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991.
The amide bond N?C activation represents a powerful strategy in organic synthesis to functionalize the historically inert amide linkage. This personal account highlights recent remarkable advances in transition‐metal‐free activation of amides by N?C bond cleavage, focusing on both (1) mechanistic aspects of ground‐state‐destabilization of the amide bond enabling formation of tetrahedral intermediates directly from amides with unprecedented selectivity, and (2) synthetic utility of the developed transformations. Direct nucleophilic addition to amides enables a myriad of powerful methods for the formation of C?C, C?N, C?O and C?S bonds, providing a straightforward and more synthetically useful alternative to acyl‐metals. 相似文献
992.
Rebecca L. Pinals Darwin Yang Daniel J. Rosenberg Tanya Chaudhary Andrew R. Crothers Dr. Anthony T. Iavarone Dr. Michal Hammel Prof. Markita P. Landry 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(52):23876-23885
When nanoparticles enter biological environments, proteins adsorb to form the “protein corona” which alters nanoparticle biodistribution and toxicity. Herein, we measure protein corona formation on DNA-functionalized single-walled carbon nanotubes (ssDNA-SWCNTs), a nanoparticle used widely for sensing and delivery, in blood plasma and cerebrospinal fluid. We characterize corona composition by mass spectrometry, revealing high-abundance corona proteins involved in lipid binding, complement activation, and coagulation. We investigate roles of electrostatic and entropic interactions driving selective corona formation. Lastly, we study real-time protein binding on ssDNA-SWCNTs, obtaining agreement between enriched proteins binding strongly and depleted proteins binding marginally, while highlighting cooperative adsorption mechanisms. Knowledge of protein corona composition, formation mechanisms, and dynamics informs nanoparticle translation from in vitro design to in vivo application. 相似文献
993.
Michal Malček Barbora Vénosová Ingrid Puškárová Jozef Kožíšek Marián Gall Lukáš Bučinský 《Journal of computational chemistry》2020,41(7):698-714
Geometry optimization, energetics, electronic structure, and topology of electron density of dicopper ( I ) and dichromium ( II ) tetrakis(μ-acetato)-diaqua complexes are studied focusing on the metal–metal interactions. The performance of broken symmetry (BS) single-determinant ab initio (Hartree–Fock, Møller–Plesset perturbation theory to the second and third orders, coupled clusters singles and doubles) and density functional theory (BLYP, B3LYP, B3LYP-D3, B2PLYP, MPW2PLYP) methods is compared to multideterminant ab initio (CASSCF, NEVPT2) methods as well as to the multipole model of charge density from a single-crystal X-ray diffraction experiment (Herich et al., Acta Cryst. 2018, B74, 681–692). In vacuo DFT geometry optimizations (improper axial water ligand orientation) are compared against the periodic ones. The singlet state is found to be energetically preferred. J coupling of ( I ) becomes underestimated for all ab initio methods used, when compared to experiment. It is concluded that the strength of the direct M─M interactions correlates closely with the J coupling magnitude at a given level of theory. The double potential well character of (II) and of the dehydrated form of (II) are considered with respect to the Cr─Cr distance. The physical effective bond order of the metal–metal interaction is small (below 0.1 e) in ( I ) and moderate (0.4 e) in ( II ). The CASSCF results overestimate the electron density of the metal–metal bond critical point by 20% and 50% in ( I ) and ( II ), respectively, when compared to the multipole model. © 2019 Wiley Periodicals, Inc. 相似文献
994.
