 相似文献
86.
Chakraborty A Wu A Witt D Lagona J Fettinger JC Isaacs L 《Journal of the American Chemical Society》2002,124(28):8297-8306
Cucurbit[6]uril (CB[6]) is a macrocyclic compound, prepared in one pot from glycoluril and formaldehyde, whose molecular recognition properties have made it the object of intense study. Studies of the mechanism of CB[n] formation, which might provide insights that allow the tailor-made synthesis of CB[n] homologues and derivatives, have been hampered by the complex structure of CB[n]. By reducing the complexity of the reaction to the formation of S-shaped (12S-18S) and C-shaped (12C-18C) methylene bridged glycoluril dimers, we have been able to probe the fundamental steps of the mechanism of CB[n] synthesis to a level that has not been possible previously. For example, we present strong evidence that the mechanism of CB[n] synthesis proceeds via the intermediacy of both S-shaped and C-shaped dimers. The first experimental determination of the relative free energies of the S-shaped and C-shaped dimers indicates a thermodynamic preference (1.55-3.25 kcal mol(-)(1)) for the C-shaped diastereomer. This thermodynamic preference is not because of self-association, solvation, or template effects. Furthermore, labeling experiments have allowed us to elucidate the mechanism of this acid-catalyzed equilibrium between the S-shaped and C-shaped diastereomers. The equilibration is an intramolecular process that proceeds with high diastereoselectivity and retention of configuration. On the basis of the broad implications of these results for CB[n] synthesis, we suggest new synthetic strategies that may allow for the improved preparation of CB[n] (n > 8) and CB[n] derivatives from functionalized glycolurils. 相似文献
87.
Jebanathirajah JA Pittman JL Thomson BA Budnik BA Kaur P Rape M Kirschner M Costello CE O'Connor PB 《Journal of the American Society for Mass Spectrometry》2005,16(12):1985-1999
The use of a new electrospray qQq Fourier transform ion cyclotron mass spectrometer (qQq-FTICR MS) instrument for biologic applications is described. This qQq-FTICR mass spectrometer was designed for the study of post-translationally modified proteins and for top-down analysis of biologically relevant protein samples. The utility of the instrument for the analysis of phosphorylation, a common and important post-translational modification, was investigated. Phosphorylation was chosen as an example because it is ubiquitous and challenging to analyze. In addition, the use of the instrument for top-down sequencing of proteins was explored since this instrument offers particular advantages to this approach. Top-down sequencing was performed on different proteins, including commercially available proteins and biologically derived samples such as the human E2 ubiquitin conjugating enzyme, UbCH10. A good sequence tag was obtained for the human UbCH10, allowing the unambiguous identification of the protein. The instrument was built with a commercially produced front end: a focusing rf-only quadrupole (Q0), followed by a resolving quadrupole (Q1), and a LINAC quadrupole collision cell (Q2), in combination with an FTICR mass analyzer. It has utility in the analysis of samples found in substoichiometric concentrations, as ions can be isolated in the mass resolving Q1 and accumulated in Q2 before analysis in the ICR cell. The speed and efficacy of the Q2 cooling and fragmentation was demonstrated on an LCMS-compatible time scale, and detection limits for phosphopeptides in the 10 amol/muL range (pM) were demonstrated. The instrument was designed to make several fragmentation methods available, including nozzle-skimmer fragmentation, Q2 collisionally activated dissociation (Q2 CAD), multipole storage assisted dissociation (MSAD), electron capture dissociation (ECD), infrared multiphoton induced dissociation (IRMPD), and sustained off resonance irradiation (SORI) CAD, thus allowing a variety of MS(n) experiments. A particularly useful aspect of the system was the use of Q1 to isolate ions from complex mixtures with narrow windows of isolation less than 1 m/z. These features enable top-down protein analysis experiments as well structural characterization of minor components of complex mixtures. 相似文献
88.
