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931.
Optimization of peak area precision of a GC–MS drug screening method using a nonparametric sign test
Granquist Linda Carlsson Andreas Jonson Sten Andersson Kjell Karlsson Per Dahlén Johan Dunne Simon 《Accreditation and quality assurance》2019,24(3):215-226
Accreditation and Quality Assurance - The optimization of a number of gas chromatography–mass spectrometry (GC–MS) parameters in order to improve peak area precision through... 相似文献
932.
Bjorn J. A. Berendsen Linda A. M. Stolker Michel W. F. Nielen 《Journal of the American Society for Mass Spectrometry》2013,24(1):154-163
We developed a procedure to determine the “identification power” of an LC-MS/MS method operated in the MRM acquisition mode, which is related to its selectivity. The probability of any compound showing the same precursor ion, product ions, and retention time as the compound of interest is used as a measure of selectivity. This is calculated based upon empirical models constructed from three very large compound databases. Based upon the final probability estimation, additional measures to assure unambiguous identification can be taken, like the selection of different or additional product ions. The reported procedure in combination with criteria for relative ion abundances results in a powerful technique to determine the (un)certainty of the selectivity of any LC-MS/MS analysis and thus the risk of false positive results. Furthermore, the procedure is very useful as a tool to validate method selectivity. Figure
933.
Di Salvo F Escola N Scherlis DA Estrin DA Bondía C Murgida D Ramallo-López JM Requejo FG Shimon L Doctorovich F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(30):8428-8436
The nitrosyl in [IrCl5(NO)]- is probably the most electrophilic known to date. This fact is reflected by its extremely high IR frequency in the solid state, electrochemical behavior, and remarkable reactivity in solution. PPh4[IrCl5(NO)] forms a crystal in which the [IrCl5(NO)]- anions are in a curious wire-like linear arrangement, in which the distance between the N--O moiety of one anion and the trans chloride of the upper one nearby is only 2.8 A. For the same complex [IrCl5(NO)]- but with a different counterion, Na[IrCl5(NO)], the anions are stacked one over the other in a side-by-side arrangement. In this case the electronic distribution can be depicted as the closed-shell electronic structure Ir III-NO+, as expected for any d(6) third-row transition metal complex. However, in PPh4[IrCl5(NO)] an unprecedented electronic perturbation takes place, probably due to NO*-Cl- acceptor-donor interactions among a large number of [IrCl5(NO)]- units, favoring a different electronic distribution, namely the open-shell electronic structure Ir IV-NO*. This conclusion is based on XANES experimental evidence, which demonstrates that the formal oxidation state for iridium in PPh4[IrCl5(NO)] is +4, as compared with +3 in K[IrCl5(NO)]. In agreement, solid-state DFT calculations show that the ground state for [IrCl5(NO)]- in the PPh4+ salt comprises an open-shell singlet with an electronic structure which encompasses half of the spin density mainly localized on a metal-centered orbital, and the other half on an NO-based orbital. The electronic perturbation could be seen as an electron promotion from a metal-chloride to a metal-NO orbital, due to the small HOMO-LUMO gap in PPh4[IrCl5(NO)]. This is probably induced by electrostatic interactions acting as a result of the closeness and wire-like spatial arrangement of the Ir metal centers, imposed by lattice forces due to pi-pi stacking interactions among the phenyl rings in PPh4+. Experimental and theoretical data indicate that in PPh4[IrCl5(NO)] the Ir-N-O moiety is partially bent and tilted. 相似文献
934.
Baltus RE Carmon KS Luck LA 《Langmuir : the ACS journal of surfaces and colloids》2007,23(7):3880-3885
Results from an investigation of the frequency response resulting from ligand binding for a genetically engineered hormone-binding domain of the alpha-estrogen receptor immobilized to a piezoelectric quartz crystal are reported. Two different approaches were used to attach a genetically altered receptor to the gold electrode on the quartz surface: (1) the mutant receptor containing a single solvent-exposed cysteine was directly attached to the crystal via a sulfur to gold covalent bond, forming a self-assembled protein monolayer, and (2) the N-terminal histidine-tagged end was utilized to attach the receptor via a 3,3-dithiobis[N-(5-amino-5-carboxypentyl)propionamide-N',N'-diacetic acid] linker complexed with nickel. Previous studies have shown that these engineered constructs bind 17beta-estradiol and are fully functional. Exposure of the receptor directly attached to the piezoelectric crystal to the known ligand 17beta-estradiol resulted in a measurable frequency response, consistent with a change in conformation of the receptor with ligand binding. However, no response was observed when the receptor immobilized via the linker was exposed to the same ligand. The presence of the linker between the quartz surface and the protein receptor does not allow the crystal to sense the conformational change in the receptor that occurs with ligand binding. These results illustrate that the immobilization strategy used to bind the receptor to the sensor platform is key to eliciting an appropriate response from this biosensor. This study has important implications for the development of QCM-based sensors using protein receptors. 相似文献
935.
