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181.
S. Bamidele Sanni Helmut Behm Paul T. Beurskens Joost P. Cornelissen Jaap G. Haasnoot Abe T. H. Lenstra 《Journal of chemical crystallography》1987,17(1):81-89
The X-ray crystal structure of the title compound, [Co(NCS)2(C6H6N4)2(H2O)2], has been determined. The crystals are monoclinic, space groupC2/c, with cell dimensionsa=15.6901(5),b=7.9248(10),c=16.1278(12) Å,=94.4(8)°V
c=1999.44 Å3,M
r=479.18,Z=4,D
x=1.5918 Mg m3,Cu K radiation (graphite crystal monochromator, =1.54051 Å), (CuK)=39.08 cm–1,F(000)=980.00 andT=290 K. Final conventionalR-factor=0.051, andR
w=0.053 for 1430 observed reflections and 141 variables. The structure was solved using the programsPatsys andDirdif. The Co atom is octahedrally coordinated (CoN2O2N2 chromophore), with only the 5-methyl-[1,2,4]-triazolo[1,5-a]pyrimidine (5mtp) ligands in thetrans positions. The triazolo pyrimidine rings are planar and coordinated through their N(3) atoms. The H2O ligands are also H-bond donors to N(4) (intramolecularly) and to the S atoms of the NSC anions (intermolecularly). 相似文献
182.
Roger L. Dekock Evert Jan Baerends Paul M. Boerrigter Jaap G. Snijders 《Chemical physics letters》1984,105(3):308-316
Results of calculations on the uranylion using the LCAO MO Hartree—Fock—Slater method including relativistic effects are reported. The highest occupied molecular orbital is calculated to be σu, consisting predominantly of U 5f character. The σu orbital is the HOMO partly because of “pushing-from-below” by the U 6p orbital, but also as a result of the change in potential of the U 5f electrons with the uranium core elections brought about by relativistic contraction of the core electrons. This effect also determines the character of the first virtual levels (δu and Φu, respectively) in equatorial ligand fields. 相似文献
183.
Browne WR de Jong JJ Kudernac T Walko M Lucas LN Uchida K van Esch JH Feringa BL 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(21):6414-6429
The electro- and spectroelectrochemical properties of dithienylhexahydro- and dithienyhexafluorocyclopentenes are reported. The large effect of variation in the central cyclopentene moieties on the redox properties of the dithienylcyclopentenes is in striking contrast to the minor effect on their photochemical properties. The electronic properties of the oxidised compounds in the +1 and +2 oxidation state are reported, and the possibility of electrochemical cyclisation and cycloreversion were explored by UV/Vis spectroelectrochemistry. The efficiency of electrochemical switching is found to be dependent both on the central cyclopentene unit and on the nature of the substituents at C5 of the thienyl rings. For the hexahydrocyclopentene-based compounds oxidative ring closure of the ring-open form is observed, while for the hexafluorocyclopentene-based compounds oxidative ring opening of the ring-closed form is observed. However, the introduction of electroactive groups such as methoxyphenyl allows oxidative ring closure to occur in the hexafluoro compounds. The effect of electrolyte, solvent and temperature on the spectroelectrochemical properties were examined, and the switching process was found to be sensitive to the donor properties of the solvent/electrolyte system employed. In addition, thermally activated reversible isomerisation of the dicationic closed form was observed. The driving force for electrochemical ring opening and closure appears to be dependent on the relative stabilisation of the dicationic ring-open and ring-closed states. This study provides insight into the factors which determine the direction of cyclisation. 相似文献
184.
Liu T Callis PR Hesp BH de Groot M Buma WJ Broos J 《Journal of the American Chemical Society》2005,127(11):4104-4113
This work reports an explanation for the unusual monoexponential fluorescence decay of 5-fluorotryptophan (5FTrp) in single-Trp mutant proteins [Broos, J.; Maddalena, F.; Hesp, B. H. J. Am. Chem. Soc. 2004, 126, 22-23] and substantially clarifies the origin of the ubiquitous nonexponential fluorescence decay of tryptophan in proteins. Our results strongly suggest that the extent of nonexponential fluorescence decay is governed primarily by the efficiency of electron transfer (ET) quenching by a nearby amide group in the peptide bond. Fluoro substitution increases the ionization potential (IP) of indole, thereby suppressing the ET rate, leading to a longer average lifetime and therefore a more homogeneous decay. We report experimental IPs for a number of substituted indoles including 5-fluoroindole, 5-fluoro-3-methylindole, and 6-fluoroindole, along with accurate ab initio calculations of the IPs for these and 20 related molecules. The results predict the IP of 5-fluorotryptophan to be 0.19 eV higher than that of tryptophan. 5-Fluoro substitution does not measurably alter the excitation-induced change in permanent dipole moment nor does it change the fluorescent state from 1La to 1Lb. In combination with electronic structure information this argues that the increased IP and the decreased excitation energy of the 1La state, together 0.3 eV, are solely responsible for the strong reduction of electron transfer quenching. 6-Fluoro substitution is predicted to increase the IP by a mere 0.09 eV. In agreement with our conclusions, the fluorescence decay curves of 6-fluorotryptophan-containing proteins are well fit using only two decay times compared to three required for Trp. 相似文献
185.
