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91.
The reaction of C6Cl5Ni(PPhMe2)2Cl with CHRCR′CH2MgX (X = Br or Cl) yields π-allylnickel compounds, (π-CHRCR′CH2)Ni(PPhMe2)C6Cl5 (Ia, R = R′ = H; Ib, R = H, R′ = CH3; Ic, R = CH3, R′ = H), which are stable in the solid state below ca. 150°C and are fairly stable in solution in the absence of oxygen. The π-allyl group was found by PMR spectroscopy to be rigid even in the presence of an excess of PPhMe2, P(OEt)3 or P(OMe)3. 相似文献
92.
Abe M Adam W Hara M Hattori M Majima T Nojima M Tachibana K Tojo S 《Journal of the American Chemical Society》2002,124(23):6540-6541
Photodenitrogenation of the diazenes 4 affords exclusively the housanes 5 through intramolecular cyclization of the spectrally detected and characterized singlet diradicals 3. The lifetime of singlet diradical 3, determined by transient absorption measurements, depends on the Y and Z substituents at the para position of the phenyl ring and has the following order: Y, Z = OMe, OMe > OMe, CN > CN, CN > OMe, H > Cl, Cl approximately CN, H approximately Me, Me > H, H. This unprecedented substituent effect reveals stabilization of the singlet 2,2-dimethoxycyclopentane-1,3-diyl diradicals 3 through radical, zwitterionic, pi-bonding, and hyperconjugative structures. 相似文献
93.
The ion-pair extraction equilibria of dibenzo-18-crown-6 (DB18C6) complexes of Na+, K+, Rb+ and Cs+ (M+) with picrate ion (Pic−) into 1,2-dichloroethane (1,2-DCE) have been studied at 25.0°C. In the case of the Rb+ and Cs+ systems, the extraction results were interpreted by taking into consideration the formation of a (DB18C6)2 -M+ complex in 1,2-DCE. The thermodynamic constants of extraction,
, and ion-pair formation in 1,2-DCE,
, of ion pairs of the DB18C6-M+ complexes with Pic− were determined. By using the distribution coefficient of M+·Pic− the thermodynamic formation constants of the DB18C6-M+ complexes in 1,2-DCE,
, were evaluated. Consequently the component equilibrium constants of the ion-pair extraction were completely determined and a contribution of these constants to the difference of
value was discussed. The
value in 1,2-DCE is quite high compared with that in solvating solvents and log
decreases linearly with increasing Gutmann donor number of solvents. 相似文献
94.
Sakamoto S Ito A Kudo K Yoshikawa S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(15):3717-3726
The introduction of a flavin chromophore on the myoglobin (Mb) surface and an effective electron-transfer (ET) reaction through the flavin were successfully achieved by utilizing the self-assembly of heterostranded coiled-coil peptides. We have prepared a semiartificial Mb, named Mb-1alphaK, in which an amphiphilic and cationic alpha-helix peptide is conjugated at the heme propionate (Heme-1alphaK). Heme-1alphaK has a covalently bound iron-protoporphyrin IX (heme) at the N terminus of a 1alphaK peptide sequence. This sequence was designed to form a heterostranded coiled-coil in the presence of a counterpart amphiphilic and anionic 1alphaE peptide sequence in a parallel orientation. Two peptides, Fla(1)-1alphaE and Fla(31)-1alphaE, both incorporating a 10-methylisoalloxazine moiety as an artificial flavin molecule, were also prepared (Fla=2-[7-(10-methyl)isoalloxazinyl]-2-oxoethyl). Heme-1alphaK was successfully inserted into apomyoglobin to give Mb-1alphaK. Mb-1alphaK recognized the flavin-modified peptides and a two-alpha-helix structure was formed. In addition, an efficient ET from reduced nicotinamide adenine dinucleotide to the heme center through the flavin unit was observed. The ET rate was faster in the presence of Fla(1)-1alphaE than in the presence of Fla(31)-1alphaE or the equivalent molecule that has no peptide chain. These results demonstrate that the introduction of a functional chromophore on the Mb surface can be achieved by using specific peptide-peptide interactions. Moreover, the dependence of the ET rate on the position of the flavin indicated that the distance between the heme active site and the flavin chromophore was regulated by the three-dimensional structure of the designed polypeptide. 相似文献
95.
Heng-dao Quan Hui-e Yang Masanori Tamura Akira Sekiya 《Journal of fluorine chemistry》2004,125(7):1169-1172
A novel fluorination reagent and catalyst, SbF5/PAF (porous aluminum fluoride), was prepared by impregnating SbCl5 into PAF and then treating with anhydrous hydrogen fluoride. The prepared reagent had an excellent catalytic activity in halogen-exchange, and also improved the properties of SbF5, such as hydroscopicity, corrosion, and toxicity. SbF5/PAF was successfully used in organic synthesis as a fluorinating reagent, and a fixed bed catalyst for F/Cl exchange. 相似文献
96.