Martin Ansorge Bohuslav Gaš Milan Boublík Michal Malý Jana Šteflová Vlastimil Hruška Gyula Vigh 《Electrophoresis》2020,41(7-8):514-522
Fourteen low molecular mass UV absorbing ampholytes containing 1 or 2 weakly acidic and 1 or 2 weakly basic functional groups that best satisfy Rilbe's requirement for being good carrier ampholytes (ΔpKa = pKamonoanion ‒ pKamonocation < 2) were selected from a large group of commercially readily available ampholytes in a computational study using two software packages (ChemSketch and SPARC). Their electrophoretic mobilities were measured in 10 mM ionic strength BGEs covering the 2 < pH < 12 range. Using our Debye-Hückel and Onsager-Fuoss laws-based new software, AnglerFish (freeware, https://echmet.natur.cuni.cz/software/download ), the effective mobilities were recalculated to zero ionic strength from which the thermodynamic pKa values and limiting ionic mobilities of the ampholytes were directly calculated by Henderson-Hasselbalch equation-type nonlinear regression. The tabulated thermodynamic pKa values and limiting ionic mobilities of these ampholytes (pI markers) facilitate both the overall and the narrow-segment characterization of the pH gradients obtained in IEF in order to mitigate the errors of analyte ampholyte pI assignments caused by the usual (but rarely proven) assumption of pH gradient linearity. These thermodynamic pKa and limiting mobility values also enable the reality-based numeric simulation of the IEF process using, for example, Simul (freeware, https://echmet.natur.cuni.cz/software/download ). 相似文献
995.
Dr. Anna Simonova Dr. Ivan Magriñá Dr. Veronika Sýkorová Dr. Radek Pohl Dr. Mayreli Ortiz Dr. Luděk Havran Prof. Dr. Miroslav Fojta Prof. Dr. Ciara K. O'Sullivan Prof. Dr. Michal Hocek 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(6):1286-1291
Three sets of 7-deazaadenine and cytosine nucleosides and nucleoside triphosphates bearing either unsubstituted ferrocene, octamethylferrocene and ferrocenecarboxamide linked through an alkyne tether to position 7 or 5, respectively, were designed and synthesized. The modified dNFcXTP s were good substrates for KOD XL DNA polymerase in primer extension and were used for enzymatic synthesis of redox-labelled DNA probes. Square-wave voltammetry showed that the octamethylferrocene oxidation potential was shifted to lower values, whilst the ferrocenecarboxamide was shifted to higher potentials, as compared to ferrocene. Tailed PEX products containing different ratios of Fc-labelled A ( dAFc ) and FcPa-labelled C ( dCFcPa ) were synthesized and hybridized with capture oligonucleotides immobilized on gold electrodes to study the electrochemistry of the redox-labelled DNA. Clearly distinguishable, fully orthogonal and ratiometric peaks were observed for the dAFc and dCFcPa bases in DNA, demonstrating their potential for use in redox coding of nucleobases and for the direct electrochemical measurement of the relative ratio of nucleobases in an unknown sequence of DNA. 相似文献
996.
Miroslav Mrlik Michal Sedlacik Vladimir Pavlinek Patrycja Bober Miroslava Trchová Jaroslav Stejskal Petr Saha 《Colloid and polymer science》2013,291(9):2079-2086
Aniline oligomers were prepared by the oxidation of aniline with p-benzoquinone in aqueous solutions of methanesulfonic acid (MSA) of various concentrations. Their molecular structures were assessed by Fourier transform infrared spectroscopy. The electrorheological (ER) behavior of their silicone oil suspensions under applied electric field has been investigated. Shear stress at a low shear rate, τ 0.9, was used as a criterion of the rigidity of internal structures created by the application of an electric field. It was established from the fitting of the dielectric spectra of the suspensions with the Havriliak–Negami model that dielectric relaxation strength, as a degree of polarization induced by an external field contributing to the enhanced ER effect, increases and relaxation time, i.e., the response of the particle to the application of the field, decreases when a higher molar concentration of MSA is used. The best values were observed for suspensions of the sample prepared in the presence of 0.5 M of MSA. This suspension creates stiff internal structures under an applied electric field strength of 2 kV mm?1 with τ 0.9 of nearly 50 Pa, which is even slightly of higher value than that obtained for standard polyaniline base ER suspension measured at the same conditions. The concentration of the MSA used in the preparation of oligomers seems to be a crucial factor influencing the conductivity, dielectric properties and, consequently, rheological behavior, and finally ER activity of their suspensions. 相似文献
997.
