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131.
Florian Venel Dr. Hiroki Nagashima Dr. Andrew G. M. Rankin Christelle Anquetil Dr. Vytautas Klimavicius Dr. Torsten Gutmann Prof. Gerd Buntkowsky Dr. Sylvie Derenne Prof. Olivier Lafon Dr. Arnaud Huguet Dr. Frédérique Pourpoint 《Chemphyschem》2021,22(18):1907-1913
Estuaries are key ecosystems with unique biodiversity and are of high economic importance. Along the estuaries, variations in environmental parameters, such as salinity and light penetration, can modify the characteristics of dissolved organic matter (DOM). Nevertheless, there is still limited information about the atomic-level transformations of DOM in this ecosystem. Solid-state NMR spectroscopy provides unique insights into the nature of functional groups in DOM. A major limitation of this technique is its lack of sensivity, which results in experimental time of tens of hours for the acquisition of 13C NMR spectra and generally precludes the observation of 15N nuclei for DOM. We show here how the sensitivity of solid-state NMR experiments on DOM of Seine estuary can be enhanced using dynamic nuclear polarization (DNP) under magic-angle spinning. This technique allows the acquisition of 13C NMR spectra of these samples in few minutes, instead of hours for conventional solid-state NMR. Both conventional and DNP-enhanced 13C NMR spectra indicate that the 13C local environments in DOM are not strongly modified along the Seine estuary. Furthermore, the sensitivity gain provided by the DNP allows the detection of 15N NMR signal of DOM, in spite of the low nitrogen content. These spectra reveal that the majority of nitrogen is in the amide form in these DOM samples and show an increased disorder around these amide groups near the mouth of the Seine. 相似文献
132.
Besides human red blood cells (RBC), a standard model used in AFM-single cell force spectroscopy (SCFS), little is known about apparent Young’s modulus (Ea) or adhesion of animal RBCs displaying distinct cellular features. To close this knowledge gap, we probed chicken, horse, camel, and human fetal RBCs and compared data with human adults serving as a repository for future studies. Additionally, we assessed how measurements are affected under physiological conditions (species-specific temperature in autologous plasma vs. 25 °C in aqueous NaCl solution). In all RBC types, Ea decreased with increasing temperature irrespective of the suspension medium. In mammalian RBCs, adhesion increased with elevated temperatures and scaled with reported membrane sialic acid concentrations. In chicken only adhesion decreased with higher temperature, which we attribute to the lower AE-1 concentration allowing more membrane undulations. Ea decreased further in plasma at every test temperature, and adhesion was completely abolished, pointing to functional cell enlargement by adsorption of plasma components. This halo elevated RBC size by several hundreds of nanometers, blunted the thermal input, and will affect the coupling of RBCs with the flowing plasma. The study evidences the presence of a RBC surface layer and discusses the tremendous effects when RBCs are probed at physiological conditions. 相似文献
133.
As a first step towards computing instanton-generated superpotentials in heterotic standard model vacua, we determine the Gromov–Witten invariants for a Calabi–Yau threefold with fundamental group π1(X)=Z3×Z3. We find that the curves fall into homology classes in H2(X,Z)=Z3⊕(Z3⊕Z3). The unexpected appearance of the finite torsion subgroup in the homology group complicates our analysis. However, we succeed in computing the complete genus-0 prepotential. Expanding it as a power series, the number of instantons in any integral homology class can be read off. This is the first explicit calculation of the Gromov–Witten invariants of homology classes with torsion. We find that some curve classes contain only a single instanton. This ensures that the contribution to the superpotential from each such instanton cannot cancel. 相似文献
134.
Pharmacological MRI (phMRI) experiments utilise fMRI time series methods to map the central effect of pharmaceutical compounds. The typical univariate maps may, however, integrate the effects of several different neurotransmitter systems or underlying mechanisms. The results may thus be spatially and/or mechanistically nonspecific. Intersubject correlation analysis based on the phMRI response amplitude can more directly identify patterns of functional connectivity underlying the central effects of an acutely administered compound. In this article, we extend this approach to experiments where the effects of one compound in modulating the response to another are of interest. Specifically, we show a modulation of the correlation structure of a probe compound (d-amphetamine) by pretreatment with the selective dopamine D3 receptor antagonist SB277011A in the rat. The strongest modifications in the correlation patterns occurred in connection with the ventral tegmental area, the source of mesolimbic dopamine projections and a key substrate in the reward system. 相似文献
135.
