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71.
Martin W. Feyereisen Rick A. Kendall Jeff Nichols David Dame Joseph T. Golab 《Journal of computational chemistry》1993,14(7):818-830
The use of a cluster of workstations as an alternative supercomputer resource is demonstrated using the ab initio direct SCF and RPA code DISCO. DISCO was implemented using several different mechanisms to achieve the requisite parallelization. The various parallel software mechanisms are characterized based upon several different criteria, including portability, ease of use, and relative efficiency. The application of direct SCF and RPA techniques to study the static polarizability of paranitroaniline is described. © 1993 John Wiley & Sons, Inc. 相似文献
72.
[reaction: see text] A general amination strategy for the N-alkynylation of carbamates, sulfonamides, and chiral oxazolidinones and imidazolidinones is described. A variety of substituted ynamides are available by deprotonation of amides with KHMDS followed by reaction with CuI and an alkynyl bromide. 相似文献
73.
Pretreatment of corn fiber by pressure cooking in water 总被引:4,自引:0,他引:4
Joseph R. Weil Ayda Sarikaya Shiang-Lan Rau Joan Goetz Christine M. Ladisch Mark Brewer Rick Hendrickson Michael R. Ladisch 《Applied biochemistry and biotechnology》1998,73(1):1-17
The pretreatment of corn fiber using liquid water at temperatures between 220 and 260°C enhances enzymatic hydrolysis. This
paper describes the laboratory reactor system currently in use for cooking of corn fiber at temperatures ranging from 200
to 260°C. The corn fiber at approx 4.4% solid/liquid slurry was treated in a 2-L, 304 SS, Parr reactor with three turbine
propeller agitators and a Proportional-Integral-Derivative (PID), controller that controlled temperature within ±1°C. Heat-up
times to the final temperatures of 220, 240, or 260°C were achieved in 50 to 60 min. Hold time at the final temperature was
less than 10 s. A serpentine cooling coil, through which tap water was circulated at the completion of the run, cooled the
reactor’s contents to 180°C within 2 min after the maximum temperature was attained. Ports in the reactor’s head plate facilitated
sampling of the slurry and monitoring the pH. A continuous pH monitoring system was developed to help observe trends in pH
during pretreatment and to assist in the development of a base (2.0M KOH) addition profile to help keep the pH within the range of 5.0 to 7.0. Enzymatic hydrolysis gave 33 to 84% conversion
of cellulose in the pretreated fiber to glucose compared to 17% for untreated fiber. 相似文献
74.
Dr. Fadlilatul Taufany Dr. Chun‐Jern Pan Feng‐Ju Lai Dr. Hung‐Lung Chou Loka Subramanyam Sarma Dr. John Rick Jhih‐Min Lin Dr. Jyh‐Fu Lee Dr. Mau‐Tsu Tang Prof. Bing‐Joe Hwang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(3):905-915
A controlled composition‐based method—that is, the microwave‐assisted ethylene glycol (MEG) method—was successfully developed to prepare bimetallic PtxRu100?x/C nanoparticles (NPs) with different alloy compositions. This study highlights the impact of the variation in alloy composition of PtxRu100?x/C NPs on their alloying extent (structure) and subsequently their catalytic activity towards the methanol oxidation reaction (MOR). The alloying extent of these PtxRu100?x/C NPs has a strong influence on their Pt d‐band vacancy and Pt electroactive surface area (Pt ECSA); this relationship was systematically evaluated by using X‐ray absorption (XAS), scanning electron microscopy (SEM) coupled with energy dispersive X‐ray spectroscopy (EDX), transmission electron microscopy (TEM), density functional theory (DFT) calculations, and electrochemical analyses. The MOR activity depends on two effects that act in cooperation, namely, the number of active Pt sites and their activity. Here the number of active Pt sites is associated with the Pt ECSA value, whereas the Pt‐site activity is associated with the alloying extent and Pt d‐band vacancy (electronic) effects. Among the PtxRu100?x/C NPs with various Pt:Ru atomic ratios (x=25, 50, and 75), the Pt75Ru25/C NPs were shown to be superior in MOR activity on account of their favorable alloying extent, Pt d‐band vacancy, and Pt ECSA. This short study brings new insight into probing the synergistic effect on the surface reactivity of the PtxRu100?x/C NPs, and possibly other bimetallic Pt‐based alloy NPs. 相似文献
75.