In this study, Saccharomyces cerevisiae yeast lysate is used to demonstrate how a simple wash procedure can improve IEF of IPG strips passively rehydrated in the presence of NaCl. By performing three 10 min washes after IPG strip rehydration and before IEF, corresponding second-dimensional gels from strips containing NaCl look similar to control strips while the second-dimensional gels of unwashed strips contains streaks and spaces devoid of protein. Up to 500 mM NaCl was added to the yeast lysate and successfully focused following this wash regime. Protein loss due to the washes was determined to be minimal by comparing replicates of washed and unwashed strips and analyzing the densities of their corresponding second-dimensional gel spots. In the event of unknown salt contamination, indicated by low voltage during focusing, it is possible to stop focusing, wash the strips, and then continue focusing with acceptable second dimension results. 相似文献
936.
Van Uytfanghe K Stöckl D Thienpont LM 《Rapid communications in mass spectrometry : RCM》2004,18(13):1539-1540
937.
During the "Standards Development and International Harmonization: AOAC INTERNATIONAL Mid-Year Meeting" held on June 29, 2011, an Expert Review Panel (ERP) reviewed the method "Determination of Vitamin B12 in Infant Formula and Adult Nutritionals by HPLC." Under the new pathway to Official Methods, the ERP adopted the method as Official First Action. The method is applicable to the determination of vitamin B12 in infant formula and adult nutritionals. Data showed an average overall intermediate precision of 6.64% RSD, an estimated quantitation limit of 0.8 microg/kg, and a detection limit of 0.2 microg/kg in prepared samples. The standard range of the method is 2 to 200 microg/L, which corresponds to an analytical range of 0.8 to 500 microg/kg. 相似文献
938.
939.
C Weeraman M Chen DJ Moffatt R Lausten A Stolow LJ Johnston 《Langmuir : the ACS journal of surfaces and colloids》2012,28(36):12999-13007
A combination of vibrational sum frequency generation spectroscopy and atomic force microscopy is used to study the changes in morphology and conformational order in monolayers prepared from three natural sphingomyelin (SM) mixtures as a function of surface pressure and cholesterol concentration. The most homogeneous SM gave monolayers with well-ordered acyl chains and few gauche defects with relatively small effects of either increasing surface pressure or cholesterol addition. Heterogeneous SM mixtures with a mixture of acyl chain lengths or with significant fractions of unsaturated acyl chains had much larger contributions from gauche defects at low surface pressure and gave increasingly well-ordered monolayers as the surface pressure increased. They also showed substantial increases in lipid chain order after cholesterol addition. Overall, these results are consistent with the strong hydrogen bonding capacity of SM leading to well-ordered monolayers over a range of surface pressures. The changes in acyl chain order for natural SMs as a function of cholesterol are relevant to formation of sphingolipid-cholesterol enriched domains in cell membranes. 相似文献
940.
Students' Attitudes Toward Science as Predictors of Gains on Student Content Knowledge: Benefits of an After‐School Program 下载免费PDF全文
Alana D. Newell Linda R. Zientek Barbara Z. Tharp Gregory L. Vogt Nancy P. Moreno 《School science and mathematics》2015,115(5):216-225
High‐quality after‐school programs devoted to science have the potential to enhance students' science knowledge and attitudes, which may impact their decisions about pursuing science‐related careers. Because of the unique nature of these informal learning environments, an understanding of the relationships among aspects of students' content knowledge acquisition and attitudes toward science may aid in the development of effective science‐related interventions. We investigated the impact of a semester‐long after‐school intervention utilizing an inquiry‐based infectious diseases curriculum (designed for use after‐school) on 63 urban students' content knowledge and aspects of their attitudes toward science. Content knowledge increased 24.6% from pretest to posttest. Multiple regression analyses indicated suggested that the “self‐directed effort” subscale of the Simpson–Troost Attitude Questionnaire—Revised best predicted increases in students' science content knowledge. The construct “science is fun for me” served as a suppressor effect. These findings suggest that future after‐school programs focusing on aspects of attitudes toward science most closely associated with gains in content knowledge might improve students' enthusiasm and academic preparedness for additional science coursework by improving student attitudes toward their perceptions of their self‐directed effort. 相似文献