Friederike A. Sandbaumhüter Claudia Gittel M. Paula Larenza-Menzies Regula Theurillat Wolfgang Thormann Christina Braun 《Electrophoresis》2021,42(17-18):1826-1831
The enantioselectivity of the pharmacokinetics of methadone was investigated in anesthetized Shetland ponies after a single intravenous (0.5 mg/kg methadone hydrochloride; n = 6) or constant rate infusion (0.25 mg/kg bolus followed by 0.25 mg/kg/h methadone hydrochloride; n = 3) administration of racemic methadone. Plasma concentrations of l -methadone and d -methadone and their major metabolites, l - and d -2-ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine (EDDP), respectively, were analyzed by CE with highly sulfated γ-cyclodextrin as chiral selector and electrokinetic analyte injection from liquid/liquid extracts prepared at alkaline pH. In both trials, the d -methadone concentrations were lower than those of l -methadone and the d -EDDP levels were lower than those of L-EDDP. For the case of a single intravenous bolus injection, the plasma concentration versus time profile of methadone enantiomers was analyzed with a two-compartment pharmacokinetic model. l -methadone showed a slower elimination rate constant, a lower body clearance, and a smaller steady-state volume of distribution than d -methadone. d -methadone and d -EDDP were eliminated faster than their respective l -enantiomers. This is the first study that outlines that the disposition of racemic methadone administered to anesthetized equines is enantioselective. 相似文献
136.
Stefan Sander Dr. Robert Müller Dr. Mike Ahrens Prof. Dr. Martin Kaupp Prof. Dr. Thomas Braun 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(57):14287-14298
The reaction of [PtCl2(COD)] (COD=1,5-cyclooctadiene) with diisopropyl-2-(3-methyl)indolylphosphine (iPr2P(C9H8N)) led to the formation of the platinum(ii ) chlorido complexes, cis-[PtCl2{iPr2P(C9H8N)}2] ( 1 ) and trans-[PtCl2{iPr2P(C9H8N)}2] ( 2 ). The cis-complex 1 reacted with NEt3 yielding the complex cis-[PtCl{κ2-(P,N)-iPr2P(C9H7N)}{iPr2P(C9H8N)}] ( 3 ) bearing a cyclometalated κ2-(P,N)-phosphine ligand, while the isomer 2 with a trans-configuration did not show any reactivity towards NEt3. Treatment of 1 or 3 with (CH3)4NF (TMAF) resulted in the formation of the twofold cyclometalated complex cis-[Pt{κ2-(P,N)-iPr2P(C9H7N)}2] ( 4 ). The molecular structures of the complexes 1–4 were determined by single-crystal X-ray diffraction. The fluorido complex cis-[PtF{κ2-(P,N)-iPr2P(C9H7N)}{iPr2P(C9H8N)}] ⋅ (HF)4 ( 5 ⋅ (HF)4) was formed when complex 4 was treated with different hydrogen fluoride sources. The Pt(ii ) fluorido complex 5 ⋅ (HF)4 exhibits intramolecular hydrogen bonding in its outer coordination sphere between the fluorido ligand and the NH group of the 3-methylindolyl moiety. In contrast to its chlorido analogue 3 , complex 5 ⋅ (HF)4 reacted with CO or the ynamide 1-(2-phenylethynyl)-2-pyrrolidinone to yield the complexes trans-[Pt(CO){κ2-(P,C)-iPr2P(C9H7NCO)}{iPr2P(C9H8N)}][F(HF)4] ( 7 ) and a complex, which we suggest to be cis-[Pt{C=C(Ph)OCN(C3H6)}{κ2-(P,N)-iPr2P(C9H7N)}{iPr2P(C9H8N)}][F(HF)4] ( 9 ), respectively. The structure of 9 was assigned on the basis of DFT calculations as well as NMR and IR data. Hydrogen bonding of HF and NH to fluoride was proven to be crucial for the existence of 7 and 9 . 相似文献
137.
138.
