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911.
V. G. Berezkin E. Yu. Sorokina A. I. Sokolov B. A. Rudenko 《Journal of Analytical Chemistry》2003,58(1):61-67
The effects of the presence of water vapor in the carrier gas and the temperature on the retention of achiral and chiral compounds, enantioselectivity, and performance of an open-tubular column with a cyclodextrin-containing phase were studied. The use of a carrier gas containing water vapor in the determination of optically active isomers, such as camphor, slightly increases the retention factor. A substantial improvement of performance characteristics of the column was found: for hydroxy compounds, the column performance increased by two to three times and the peak symmetry improved by more than twice. 相似文献
912.
Feijtel TC 《SAR and QSAR in environmental research》1995,3(3):237-245
Abstract Impending changes in EEC legislation have accelerated the need to define the principles and practical considerations of the use of QSARs in priority setting and risk assessment. It is important to delineate the limitations of this approach and to review whether and how this information should be used in the risk assessment. The value and limitations of QSARs for use in priority setting and risk assessment will not be discussed in detail since the European Chemical Industry Ecology and Toxicology Centre (ECETOC) has only recently established a Task Force to tackle this issue. The terms of reference of the Task Force are: (1) compare the predictions obtained with QSARs to measured data using ECETOC databases and other sources of data and comment on the validity and applicability of such QSARs; (2) identify and review software packages which are available for accessing and using appropriate QSARs; (3) identify those aspects of environmental distribution, fate and effects where the further development of QSARs is desirable and feasible; and (4) provide a scientific basis for ECETOC's contribution to the activities of the European Chemicals Bureau (ECB) in this area. In this short paper, only an initial and personal evaluation is made of when and where to use QSARs in the priority setting and risk assessment process within the regulatory framework. Some critical remarks and suggestions are provided to guide future developments and integration of QSARs in the risk assessment process. 相似文献
913.
Capillary electrophoresis (CE) with head-column field-amplified sample stacking (FASS) in presence of a water plug inserted at the capillary tip is a robust approach providing a more than 1000-fold sensitivity enhancement when applied to low-conductivity samples that are analyzed in an integrated instrument. Employing modular systems comprising a small hydrodynamic buffer flow (siphoning) towards the capillary end and featuring UV absorption or electrospray ionization mass spectrometric (MS) detection, insertion of a water plug is demonstrated to deteriorate the performance of head-column FASS or making it unfunctional. Electroinjection in the absence of the water plug can be employed instead and is shown to provide a ng/ml sensitivity when applied to low conductivity samples. With some suction of sample into the capillary during electroinjection, contamination of the sample vial with buffer is thereby largely avoided. Electroinjection applied to the CE-ion trap MS-MS and MS-MS-MS analysis of twofold diluted urines, urinary solid-phase extracts and urinary liquid-liquid extracts is shown to provide much improved sensitivity compared to hydrodynamic injection of these samples. With electroinjection from diluted urine and urinary solid-phase extracts, the presence of free opioids and their glucuronic acid conjugates can be unambiguously confirmed in urines that were collected after single-dose administration of small amounts of opioids (tested with about 7 mg codeine and 25 mg dihydrocodeine, respectively). Thus, CE-multiple MS with direct electroinjection of opioids from untreated urines could prove to become a rapid and simple approach for unambiguous urinary testing of drug abuse. Procedures leading to the reduction of siphoning in modular CE setups are briefly discussed as well. 相似文献
914.
A series of sterically demanding diporphyrins H2(por)-X-(por)H2 ligands that contain spacers (X) with different degrees of flexibility were synthesized from the trimesitylporphyrin derivatives 5-(4-hydroxyphenyl)-10,15,20-trimesitylporphyrin (TMP-OH)H2 (1a) and 5-(2,6-dimethyl-4-hydroxyphenyl)-10,15,20-trimesityl-porphyrin, (DMTMP-OH)H2 (1b). The monomeric porphyrins 1a,b, which have steric demands similar to that of tetramesitylporphyrin, (TMP)H2, and carry a hydroxyl functional group at the para position of one of the mesophenyl substituents, were constructed from reaction of pyrrole with two aromatic aldehydes by a mixed aldehyde condensation approach. The diporphyrins with alkyl diether tethers were obtained stepwise from reactions of the hydroxy functionalized porphyrins 1a,b with dibromides Br(CH2)nBr. The diporphyrin which contains a more rigid m-xylylene spacer, was made directly from reaction of 1b with alpha,alpha'-dibromo-m-xylene. Rhodium was inserted into the porphyrins using Rh2(CO)2Cl2 and converted to dimethyl complexes Me-Rh(Por)-X-(Por)Rh-Me. The dirhodium(II) derivatives .Rh(por)-X-(por)Rh.) were generated by photolysis of the dimethyl complexes and observed to occur as stable bimetalloradicals because the ligand steric demands prohibit Rh(II)-Rh(II) bonding. EPR spectra of the dirhodium(II) derivatives, triphenyl phospine adducts, and dioxygen complexes are reported. The kinetic advantage of bimetalloradical complexes for substrate reactions that have two metal-centered radicals in the transition state is demonstrated by reactions of dihydrogen with dirhodium(II) bimetalloradical complexes. 相似文献
915.
