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921.
Striolo A McCabe C Cummings PT Chan ER Glotzer SC 《The journal of physical chemistry. B》2007,111(42):12248-12256
Polyhedral oligomeric silsesquioxanes (POSS) are multifunctional molecules that can be employed as building blocks to develop nanocomposite materials whose mechanical properties often improve upon those of traditional polymeric materials. We report here molecular simulation results for the effective potential of mean force between octamethyl POSS monomers and between POSS monomers in which one methyl group has been substituted by a linear alkane chain of nine carbon atoms in liquid normal hexane at 300 and 400 K. The results are discussed and compared to available data for the effective interactions between octamethyl POSS monomers in normal hexadecane. Our results show that the effective short-ranged POSS-POSS attraction is significantly weaker in hexane than it is in hexadecane, perhaps explaining why normal hexane is often the solvent of choice for the preparation of POSS-containing materials. Additionally, we provide results for the radial distribution functions between selected sites in the POSS monomers that can be used both to understand the association between POSS monomers in solution and to parametrize coarse-grained simulation models. Such models will be used to study the formation of POSS-containing supramolecular structures such as lamellae or micelles that are currently not accessible by atomistic simulation and can be compared to experimental observations. 相似文献
922.
Alberto Girlando Cristina Sissa Francesca Terenziani Anna Painelli Anna Chwialkowska Geoffrey J Ashwell 《Chemphyschem》2007,8(15):2195-2201
We report visible, Raman, and infrared spectra of self-assembled monolayers (SAMs) formed by the donor-(pi-bridge)-acceptor chromophore, Z-beta-[N-(omega-acetylthioalkyl)-4-quinolinium]-alpha-cyano-4-styryldicyanomethanide (CH3CO-S-CnH2n-Q3CNQ where n=8, 10), on gold-coated substrates. The data are compared with the spectra collected for the same compound in solution and in the solid state, and with those obtained for a Langmuir-Blodgett (LB) monolayer of C16H33-Q3CNQ deposited on gold. Spectral analysis confirms that in solution, in the solid state and in the LB film the chromophore has a zwitterionic (D+-pi-A-) ground state. At variance with this well-known result, our data show that in SAMs deposited on gold the chromophore has a more neutral, quinoid ground state. We relate this difference to the different packing of the molecules in the two different films: in SAMs in fact the chromophores stand almost vertical with respect to the substrate, whereas in LB films they make an angle of about 45 degrees. The Q3CNQ molecule is a well-known molecular rectifier, and for SAMs we were able to check the direction of electron flow at forward bias on the same samples that have been characterized spectroscopically, shedding light on the rectification mechanism. 相似文献
923.
Valentina Domenici Carlo Alberto Veracini Katalin Fodor-Csorba Giacomo Prampolini Ivo Cacelli Andrjia Lebar Bostjan Zalar 《Chemphyschem》2007,8(16):2321-2330
The orientational properties of the banana-shaped liquid crystal 4-chloro-1,3-phenylenebis{4-[4'-(10-undecenyloxy)]benzoyloxy} benzoate (ClPbis11BB) are reported in the nematic phase under the effect of an external magnetic field. A new hypothesis, which states that the central ring of the aromatic core is oriented perpendicularly to the external magnetic field, is proposed. In support of this hypothesis, a series of studies based on (2)H NMR spectroscopy, both in the bulk and in solution, are discussed. (2)H NMR measurements on three selectively deuterium-labelled isotopomers are presented, together with DFT results from B3LYP/cc-pvDz calculations performed on the aromatic core. The rather flat shape of the investigated intramolecular energy surface allows for several different conformations to be populated, the computed magnetic susceptibilities of which are consistent with the proposed hypothesis of peculiar orientation of banana-shaped molecules. Moreover, the orientation of the magnetic susceptibility tensor is shown to be strongly dependent on the internal conformation of the banana-shaped molecules. 相似文献
924.
Petroselli G Erra-Balsells R Cabrerizo FM Lorente C Capparelli AL Braun AM Oliveros E Thomas AH 《Organic & biomolecular chemistry》2007,5(17):2792-2799
UV-A radiation (320-400 nm) induces damages to the DNA molecule and its components through photosensitized reactions. Pterins, heterocyclic compounds widespread in biological systems, participate in relevant biological processes and are able to act as photosensitizers. We have investigated the photosensitization of 2'-deoxyadenosine-5'-monophosphate (dAMP) by pterin (PT) in aqueous solution under UV-A radiation. The effect of pH was evaluated, the participation of oxygen was investigated and the products analyzed. Kinetic studies revealed that the reactivity of dAMP towards singlet oxygen (1O2) is very low and that this reactive oxygen species does not participate in the mechanism of photosensitization, although it is produced by PT upon UV-A excitation. In contrast, analysis of irradiated solutions by means of electrospray ionization mass spectrometry strongly suggested that 8-oxo-7,8-dihydro-2'-deoxyadenosine-5'-monophosphate (8-oxo-dAMP) was produced, indicating that the photosensitized oxidation takes place via a type I mechanism (electron transfer). 相似文献
925.
