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961.
Franziska Dahlmann Dennis F. Dinu Dr. Pavol Jusko Christine Lochmann Thomas Gstir Aravindh N. Marimuthu Prof. Dr. Klaus R. Liedl Prof. Dr. Sandra Brünken Prof. Dr. Roland Wester 《Chemphyschem》2023,24(15):e202300262
We present infrared predissociation spectra of C2N−(H2) and C 3N−(H2) in the 300–1850 cm−1 range. Measurements were performed using the FELion cryogenic ion trap end user station at the Free Electron Lasers for Infrared eXperiments (FELIX) laboratory. For C2N−(H2), we detected the CCN bending and CC−N stretching vibrations. For the C3N−(H2) system, we detected the CCN bending, the CC−CN stretching, and multiple overtones and/or combination bands. The assignment and interpretation of the presented experimental spectra is validated by calculations of anharmonic spectra within the vibrational configuration interaction (VCI) approach, based on potential energy surfaces calculated at explicitly correlated coupled cluster theory (CCSD(T)-F12/cc-pVTZ−F12). The H2 tag acts as an innocent spectator, not significantly affecting the C2,3N− bending and stretching mode positions. The recorded infrared predissociation spectra can thus be used as a proxy for the vibrational spectra of the bare anions. 相似文献
962.
Hassler BL Dennis M Laivenieks M Zeikus JG Worden RM 《Applied biochemistry and biotechnology》2007,143(1):1-15
Bioelectronic interfaces that facilitate electron transfer between the electrode and a dehydrogenase enzyme have potential
applications in biosensors, biocatalytic reactors, and biological fuel cells. The secondary alcohol dehydrogenase (2° ADH)
from Thermoanaerobacter ethanolicus is especially well suited for the development of such bioelectronic interfaces because of its thermostability and facile
production and purification. However, the natural cofactor for the enzyme, β-nicotinamide adenine dinucleotide phosphate (NADP+), is more expensive and less stable than β-nicotinamide adenine dinucleotide (NAD+). PCR-based, site-directed mutagenesis was performed on 2° ADH in an attempt to adjust the cofactor specificity toward NAD+ by mutating Tyr218 to Phe (Y218F 2° ADH). This mutation increased the K
m(app) for NADP+ 200-fold while decreasing the K
m(app) for NAD+ 2.5-fold. The mutant enzyme was incorporated into a bioelectronic interface that established electrical communication between
the enzyme, the NAD+, the electron mediator toluidine blue O (TBO), and a gold electrode. Cyclic voltammetry, impedance spectroscopy, gas chromatography,
mass spectrometry, constant potential amperometry, and chronoamperometry were used to characterize the mutant and wild-type
enzyme incorporated in the bioelectronic interface. The Y218F 2° ADH exhibited a fourfold increase in the turnover ratio compared
to the wild type in the presence of NAD+. The electrochemical and kinetic measurements support the prediction that the Rossmann fold of the enzyme binds to the phosphate
moiety of the cofactor. During the 45 min of continuous operation, NAD+ was electrically recycled 6.7 × 104 times, suggesting that the Y218F 2° ADH-modified bioelectronic interface is stable. 相似文献
963.
The mechanism of reduction of benzoyl cyanide, 6, p-methoxybenzoyl cyanide, 7, and p-chlorobenzoyl cyanide, 8, has been studied in acetonitrile (6 and 7), N,N-dimethylformamide (6), and acetonitrile containing water (all three compounds). The reaction proceeds by initial reduction to form the anion radical followed by dimerization to produce an intermediate dianion, the dianion of the dicyanohydrin of benzil. The latter loses cyanide to give the anion of the monocyanohydrin of benzil, which undergoes two parallel reactions: expulsion of cyanide to give the corresponding benzil and rearrangement to the monoanion of mandelonitrile benzoate. The addition of water brings about an increase in the dimerization rate constant and an associated increase in the amount of benzil that is produced. The standard potentials for the initial reduction step have been evaluated, and their dependence on the substituent is discussed. The dimerization rate constants have also been evaluated. 相似文献
964.
A new distyryl boron dipyrromethene (BODIPY) with two bis(1,2,3‐triazole)amino substituents has been prepared by typical Knoevenagel condensation followed by click reaction. The compound selectively binds to Cu2+ and Hg2+ ions in CH3CN/H2O (1:1 v/v) to give remarkably blueshifted electronic absorption and fluorescence bands as a result of inhibition of the intramolecular charge‐transfer process upon binding to these metal ions. The color changes can be easily seen by the naked eye. The binding stoichiometry between this probe and Cu2+ ions has been determined to be 1:2 by a Job plot of the fluorescence data with a binding constant of ((6.2±0.6)×109) M ?2. The corresponding value for Hg2+ ions is about sixfold smaller. 相似文献
965.