Alena Vollmannova Janettte Musilova Tomas Toth Julius Arvay Judita Bystricka Michal Medvecky 《International journal of environmental analytical chemistry》2013,93(14-15):1445-1451
The aim of this study was to determine the content of Cu, Zn, Cd and Pb and the total polyphenol (TP) content as well as the total antioxidant capacity (TAC) in wild cranberries and blueberries collected from different localities of the Slovakia and to compare them with properties of six cranberry and six highbush blueberry cultivars obtained from the research centre. Compared with cultivated cranberries (Cu, Zn, Cd and Pb content: 0.642, 1.496, 0.015 and 0.050 mg/kg FM) in wild fruits, higher Cu (by 37%) and lower Zn, Cd and Pb (by 8%, 7% and 44% respectively) were determined using atomic absorption spectrometry method. In wild blueberries, higher Cu, Zn and Pb (by 16%, 209% and 80% respectively) and similar Cd contents were determined compared with cultivated fruits (Cu, Zn, Cd and Pb content: 0.483, 0.541, 0.003 and 0.055 mg/kg FM). The TP contents estimated by spectrophotometry using Folin–Ciocalteau reagent were in intervals 1405–3161 (cranberries) and 1300–3077 (blueberries) expressed as mg GAE/kg FM. While the average TP content determined in wild cranberries was by 31% lower than that in cultivated cranberries, in wild blueberries it was by 97% higher compared with highbush blueberry cultivars. The values of TAC determined by spectrophotometry method using 2,2-diphenyl-1-picrylhydrazyl were in range 20.67–22.22 (cranberries) and 14.03–24.79 (blueberries) expressed as mmol TE/kg FM. In wild cranberries and blueberries, the lower average TAC values compared with cultivated berries were determined (by 1% and 28%, respectively). 相似文献
998.
The application of secondary temperature models on growth rates of Lactobacillus rhamnosus GG, the much studied probiotic bacterium, is investigated. Growth parameters resulting from a primary fitting were modelled against temperature using the following models: Hinshelwood model (H), Ratkowsky extended model (RTK2), Zwietering model (ZWT), and cardinal temperature model with inflection (CTMI). As experienced by other authors, the RTK2, ZWT, and CTMI models provided the best statistical indices related to fitting the experimental data. Moreover, with the biological background, the following cardinal temperatures of L. rhamnosus GG resulted from the study by the model application: t min = 2.7°C, t opt = 44.4°C, t max = 52.0°C. The growth rate of the strain under study at optimal temperature was 0.88 log10(CFU mL?1 h?1). 相似文献
999.
Anthocyanins present in the grapes of nine grapevine (Vitis vinifera L.) varieties and ten interspecific hybrids were compared. Total anthocyanin levels were determined in fresh grapes and the values ranged from 0.50 g kg?1 to 4.99 g kg?1. A total of twenty-two different anthocyanins were identified. Malvidin 3-glucoside was the most abundant anthocyanin, with concentrations ranging from 30 % to 64 % of the totals observed. The ratio of acetylated to coumaroylated malvidin and peonidin derivatives ranged from 0.09 (variety: Regent) to 1.34 (variety: Cerason), depending on the variety. Diglucosylated anthocyanins were not found in particular interspecific hybrids such as the teinturier XIV 26–56, Laurot, Merlan, and Nativa. 相似文献
1000.
Katarzyna Wrzosek Pavel Ačai Michal Gramblička Milan Polakovič 《Chemical Papers》2013,67(12):1537-1547
Adsorption of human immunoglobulin G (IgG) on a commercial cation exchanger with a grafted polymer layer was investigated at pH 4.5 and in the NaCl concentration range of 0–150 mM. Adsorption equilibrium was determined in static batch experiments and verified in batch uptake experiments. Parameters of the Langmuir isotherm were estimated for each salt concentration separately. The batch uptake experiments provided also the estimates of effective pore diffusion coefficients of IgG for individual protein and salt concentrations. The values of the effective pore diffusion coefficient depended strongly on both factors. They increased by about 5–15 times with the NaCl concentration and decreased about three times with the protein concentration. The quality of the estimated parameters was confirmed by frontal experiments described by the general rate model of chromatography. 相似文献