Rick L. Paul W. Clay Davis Lee Yu Karen E. Murphy William F. Guthrie Dennis D. Leber Colleen E. Bryan Thomas W. Vetter Gulchekhra Shakirova Graylin Mitchell David J. Kyle Jeffery M. Jarrett Kathleen L. Caldwell Robert L. Jones Steven Eckdahl Michelle Wermers Melissa Maras C. D. Palmer M. F. Verostek C. M. Geraghty Amy J. Steuerwald Patrick J. Parsons 《Journal of Radioanalytical and Nuclear Chemistry》2014,299(3):1555-1563
Radiochemical neutron activation analysis (RNAA) was used to measure arsenic at four levels in standard reference material (SRM) 955c Toxic Elements in Caprine Blood and at two levels in SRM 2668 Toxic Elements in Frozen Human Urine for the purpose of providing mass concentration values for certification. Samples were freeze-dried prior to analysis followed by neutron irradiation for 3 h at a fluence rate of 1 × 1014 cm?2 s?1. After sample dissolution in perchloric and nitric acids, arsenic was separated from the matrix either by retention on hydrated manganese dioxide (urine) or by extraction into zinc diethyldithiocarbamate in chloroform (blood). 76As was quantified by gamma-ray spectroscopy. Differences in chemical yield and counting geometry between samples and standards were monitored by measuring the count rate of a 77As tracer added before sample dissolution. RNAA results were combined with inductively coupled plasma-mass spectrometry values from National Institute of Standards and Technology and collaborating laboratories to provide certified values of 10.81 ± 0.54 and 213.1 ± 0.73 μg/L for SRM 2668 Levels I and II, and certified values of 21.66 ± 0.73, 52.7 ± 1.1, and 78.8 ± 4.9 μg/L for SRM 955c Levels II–IV, respectively. Because of discrepancies between values obtained by different methods for SRM 955c Level I, an information value of <5 μg/L was assigned for this material. 相似文献
76.
The photochemistry of 1,2-dihydronaphthalene oxide (254 nm) was reexamined and indan was found to be a primary photoproduct, as well as the traditionally assumed secondary photoproduct. Quenching studies demonstrated that indan, as a primary photoproduct, is derived from a triplet pathway, competing with a singlet route, back to the ground state surface. CASSCF calculations strongly suggest that the triplet pathway consists of a dissociation of the oxirane moiety to give a triplet carbene and aldehyde, which via hydrogen abstraction-decarbonylation-ISC recloses to give indan. Conical intersections corresponding to the presumed 1,2-hydrogen shift and 1,2-alkyl shift to give 2-tetralone and 1-indancarbaldehyde, respectively, were located computationally. 相似文献
77.
Wang D Liu J Huo Q Nie Z Lu W Williford RE Jiang YB 《Journal of the American Chemical Society》2006,128(42):13670-13671
A new, surface-mediated method to grow transparent, oriented, and well-defined nanocrystalline anatase TiO2 films has been developed. The morphology of crystals is tunable from octahedral pyramids to truncate octahedral pyramids. These novel nanocrystalline films could have implications not only for practical applications but also for understanding the structure and orientation dependent properties of the important anatase material. 相似文献
78.
A method for treating charge transfer interactions in classical potential models is developed and applied to water. In this method, a discrete amount of charge is transferred for each hydrogen bond formed. It is designed to be simple to implement, to be applicable to a variety of potential models, and to satisfy various physical requirements. The method does not transfer charge at large intramolecular distances, it does not result in a conductive liquid, and it can be easily parameterized to give the correct amount of charge transfer. Two charge transfer models are developed for a polarizable and a non-polarizable potential. The models reproduce many of the properties of liquid water, including the structure, the diffusion constant, and thermodynamic properties over a range of temperatures. 相似文献
79.
Anna V. Bay Keegan P. Fitzpatrick Rick C. Betori Prof. Karl A. Scheidt 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(23):9228-9233
As a key element in the construction of complex organic scaffolds, the formation of C−C bonds remains a challenge in the field of synthetic organic chemistry. Recent advancements in single-electron chemistry have enabled new methods for the formation of various C−C bonds. Disclosed herein is the development of a novel single-electron reduction of acyl azoliums for the formation of ketones from carboxylic acids. Facile construction of the acyl azolium in situ followed by a radical–radical coupling was made possible merging N-heterocyclic carbene (NHC) and photoredox catalysis. The utility of this protocol in synthesis was showcased in the late-stage functionalization of a variety of pharmaceutical compounds. Preliminary investigations using chiral NHCs demonstrate that enantioselectivity can be achieved, showcasing the advantages of this protocol over alternative methodologies. 相似文献
80.
Sabine V. Auras Dr. Richard van Lent Dr. Dima Bashlakov Jessika M. Piñeiros Bastidas Tycho Roorda Rick Spierenburg Assoc. Prof. Ludo B. F. Juurlink 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(47):21159-21165
We determine absolute reactivities for dissociation at low coordinated Pt sites. Two curved Pt(111) single-crystal surfaces allow us to probe either straight or highly kinked step edges with molecules impinging at a low impact energy. A model extracts the average reactivity of inner and outer kink atoms, which is compared to the reactivity of straight A- and B-type steps. Local surface coordination numbers do not adequately capture reactivity trends for H2 dissociation. We utilize the increase of reactivity with step density to determine the area over which a step causes increased dissociation. This step-type specific reactive area extends beyond the step edge onto the (111) terrace. It defines the reaction cross-section for H2 dissociation at the step, bypassing assumptions about contributions of individual types of surface atoms. Our results stress the non-local nature of H2 interaction with a surface and provide insight into reactivity differences for nearly identical step sites. 相似文献