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51.
Michał Dąbrowski Dr. Przemysław Wyrębek Dr. Damian Trzybiński Prof. Krzysztof Woźniak Prof. Karol Grela 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(17):3782-3794
Robust, selective, and stable in the presence of ethylene, ruthenium olefin metathesis pre-catalyst, {[3-benzyl-1-(10-phenyl-9-phenanthryl)]-2-imidazolidinylidene}dichloro(o-isopropoxyphenylmethylene)ruthenium(II), Ru-3 , bearing an unsymetrical N-heterocyclic carbene (uNHC) ligand, has been synthesized. The initiation rate of Ru-3 was examined by ring-closing metathesis and cross-metathesis reactions with a broad spectrum of olefins, showing an unprecendented selectivity. It was also tested in industrially relevant ethenolysis reactions of olefinic substrates from renewable feedstock with very good yields and selectivities. 相似文献
52.
Ewelina Nawrot 《Journal of fluorine chemistry》2006,127(7):943-947
N-Aryl substituted amides react with chlorodifluoromethane in the presence of concentrated aqueous sodium hydroxide and benzyltriethylammonium chloride (TEBAC) as a catalyst in benzene (phase-transfer catalysis, PTC), affording mixtures of N- and O-difluoromethyl substituted derivatives. Amide anions are involved in this process. The reaction carried out with oximes gives O-difluoromethyl oxime ethers. 相似文献
53.
Halina Polkowska-Motrenko Rajmund S. Dybczyński Ewelina Chajduk 《Accreditation and quality assurance》2010,15(4):245-250
This paper presents the work done by the Institute of Nuclear Chemistry and Technology (INCT), Warsaw on a procedure of the
certification of matrix reference materials (CRMs) for inorganic trace analysis. The INCT has been involved in preparation
and certification of that type of CRMs since 1986 till now. The certification of CRMs is performed on the basis of statistical
evaluation of the data obtained from the worldwide interlaboratory comparison. The initially adopted certification procedure
has been developed, and the final shape is presented and discussed. The modifications are connected with the new demands of
the international standards. The results of analysis of candidate CRMs obtained by the potentially primary procedures based
on radiochemical neutron activation analysis (RNAA) and results of analysis of CRM accompanying candidate RMs are applied
in the certification process for quality assurance purpose. 相似文献
54.
Terahertz spectroscopy provides a noninvasive and nondestructive method for detecting and identifying concealed explosives. In this work, the room-temperature and cryogenic terahertz spectra of two common improvised explosive oxidizers, namely, potassium nitrate (KN) and ammonium nitrate (AN), are presented, along with detailed solid-state density functional theory (DFT) analyses of the crystalline structures and spectral features. At both 294 and 78 K, KN exhibits two terahertz absorption features below 100 cm(-1) that have been assigned through DFT simulations to arise from hindered nitrate rotations in the KN-II crystalline polymorph. The terahertz spectrum of AN exhibits a pronounced temperature dependence. The 294 K spectrum is free of any absorptions, whereas the 78 K spectrum consists of several narrow and intense peaks. The origin of this large difference is the polymorphic transition that occurs during cooling of AN, where room-temperature AN-IV is converted to AN-V at 255 K. The 78 K terahertz spectrum of AN is assigned here to various ion rotations and translations in the AN-V polymorph lattice. The analysis of the room-temperature AN-IV terahertz spectrum proved to be more complicated. The solid-state DFT simulations predicted that the room-temperature crystal structure of AN is not very well described using the standard Pmmn space-group symmetry as previously believed. The AN-IV polymorph actually belongs to the Pmn2(1) space group, and the perceived Pmmn symmetry results from vibrational averaging through nitrate rotations. This newly observed Pmn2(1) crystal symmetry for room-temperature AN is the reason for the absence of absorption features in the 294 K terahertz spectrum of AN and provides new insight into the polymorphic transitions of this ionic solid. 相似文献
55.
56.
The reaction of benzylthioarylboronic acids protected as N‐butyldiethanolamine esters or as triisopropoxyborates with organolithium bases or lithium diisopropylamide (LDA) has been investigated. The benzylic lithiation occurs selectively using LDA at − 68 °C. The stability of the resultant borio‐lithio intermediates is strongly influenced by the position of the boron atom in the phenyl ring. The reaction with various electrophiles affords new arylboronic acids substituted in the benzylic position. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
57.