Temperature-programmed reaction spectroscopy (TPRS) and direct, isothermal reaction-rate measurements were employed to investigate the oxidation of CO on Pt(111) covered with high concentrations of atomic oxygen. The TPRS results show that oxygen atoms chemisorbed on Pt(111) at coverages just above 0.25 ML (monolayers) are reactive toward coadsorbed CO, producing CO(2) at about 295 K. The uptake of CO on Pt(111) is found to decrease with increasing oxygen coverage beyond 0.25 ML and becomes immeasurable at a surface temperature of 100 K when Pt(111) is partially covered with Pt oxide domains at oxygen coverages above 1.5 ML. The rate of CO oxidation measured as a function of CO beam exposure to the surface exhibits a nearly linear increase toward a maximum for initial oxygen coverages between 0.25 and 0.50 ML and constant surface temperatures between 300 and 500 K. At a fixed CO incident flux, the time required to reach the maximum reaction rate increases as the initial oxygen coverage is increased to 0.50 ML. A time lag prior to the reaction-rate maximum is also observed when Pt oxide domains are present on the surface, but the reaction rate increases more slowly with CO exposure and much longer time lags are observed, indicating that the oxide phase is less reactive toward CO than are chemisorbed oxygen atoms on Pt(111). On the partially oxidized surface, the CO exposure needed to reach the rate maximum increases significantly with increases in both the initial oxygen coverage and the surface temperature. A kinetic model is developed that reproduces the qualitative dependence of the CO oxidation rate on the atomic oxygen coverage and the surface temperature. The model assumes that CO chemisorption and reaction occur only on regions of the surface covered by chemisorbed oxygen atoms and describes the CO chemisorption probability as a decreasing function of the atomic oxygen coverage in the chemisorbed phase. The model also takes into account the migration of oxygen atoms from oxide domains to domains with chemisorbed oxygen atoms. According to the model, the reaction rate initially increases with the CO exposure because the rate of CO chemisorption is enhanced as the coverage of chemisorbed oxygen atoms decreases during reaction. Longer rate delays are predicted for the partially oxidized surface because oxygen migration from the oxide phase maintains high oxygen coverages in the coexisting chemisorbed oxygen phase that hinder CO chemisorption. It is shown that the time evolution of the CO oxidation rate is determined by the relative rates of CO chemisorption and oxygen migration, R(ad) and R(m), respectively, with an increase in the relative rate of oxygen migration acting to inhibit the reaction. We find that the time lag in the reaction rate increases nearly exponentially with the initial oxygen coverage [O](i) (tot) when [O](i) (tot) exceeds a critical value, which is defined as the coverage above which R(ad)R(m) is less than unity at fixed CO incident flux and surface temperature. These results demonstrate that the kinetics for CO oxidation on oxidized Pt(111) is governed by the sensitivity of CO binding and chemisorption on the atomic oxygen coverage and the distribution of surface oxygen phases. 相似文献
89.
Heteronuclear diethylcarbamato complexes of the form Co(n)()Mg(6)(-)(n)()(Et(2)NCO(2))(12) were prepared from the isostructural homonuclear precursors Mg(6)(Et(2)NCO(2))(12), 1, and Co(6)(Et(2)NCO(2))(12), 2, via a solvothermal methodology. Two materials were selected for single-crystal X-ray diffraction analysis: Co(1.6)Mg(4.4)(Et(2)NCO(2))(12) and Co(2.7)Mg(3.3)(Et(2)NCO(2))(12). Both compounds crystallize in the orthorhombic space group Ccca, as do 1 and 2. The molecular structure is best described as two trinuclear M(3) units cross-linked by diethylcarbamate ligands and twisted about one another, so that the complex has overall D(2) symmetry and is chiral. Each trinuclear unit consists of two terminal pentacoordinate metal ions and one central hexacoordinate metal ion. The X-ray diffraction data were unambiguous that the Co(2+) ions migrate exclusively to the pentacoordinate sites in the heteronuclear complexes, thus demonstrating that metal ion scrambling at the molecular level must occur. The composition of individual crystals can be continuously varied for Co(2+) mole fractions chi(Co) < 0.5, and the a and c unit cell distances are linearly related to chi(Co). This indicates that the compounds behave as solid solutions. There appears to be either a chemical or crystallographic phenomenon inherent in the synthetic methodology that prevents isolation of heteronuclear materials having chi(Co) > 0.5. Solution electronic spectroscopy and molecular weight measurements show that 2 can dissociate in chloroform and cyclohexane solution to give a dimeric complex 2'. This behavior contrasts with the stability of 1 in solution, as shown by NMR. The kinetic rate profile for formation of Co(n)Mg(6-n)(Et(2)NCO(2))(12) reveals saturation kinetics and is consistent with direct attack by 2' on 1 to give the heteronuclear complex via a higher nuclearity intermediate. This study illustrates a general method for the preparation of solids based on heteronuclear Werner-type complexes of the M(6)(Et(2)NCO(2))(12) structure type, and the mechanism by which such compounds can be formed from isostructural homonuclear precursors. 相似文献
90.
We report on the coupling of a polymer-based microfluidic chip to a MALDI-TOF MS using a rotating ball interface. The microfluidic chips were fabricated by micromilling a mold insert into a brass plate, which was then used for replicating polymer microparts via hot embossing. Assembly of the chip was accomplished by thermally annealing a cover slip to the embossed substrate to enclose the channels. The linear separation channel was 50 microm wide, 100 microm deep, and possessed an 8 cm effective length separation channel with a double-T injector (V(inj) = 10 nL). The exit of the separation channel was machined to allow direct contact deposition of effluent onto a specially constructed rotating ball inlet to the mass spectrometer. Matrix addition was accomplished in-line on the surface of the ball. The coupling utilized the ball as the cathode transfer electrode to transport sample into the vacuum for desorption with a 355 nm Nd:YAG laser and analyzed on a TOF mass spectrometer. The ball was cleaned online after every rotation. The ability to couple poly(methylmethacrylate) microchip electrophoresis devices for the separation of peptides and peptide fragments produced from a protein digest with subsequent online MALDI MS detection was demonstrated. 相似文献