186.
Shenton MJ Bradley JW van den Berg JA Armour DG Stevens GC 《The journal of physical chemistry. B》2005,109(47):22085-22088
Ultralow energy Ar+ and O+ ion beam irradiation of low density polyethylene has been carried out under controlled dose and monoenergetic conditions. XPS of Ar+-treated surfaces exposed to ambient atmosphere show that the bombardment of 50 eV Ar+ ions at a total dose of 10(16) cm(-2) gives rise to very reactive surfaces with oxygen incorporation at about 50% of the species present in the upper surface layer. Using pure O+ beam irradiation, comparatively low O incorporation is achieved without exposure to atmosphere (approximately 13% O in the upper surface). However, if the surface is activated by Ar+ pretreatment, then large oxygen contents can be achieved under subsequent O+ irradiation (up to 48% O). The results show that for very low energy (20 eV) oxygen ions there is a dose threshold of about 5 x 10(15) cm(-2) before surface oxygen incorporation is observed. It appears that, for both Ar+ and O+ ions in this regime, the degree of surface modification is only very weakly dependent on the ion energy. The results suggest that in the nonequilibrium plasma treatment of polymers, where the ion flux is typically 10(18) m(-2) s(-1), low energy ions (<50 eV) may be responsible for surface chemical modification. 相似文献
187.
van Zutphen S Robillard MS van der Marel GA Overkleeft HS den Dulk H Brouwer J Reedijk J 《Chemical communications (Cambridge, England)》2003,(5):634-635
A method for obtaining potentially anti-tumour active dinuclear platinum coordination compounds via solid-phase inorganic synthesis is described for the first time. 相似文献
188.
Uchida K Sukata S Matsuzawa Y Akazawa M de Jong JJ Katsonis N Kojima Y Nakamura S Areephong J Meetsma A Feringa BL 《Chemical communications (Cambridge, England)》2008,(3):326-328
Dithienylhexafluorocyclopentene with (R)- or (S)-N-phenylethylamide substituents formed rod-like and 0.2-1.0 microm-thick platelike crystals by sublimation; upon UV irradiation, the crystals bent concavely to the incident light and finally rolled crystals were obtained; the bent crystals were reconverted to flat crystals by visible light irradiation. 相似文献
189.
Thomas La Cour Jansen Sten Rettrup C. R. Sarma Jaap G. Snijders Paolo Palmieri 《International journal of quantum chemistry》1999,73(1):23-27
In the present article, we outline a simple scheme for generating configuration interaction matrix elements for spin–orbit interactions in molecules. The procedure leads to a close parallelism with spin‐free permutation‐group approaches. Unitary shift operators were successfully used on the orbital space to generate the matching permutations necessary to evaluate the required matrix elements. The procedure is adequately illustrated using examples. ©1999 John Wiley & Sons, Inc. Int J Quant Chem 73: 23–27, 1999 相似文献
190.
Ton Vries Hans Wynberg Erik van Echten Jan Koek Wolter ten Hoeve Richard M. Kellogg Quirinus B. Broxterman Adri Minnaard Bernard Kaptein Sietse van der Sluis Lumbertus Hulshof Jaap Kooistra 《Angewandte Chemie (International ed. in English)》1998,37(17):2349-2354
The resolution of racemates is revolutionized with the method presented here, in which mixtures (“families”) of structurally and stereochemically related resolving agents are used to precipitate salts of acidic or basic racemates rapidly and dependably. The racemate is usually separated in a single operation into enantiomers—the enantiomeric excesses and yields are good to excellent. Reagent mixtures with racemic or achiral components have also been developed. 相似文献