Simons electrochemical fluorination (ECF) of 1,4-dimethyl-1,4-homopiperazine, methyl 4-ethylhomopiperazin-1-ylacetate and 1,4-bis(methoxycarbonylmethyl)-1,4-homopiperazine was studied. For comparison, ECF of three piperazines with a N-(methoxycarbonylmethyl) group(s) was also studied. ECF of 1,4-dimethyl-1,4-homopiperazine gave a low yield of corresponding perfluoro(1,4-dimethyl-1,4-homopiperazine) together with perfluoro(2,6-diaza-2,6-dimethylheptane) as the major product. Corresponding perfluoro(homopiperazines) with mono- and/or di-(fluorocarbonyldifluoromethyl) groups [CF2C(O)F] at the 1- and/or 4-position were formed in low yields from methyl 4-ethylhomopiperazin-1-ylacetate and 1,4-bis(methoxycarbonylmethyl)-1,4-homopiperazine, respectively. These new seven-membered perfluoro(1,4-dialkyl-1,4-homopiperazines) were accompanied by the formation of mono- and/or di-basic linear perfluoroacid fluorides resulting from the CC bond scission at the 2- and 3-positions of the ring. From mono- and/or di-N-(methoxycarbonylmethyl)-substituted piperazines, corresponding perfluoropeperazines having the acid fluoride group(s) were formed in low yields. 相似文献
97.
Takiue T Hirose D Murakami D Sakamoto H Matsubara H Aratono M 《The journal of physical chemistry. B》2005,109(34):16429-16434
The interfacial tension gamma of the hexane solution of 1H,1H-perfluorononanol (FDFC(9)OH) and its omega-hydrogenated analogue, 1H,1H,9H-perfluorononanol (HDFC(9)OH), against water was measured as a function of pressure and concentration at 298.15 K in order to clarify the effect of omega-dipole on the orientation of fluorononanol molecules from the viewpoint of volume. The adsorbed films of both alcohols exhibit two kinds of phase transitions among three different states: the gaseous, expanded, and condensed states. The partial molar volume changes of adsorption - in the expanded and condensed states were evaluated and compared between the two systems. The - values of both alcohols are negative, and thus the alcohol molecules have smaller volume in the adsorbed film than in the bulk solution. Furthermore, the value was obtained through the evaluation of by the density measurement of the bulk hexane solution. It was found that the value of HDFC(9)OH is smaller than that of FDFC(9)OH in the condensed state. On the basis of three matters concerning the molecular structure of alcohols, the occupied area at the interface, and the orientation of FDFC(9)OH in the adsorbed film deduced from the earlier results of X-ray reflectivity measurement, the mean tilt angle of HDFC(9)OH from the interface normal in the condensed film was estimated to be 15 degrees . The thermodynamic estimation demonstrated here is highly valuable one to provide structure information on an adsorbed film. 相似文献
98.
Shingo KomatsuYouichi Sakamoto Toshiyasu Suzuki Shizuo Tokito 《Journal of solid state chemistry》2002,168(2):470-473
Perfluoro-1,3,5-tris(p-quaterphenyl)benzene (PF-13Y) and perfluoro-1,3,5-tris(p-quinquephenyl)benzene (PF-16Y) have been synthesized and characterized. They showed higher glass transition temperatures compared with perfluoro-1,3,5-tris(p-terphenyl)benzene (PF-10Y). Organic light-emitting diodes were fabricated using these materials as the electron-transport layers. PF-13Y and -16Y are better electron transporters than PF-10Y. The electron mobilities of PF-10Y and Alq3 were measured by the time-of-flight technique. PF-10Y showed higher electron mobilities (10−4 cm2/V s) and weaker electric field dependence compared with Alq3. 相似文献
99.
Miki Murata Hiyoruki Yamasaki Tsukasa Ueta Masayuki Nagata Masanori Ishikura Shinji Watanabe Yuzuru Masuda 《Tetrahedron》2007,63(19):4087-4094
The general and efficient silylation of aryl halides has been developed utilizing triethoxysilane and a rhodium catalyst. The substrate scope is broad and includes ortho-, meta-, and para-substituted electron-rich and -deficient aryl iodides. In addition, the silylation of aryl bromides and fluoroalkanesulfonates proceeded in the presence of tetra-n-butylammonium iodide. 相似文献
100.