The growth rate of isotactic polypropylene is deduced from microscopic observations during isothermal crystallizations. A change in the growth regime is observed at 138 C and interpreted as a Regime III Regime II transition, according to Hoffman's kinetic theory of polymer crystallization. A Regime II Regime I transition is also theoretically predicted at 155 C, i. e. at a temperature outside the investigated temperature range. The Regime III Regime II transition is related to the positive to negative change in the spherulite birefringence, which is generally attributed to a change in the organization of crystalline lamellae: quadritic arrays of intercrossing lamellae atT
c < 138 C (Regime III) and preferentially radiating lamellae atT
c > 138 C (Regime II). It is suggested that such a morphological change could be interpreted using the concept of non-adjacent re-entry introduced in Hoffman's kinetic theory. This interpretation could also explain the interspherulitic ruptures observed in negative spherulites. 相似文献
916.
Nanosecond flash photolysis has been carried out on benzophenone solutions in benzene and acetonitrile in presence of oxygen- and sulfur-containing reductants such as anisole, thioanisole, dibutyl sulfide and methyl 2-octyl ether. The quantum yield of ketyl formation is compared to previous results on the quantum yields of the final benzophenone disappearance. This comparison is also related to previous data on benzophenone reduction by nitrogen-containing reductants such as amines and amides and suggests a general mechanism for benzophenone photoreduction by heteroatom-containing donors. 相似文献
917.
Mesoionic thiazolones and selenazolones react with dimethyl acetylene dicarboxylate to give thiophenes or pyridones. We show that the reactivity of the mesoionic thiazolones towards dimethyl acetylene dicarboxylate may be explained by second order perturbation theory, limited to frontier orbitals. The influence of the temperature and of the nature of the substituants on the evolution of the primary cycloadduct can be explained by a competition between a retro Diels-Alder reaction giving a thiophene and a desulfurisation or a deselenurisation giving a pyridone. 相似文献
918.
The free NH3 molecule and the [Zn(NH3)4]2+ ion were studied by the kinematic coupling approach. The pure effects of this coupling were found to be small, and some modifications had to be introduced in order to get a reasonable force field. The force constants deduced for the skeletal vibrations are comparable with those of a quasi-exact force field. Calculated frequencies for [68Zn(NH3)4]2+ and [64Zn(ND3)4]2+ are reported in addition to those of [64Zn(NH3)4]2+. Mean amplitudes of vibration for [64Zn(NH3)4]2+ are given. 相似文献
919.
A high performance liquid chromatographic (HPLC) method is described for the determination of the four major aflatoxins, B1, B2, G1 and G2, in peanut products. The aflatoxins are extracted by adapting a procedure developed by Pons (1) at the SRRC, USDA, and quantitated utilizing a new 5 mum reverse-phase column with NaCl/acetontrile/methanol mobile phase (3 + 1 + 1). The 5 mum column achieved baseline resolution of each of the four aflatoxins. Retention times and peak heights were reproducible. The procedure was successfully applied to several types of peanut products and was applicable to both roasted and unroasted peanuts, which is a decided advantage over the current CB and BF extraction methods. Additionally, it can be used for sweetened peanut matrixes with no interferences in the chromatography. The total time required for sample preparation and aflatoxin determination is less than 1.5 hours. 相似文献
920.
Zusammenfassung Die komplexe Koazervation im SystemG-A-H2O kann als zweistufiger Prozeß aufgefaßt werden. Das erste Stadium ist die Bildung des elektrisch neutralen Komplexes zwischen G und A unter Einfluß der elektrostatischen Anziehungskräfte. Die Stöchiometrie der gewonnenen Verbindung wird durch die Äquivalenz der Makroionen bestimmt.Nur elektrisch neutrale Komplexe können die neue Phase, d. h. das komplexe Koazervat bilden. Deshalb muß die Zusammensetzung der koazervaten Phase von pH abhängen und bei Veränderung des Verhältnisses der Polymere im Gemisch unveränderlich bleiben.Bei einem Verhältnis der Polymere, kleiner als das stöchiometrische, ist die Bildung geladener Komplexe möglich.Den Prozeß der komplexen Koazervation kann man mittels der Methode der Trübungsmessung bei Cs<6·10–3 g/100 g untersuchen. Hierbei ist die optische Dichte proportional der Menge des komplexen Koazervats oder des elektrisch neutralen Komplexes im System. 相似文献