Excellent passivation of thin silicon wafers by HF‐free hydrogen plasma etching using an industrial ICPECVD tool
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Muzhi Tang Jia Ge Johnson Wong Zhi Peng Ling Torsten Dippell Zhenhao Zhang Marco Huber Manfred Doerr Oliver Hohn Peter Wohlfart Armin Gerhard Aberle Thomas Mueller 《固体物理学:研究快报》2015,9(1):47-52
In this work, hydrogen plasma etching of surface oxides was successfully accomplished on thin (~100 µm) planar n‐type Czochralski silicon wafers prior to intrinsic hydrogenated amorphous silicon [a‐Si:H(i)] deposition for heterojunction solar cells, using an industrial inductively coupled plasma‐enhanced chemical vapour deposition (ICPECVD) platform. The plasma etching process is intended as a dry alternative to the conventional wet‐chemical hydrofluoric acid (HF) dip for solar cell processing. After symmetrical deposition of an a‐Si:H(i) passivation layer, high effective carrier lifetimes of up to 3.7 ms are obtained, which are equivalent to effective surface recombination velocities of 1.3 cm s–1 and an implied open‐circuit voltage (Voc) of 741 mV. The passivation quality is excellent and comparable to other high quality a‐Si:H(i) passivation. High‐resolution transmission electron microscopy shows evidence of plasma‐silicon interactions and a sub‐nanometre interfacial layer. Using electron energy‐loss spectroscopy, this layer is further investigated and confirmed to be hydrogenated suboxide layers. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim) 相似文献
139.
Enzymatic Conversion of Flavonoids using Bacterial Chalcone Isomerase and Enoate Reductase
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Dipl.‐Biol. Mechthild Gall Dipl.‐Biochem. Maren Thomsen Dipl.‐Biochem. Christin Peters Dr. Ioannis V. Pavlidis M. Sc. Patrick Jonczyk M. Sc. Philipp P. Grünert Dr. Sascha Beutel Prof. Dr. Thomas Scheper Egon Gross Dr. Michael Backes Dr. Torsten Geißler Dr. Jakob P. Ley Dr. Jens‐Michael Hilmer Dr. Gerhard Krammer Dr. Gottfried J. Palm Prof. Dr. Winfried Hinrichs Prof. Dr. Uwe T. Bornscheuer 《Angewandte Chemie (International ed. in English)》2014,53(5):1439-1442
Flavonoids are a large group of plant secondary metabolites with a variety of biological properties and are therefore of interest to many scientists, as they can lead to industrially interesting intermediates. The anaerobic gut bacterium Eubacterium ramulus can catabolize flavonoids, but until now, the pathway has not been experimentally confirmed. In the present work, a chalcone isomerase (CHI) and an enoate reductase (ERED) could be identified through whole genome sequencing and gene motif search. These two enzymes were successfully cloned and expressed in Escherichia coli in their active form, even under aerobic conditions. The catabolic pathway of E. ramulus was confirmed by biotransformations of flavanones into dihydrochalcones. The engineered E. coli strain that expresses both enzymes was used for the conversion of several flavanones, underlining the applicability of this biocatalytic cascade reaction. 相似文献
140.
C,C‐ and N,C‐Coupled Dimers of 2‐Aminotetraphenylporphyrins: Regiocontrolled Synthesis,Spectroscopic Properties,and Quantum‐Chemical Calculations
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Dr. Torsten Bruhn Dipl.‐Chem. Franziska Witterauf Dr. Daniel C. G. Götz Carina T. Grimmer Dipl.‐Chem. Max Würtemberger Prof. Dr. Udo Radius Prof. Dr. Gerhard Bringmann 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(14):3998-4006
β,β′‐Bisporphyrins are intrinsically chiral porphyrin dimers with fascinating properties. The configurational stability at their axes can be directed by variation of the central metal atoms. Herein, we present a regioselective functionalization of the monomeric 2‐amino‐tetraphenyl‐porphyrin as a versatile substrate for dimerization by oxidative coupling. By simple variation of the reaction conditions (solvent and oxidant), the oxidation selectively gave either the axially chiral C,C‐coupled diaminobisporphyrin in high yields or, under Ullmann conditions, the twofold N,C‐linked achiral dimer, also in good yields. A generalized mechanism for the coupling reaction is proposed based on DFT calculations. The axially chiral β,β′‐coupled porphyrin dimers were isolated as racemic mixtures, but can be resolved by HPLC on a chiral phase. TDDFT and coupled‐cluster calculations were used to explain the spectroscopic properties of the aminoporphyrins and their dimers and to elucidate the absolute configurations of the C,C‐coupled bisporphyrins. 相似文献