Nowicka AM Zabost E Donten M Mazerska Z Stojek Z 《Analytical and bioanalytical chemistry》2007,389(6):1931-1940
A method is presented for the electroanalytical characterization of interactions of dsDNA with a drug, under conditions that
both agents are dissolved in the phosphate buffer solution and both are electroactive. Normal pulse, square wave, differential
pulse, and cyclic voltammetries were employed in the measurements of the drug and dsDNA oxidation signals at carbon electrodes.
UV–Vis spectroscopy was used as a non-electrochemical method to support the electroanalytical data. An anticancer drug, C-1311
(5-diethylaminoethyl-amino-8-hydroxyimidazoacridinone), has been selected for the examination. Normal pulse voltammetry was
particularly useful in showing that under the conditions employed neither dsDNA nor the drug were adsorbed at the electrode
surface. Necessary conditions for the appearance of the well-defined dsDNA voltammetric signal (guanine peak) are: rigorous
chemical and biological purity in the cell and appropriate purity of DNA. An analysis of the obtained results confirmed that
there were two modes of interaction between C-1311 and dsDNA: by intercalation and electrostatically. In the presence of excess
NaCl the electrostatic interactions deteriorate. The binding constants (K
1 and K
2, respectively) and the number (n) of nucleic base pairs (bp) and the number (m) of phosphate groups (pg) interacting with one molecule of drug have been determined. For strong interactions (intercalation)
the values of the binding constant, K
1, and the binding-site size, n, equal 3.7 × 104 M−1 and 2.1, respectively. For the weak electrostatic interactions the K
2 and m parameters equal 0.28 × 104 M−1 and 4.7. The intercalation process is rather slow and its rate (the conditions of pseudo-first-order reaction) was estimated
to equal 7 × 10−4 s−1. The possibility of independent determination of both interacting agents was very useful in the study.
Figure Intercalation of C-1311 into a dsDNA fragment 相似文献
58.
Dr. Joice Thomas Dr. Liliana Dobrzańska Prof. Luc Van Meervelt Prof. Mario Alfredo Quevedo Prof. Krzysztof Woźniak Marcin Stachowicz Prof. Mario Smet Prof. Wouter Maes Prof. Wim Dehaen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(3):979-987
A synthetic route towards homodiselenacalix[4]arene macrocycles is presented, based on the dynamic covalent chemistry of diselenides. The calixarene inner rim is decorated with either alkoxy or tert‐butyl ester groups. Single‐crystal X‐ray analysis of two THF solvates with methoxy and ethoxy substituents reveals the high similarity of their molecular structures and alterations on the supramolecular level. In both crystal structures, solvent channels are present and differ in both shape and capacity. Furthermore, the methoxy‐substituted macrocycle undergoes a single‐crystal‐to‐single‐crystal transformation during which the molecular structure changes its conformation from 1,3‐alternate (loaded with THF/water) to 1,2‐alternate (apohost form). Molecular modelling techniques were applied to explore the conformational and energetic behaviour of the macrocycles. 相似文献
59.
60.
Ng KM Che CM Wo SK Tam PK Lau AS 《Rapid communications in mass spectrometry : RCM》2006,20(10):1545-1550
Ginsenosides containing different numbers of glycosyl groups can be easily differentiated based on the formation of characteristic ginsenoside-acetate adduct anions and deprotonated ginsenosides generated by electrospray ionization (ESI) of methanolic solutions of ginsenosides (M) and ammonium acetate (NH4OAc). Ginsenosides containing two glycosyl groups gave a characteristic mass spectral pattern consisting of [M+2OAc]2-, [M-H+OAc]2- and [M-2H]2- ions with m/z values differing by 30 Th, while this mass spectral pattern was not observed for ginsenosides containing one glycosyl group. Formation of [M+2OAc]2- was influenced by the chain length of glycosyl groups and was used to differentiate the ginsenosides containing different combinations of monosaccharide and disaccharide units in the glycosyl groups. Under identical collisional activation conditions, [M+OAc]-, [M-H+OAc]2- and [M+2OAc]2- underwent proton abstractions predominantly to generate [M-H]-, [M-2H]2- and [M-H+OAc]2- ions, respectively. The ion intensity ratios, I[M-H](-/I) [M+OAc]-, I[M-2H](2-/I) [M-H+2OAc]2- and I[M-H+OAc](2-/I) [M+OAc]2-, being sensitive to the structural differences of ginsenosides, could differentiate the isomeric ginsenosides, including (i) Rf, F11 and Rg1, (ii) Rd and Re, and (iii) Rb2 and Rc. Additionally, NH4OAc was found to enhance the sensitivity of detection of ginsenosides in the form of [M-H]- down to the femtomole level. 相似文献