Gd‐DTPA‐Dopamine‐Bisphytanyl Amphiphile: Synthesis,Characterisation and Relaxation Parameters of the Nanoassemblies and Their Potential as MRI Contrast Agents 下载免费PDF全文
Abhishek Gupta Dr. Scott A. Willis Lynne J. Waddington Dr. Tim Stait‐Gardner Dr. Liliana de Campo Prof. Dennis W. Hwang Dr. Nigel Kirby Prof. William S. Price Dr. Minoo J. Moghaddam 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(40):13950-13960
Here, a new amphiphilic magnetic resonance imaging (MRI) contrast agent, a GdIII‐chelated diethylenetriaminepentaacetic acid conjugated to two branched alkyl chains via a dopamine spacer, Gd‐DTPA‐dopamine‐bisphytanyl (Gd‐DTPA‐Dop‐Phy), which is readily capable of self‐assembling into liposomal nanoassemblies upon dispersion in an aqueous solution, is reported. In vitro relaxivities of the dispersions were found to be much higher than Magnevist, a commercially available contrast agent, at 0.47 T but comparable at 9.40 T. Analysis of variable temperature 17O NMR transverse relaxation measurements revealed the water exchange of the nanoassemblies to be faster than that previously reported for paramagnetic liposomes. Molecular reorientation dynamics were probed by 1H NMRD profiles using a classical inner and outer sphere relaxation model and a Lipari–Szabo “model‐free” approach. High payloads of GdIII ions in the liposomal nanoassemblies made solely from the Gd‐DTPA‐Dop‐Phy amphiphiles, in combination with slow molecular reorientation and fast water exchange makes this novel amphiphile a suitable candidate to be investigated as an advanced MRI contrast agent. 相似文献
966.
A simple detection method using ultra-performance liquid chromatography electrospray ionisation tandem mass spectrometry (UPLC-ESI-MS-MS) coupled with the sample dilution method for determining trace microcystin-LR (MC-LR) in drinking water is presented. The limit of detection (LOD) was 0.04 μg/L and the limit of quantitation (LOQ) was 0.1 μg/L. Water matrix effects of ionic strength, dissolved organic carbon (DOC) and pH were examined. The results indicate that signal detection intensity for MC-LR was significantly suppressed as the ionic strength increased from ultrapure water condition, whereas it increased slightly with solution pH and DOC at low concentrations. However, addition of methanol (MeOH) into the sample was able to counter the signal suppression effects. In this study, dilution of the tap water sample by adding 4% MeOH (v/v) was observed to be adequate to compensate for the signal suppression. The recoveries of the samples fortified with MC-LR (0.2, 1, and 10 μg/L) for three different tap water samples ranged from 84.4% to 112.9%. 相似文献
967.
Heitmann D Pape T Hepp A Mück-Lichtenfeld C Grimme S Hahn FE 《Journal of the American Chemical Society》2011,133(29):11118-11120
Reaction of the N,N'-diisobutyl-substituted benzannulated N-heterocyclic plumbylene (NHPb) 1 with [Pd(PPh(3))(4)] and [Pt(PPh(3))(4)] gave the complexes [M(NHPb)(PPh(3))(3)] (M = Pd [2], Pt [3]). X-ray diffraction studies of both complexes showed an angle of ~125° between the plumbylene plane and the transition-metal-Pb axis, indicating coordination of the transition metal to the empty π orbital of the plumbylene Pb atom. The experimentally determined metric parameters of complexes [2] and [3] are discussed on the basis of DFT calculations. 相似文献
968.
Even though quantum mechanical tunnelling has been appearing recurrently mostly in theoretical studies that emphasize its decisive role for many chemical reactions, it still appears suspicious to most organic chemists. Recent experiments in combination with powerful computational approaches, however, have demonstrated that tunnelling must be included to fully understand chemical reactivity. Here we provide an overview of the importance of tunnelling in organic chemical reactions. 相似文献
969.
Everson Kandare Baljinder K. Kandola Dennis Price Shonali Nazaré Richard A. Horrocks 《Polymer Degradation and Stability》2008,93(11):1996-2006
The thermal degradation behaviours of flame-retarded unsaturated polyester resin formulations containing ammonium polyphosphate (APP), Cloisite 25A nanoclay and zinc based smoke suppressants have been studied using thermogravimetric analysis (TGA) combined with infrared analysis of the evolved gases (EGA) and pyrolysis/gas chromatography-mass spectrometry (GC/MS). In TGA-EGA experiments, the mass loss as a function of temperature has been correlated with the evolution of carbon monoxide (CO) and carbon dioxide (CO2) and oxygen (O2) consumption as measured by an oxygen analyser. The effect of APP, Cloisite 25A and the smoke suppressants on the evolution of CO and CO2 has been examined. The decomposition behaviour of flame-retarded polyester resins under isothermal pyrolytic conditions was investigated and the evolved gaseous products were collected and qualitatively and semi-quantitatively analysed via GC/MS. The addition of APP does not yield many new gaseous products relative to the unmodified polyester resin neither does the presence of zinc borate (ZB) and zinc stannate (ZS) together with APP. Possible chemical interactions are discussed in an attempt to explain the observed results. 相似文献
970.
Pata V Ahmed F Discher DE Dant N 《Langmuir : the ACS journal of surfaces and colloids》2004,20(10):3888-3893
The commonly held model for membrane dissolution by detergents/surfactants requires lipid transport from the inner to the outer bilayer leaflet ('flip-flop'). Although applicable to many systems, it fails in cases where cross-bilayer transport of membrane components is suppressed. In this paper we investigate the mechanism for surfactant-induced solubilization of polymeric bilayers. To that end, we examine the dissolution of a series of increasingly thick, polymer-based vesicles (polymersomes) by a nonionic surfactant, Triton X-100, using dynamic light scattering. We find that increasing the bilayer thickness imparts better resistance to dissolution, so that the concentration required for solubilization, after a fixed amount of time, increases nearly linearly with membrane thickness. Combining our experimental data with a theoretical model, we show that the dominant mechanism for the surfactant-induced dissolution of polymeric vesicles, where polymer flip-flop across the membrane is suppressed, is the surfactant transport through the bilayer. This mechanism is different both qualitatively and quantitatively from the mechanisms by which surfactants dissolve pure lipid vesicles. 相似文献