Alberto Hernn‐Gmez Emma Herd Eva Hevia Alan R. Kennedy Paul Knochel Konrad Koszinowski Sophia M. Manolikakes Robert E. Mulvey Christoph Schnegelsberg 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(10):2744-2748
The pivalates RZnOPiv⋅Mg(OPiv)X⋅n LiCl (OPiv=pivalate; R=aryl; X=Cl, Br, I) stand out amongst salt‐supported organometallic reagents, because apart from their effectiveness in Negishi cross‐coupling reactions, they show more resistance to attack by moist air than conventional organometallic compounds. Herein a combination of synthesis, coupling applications, X‐ray crystallographic studies, NMR (including DOSY) studies, and ESI mass spectrometric studies provide details of these pivalate reagents in their own right. A p‐tolyl case system shows that in [D8]THF solution these reagents exist as separated Me(p‐C6H4)ZnCl and Mg(OPiv)2 species. Air exposure tests and X‐ray crystallographic studies indicate that Mg(OPiv)2 enhances the air stability of aryl zinc species by sequestering H2O contaminants. Coupling reactions of Me(p‐C6H4)ZnX (where X=different salts) with 4‐bromoanisole highlight the importance of the presence of Mg(OPiv)2. Insight into the role of LiCl in these multicomponent mixtures is provided by the molecular structure of [(THF)2Li2(Cl)2(OPiv)2Zn]. 相似文献
926.
Pitois A de las Heras LA Zampolli A Menichetti L Carlos R Lazzerini G Cionini L Salvatori PA Betti M 《Analytical and bioanalytical chemistry》2006,384(3):751-760
Boron neutron capture therapy (BNCT) is a bimodal radiotherapeutic treatment based on the irradiation of neoplastic tissues
with neutrons after the tissues have selectively accumulated molecules loaded with nuclides with large neutron capture cross-sections
(such boron-10). Boron-10 carriers have been tested to a limited extent, and clinical trials have been conducted on sulfhydryl
borane (10B-BSH) and boronophenylalanine (10B-BPA). However, precise and accurate measurements of boron-10 concentrations (0.1–100 μg/g) in specimens and samples of limited
size (μg scale) are needed in order to be able to biologically characterise new compounds in predictive tissue dosimetry,
toxicology and pharmacology studies as well as in clinical investigations. A new approach based on fast separation and detection
of 10B-BPA performed by coupling capillary electrophoresis to electrospray mass spectrometry is reported. This method allows the
quantitative analysis and characterisation of 10B-BPA in a short time with a high separation efficiency. Detection limits of 3 μM for 10B-BPA and 30 ng/mL for 10B were obtained with CE–ESI–MS. A quantification limit of 10 μM for 10B-BPA (100 ng/mL for 10B) was attained. The total boron-10 concentration was determined by high-resolution inductively coupled mass spectrometry
in order to validate the method. Boron-10 isotope measurements were carried out by HR–ICP–MS at medium resolution (R=4000)
due to the presence of an isobaric interference at mass 10. Good agreement was obtained between the values from CE–ESI–MS
and those from HR–ICP–MS. The method has been successfully used to determine the 10B-BPA in two lines of cultured cells. 相似文献
927.
Guadalupe Z Soldevilla A Sáenz-Navajas MP Ayestarán B 《Journal of chromatography. A》2006,1112(1-2):112-120
A multiple-step analytical method was developed to improve the analysis of polymeric phenolics in red wines. With a common initial step based on the fractionation of wine phenolics by gel permeation chromatography (GPC), different analytical techniques were used: high-performance liquid chromatography-diode array detection (HPLC-DAD), HPLC-mass spectrometry (MS), capillary zone electrophoresis (CZE) and spectrophotometry. This method proved to be valid for analyzing different families of phenolic compounds, such as monomeric phenolics and their derivatives, polymeric pigments and proanthocyanidins. The analytical characteristics of fractionation by GPC were studied and the method was fully validated, yielding satisfactory statistical results. GPC fractionation substantially improved the analysis of polymeric pigments by CZE, in terms of response, repeatability and reproducibility. It also represented an improvement in the traditional vanillin assay used for proanthocyanidin (PA) quantification. Astringent proanthocyanidins were also analyzed using a simple combined method that allowed these compounds, for which only general indexes were available, to be quantified. 相似文献
928.
929.
930.
Santos EM Araújo AN Couto CM Montenegro MC 《Analytical and bioanalytical chemistry》2006,384(4):867-875
The construction and general performance of new valproate-selective electrodes based on manganese(III) tetraphenylporphyrin
[Mn(III)TPP-Cl], as an ionophore, are presented. The ionophore was incorporated into PVC and ceramic membranes (sol–gel) based
on methyltriethoxysilane. The influence of membrane composition and pH and the effect of lipophilic cationic and anionic additives
in PVC membranes were investigated concerning their influence on the slope, response time, selectivity and lifetime of the
electrodes. The PVC membrane without additive and the sol–gel membrane presented slopes and practical limits of detection
of −60.8 mV dec−1 and 5x10−6 mol l−1 and −60.3 mV dec−1 and 1×10−4 mol l−1, respectively. The sol–gel membranes displayed higher selectivity for valproate when compared with PVC membranes. These two
types of electrodes were coupled to a sequential-injection analysis (SIA) system for the direct determination of valproate
in pharmaceutical formulations. The association of Mn(III)TPP-Cl with the sol–gel support inserted in a SIA system provided
potentiometric sensors with an analytical range of 1x10−3–5x10−2 mol l−1, with a sample rate of 55 samples per hour and a sample and carrier consumption of 140 and 2,500 μl per determination, respectively. 相似文献