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101.
Prof. Fangfang Pan Yingchun Chen Siyu Li Minzhi Jiang Prof. Kari Rissanen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(31):7485-7488
Co-crystallizing iodine with a simple dicationic salt (1,8-diammoniumoctane chloride) results in the clathration of the iodine (I2) molecules inside trigonal and hexagonal helical channels of the crystal lattice with 72 wt % overall I2 loading. The I2 inside the bigger trigonal channel forms a I−I⋅⋅⋅I−I⋅⋅⋅I−I halogen-bonded infinite helical chain, while the I2 in the smaller hexagonal channel is disordered. In both channels the I2 interaction with the channel wall happens through I−I⋅⋅⋅Cl− halogen bonds. The helical channels in the crystal lattice are constructed via the strong charge-assisted H2N+H⋅⋅⋅Cl− hydrogen bonds between the dications and the chloride anions. The structure shows a marked similarity with the well-known starch–I2 system, and thus may provide insight for the yet unresolved structure of the I2 in the helical starch channel. 相似文献
102.
A new, short and highly diastereoselective synthetic route aiming at the C(33)-C(37) fragment of Amphotericin B has been developed. Studies with a model aldehyde (benzaldehyde) have given very promising results: the desired stereochemistry of all four stereocenters of the target molecule has been achieved with high diastereoselection. The stereochemistry of three key intermediates and the target segment has been confirmed by X-ray crystallography. 相似文献
103.
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105.
The magnitude of the -effects on13C chemical shifts was studied as function of theN-substitution [Me, Et, Bu, CH2C6H5, CH2CH2C6H5, Pri, But, Bus, c-C6H11, CH(CH3)C6H5, But, or Ph] for several benzylamines,o-aminomethylphenols and 3,4-dihydro-2H-1,3-benzoxazines. A correlation between the c-values and the steric substituent constants (E
s
) of theN-substituents proved useful in characterizing the variation of the -effects along with the conformational factors. The diastereospecificity of the -effects is discussed for purposes of configurational assignments.For part 2, see Ref. 1. This paper is also Part 5 in the series Studies on the Benzoxazine Series. 相似文献
106.
Asymmetric Synthesis of Spirocyclic β‐Lactams through Copper‐Catalyzed Kinugasa/Michael Domino Reactions
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Tao Shu Long Zhao Sun Li Dr. Xiang‐Yu Chen Dr. Carolina von Essen Prof. Dr. Kari Rissanen Prof. Dr. Dieter Enders 《Angewandte Chemie (International ed. in English)》2018,57(34):10985-10988
The first copper‐catalyzed highly chemo‐, regio‐, diastereo‐, and enantioselective Kinugasa/Michael domino reaction for the desymmetrization of prochiral cyclohexadienones is described. In the presence of a chiral copper catalyst, alkyne‐tethered cyclohexadienones couple with nitrones to generate the chiral spirocyclic lactams with excellent stereoselectivity (up to 97 % ee, >20:1 dr). The new method provides direct access to versatile highly functionalized spirocyclic β‐lactams possessing four contiguous stereocenters, including one quaternary and one tetra‐substituted stereocenter. 相似文献
107.
Eskola AJ Geppert WD Rissanen MP Timonen RS Halonen L 《The journal of physical chemistry. A》2005,109(24):5376-5381
The kinetics of the reactions of chlorinated methyl radicals (CH2Cl, CHCl2, and CCl3) with NO2 have been studied in direct measurements at temperatures between 220 and 360 K using a tubular flow reactor coupled to a photoionization mass spectrometer. The radicals have been homogeneously generated at 193 or 248 nm by pulsed laser photolysis of appropriate precursors. Decays of radical concentrations have been monitored in time-resolved measurements to obtain the reaction rate coefficients under pseudo-first-order conditions with the amount of NO2 being in large excess over radical concentrations. The bimolecular rate coefficients of all three reactions are independent of the bath gas (He or N2) and pressure within the experimental range (1-6 Torr) and are found to depend on temperature as follows: k(CH2Cl + NO2) = (2.16 +/- 0.08) x 10(-11) (T/300 K)(-1.12+/-0.24) cm3 molecule(-1) s(-1) (220-363 K), k(CHCl2 + NO2) = (8.90 +/- 0.16) x 10(-12) (T/300 K)(-1.48+/-0.13) cm3 molecule(-1) s(-1) (220-363 K), and k(CCl3 + NO2) = (3.35 +/- 0.10) x 10(-12) (T/300 K)(-2.2+/-0.4) cm3 molecule(-1) s(-1) (298-363 K), with the uncertainties given as one-standard deviations. Estimated overall uncertainties in the measured bimolecular reaction rate coefficients are about +/-25%. In the reactions CH2Cl + NO2, CHCl2 + NO2, and CCl3 + NO2, the products observed are formaldehyde, CHClO, and phosgene (CCl2O), respectively. In addition, a weak signal for the HCl formation has been detected for the CHCl2 + NO2 reaction. 相似文献
108.
Sara Busi Manu Lahtinen Reijo Sillanp Kari Rissanen 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(10):m458-m460
The title compound, (C16H20N)2[Fe2Br6O], crystallizes with one dibenzyldimethylammonium cation and one half of a μ‐oxo‐bis[tribromoferrate(III)] anion in the asymmetric unit. The bridging oxo group is situated on an inversion centre, resulting in a linear conformation for the Fe—O—Fe unit. The iron(III) cations have tetrahedral geometry, with bond angles in the range 106.8 (1)–112.2 (1)°. The ion pairs are held together by Coulombic forces and C—H⋯Br hydrogen bonds. Each Br− anion forms one hydrogen bond. No C—H⋯O hydrogen bonds are found between the O atom in the Fe—O—Fe unit and surrounding counter‐cations, consistent with the linear configuration of the Fe—O—Fe unit. 相似文献
109.
Kari Dahl Astrid Hald Poul J?rgensen Ivar Martinsen Yngvar Thomassen 《Fresenius' Journal of Analytical Chemistry》1990,338(4):526-529
Summary Studies have been made of both short and long term stability of trace elements in lyophilized human body fluid reference materials, as well as the stability of mercury in reconstituted urine solutions. No detectable concentration changes for mercury, lead and aluminium occurred during the 5-year period. There are large differences in the amounts of mercury loss among different reconstituted materials. Addition of traces of gold to the solutions minimized the mercury loss and increased the useable time of the reconstituted material from hours to 8 days. A certification process based on direct determinations by reference laboratories and by comparison against master lots of the same material and against similar certified reference materials is presented. Values for calcium, copper and mercury obtained from reference laboratories and using the data transfer principle have been assigned in new batches of urine and serum. 相似文献
110.
Using an STO -3G basis set, energy localized molecular orbitals (LMO ) were determined for the ten electron series HF, H2O, NH3, and CH4 as well as for CH3OH and C2H2F2. The method of conjugate gradients is shown to be a viable alternative to other non-eigenvalue methods. The characterization of the LMO in terms of first and second moment measures indicates that the STO -3G basis set LMO may be accurately correlated to larger sp basis set LMO . Also, it is shown that the first and second moment measures display a good linear correlation with the classical concept of electronegativity. 相似文献