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101.
Angela Šurca Vuk Boris Orel Goran Dražič 《Journal of Solid State Electrochemistry》2001,5(7-8):437-449
In this paper we generalize the IR spectroscopic properties of M3+VO4 (M=Fe, In) orthovanadate and Fe2V4O13 films. The films were prepared using the sol-gel synthesis route from M3+ nitrates and vanadium oxoisopropoxide. The vibrational bands in the IR absorbance spectra of the films are classified in
terms of terminal V-O stretching (1050–880 cm–1), bridging V-O...Fe and V...O...Fe stretching (880–550 cm–1), mixed V-O-V deformations and Fe-O stretching (<550 cm–1) modes. Ex situ IR spectra of films were measured after consecutive charging/discharging to various intercalation coefficients x and correlated to the current peaks in the cyclic voltammetry curves measured in 1 M LiClO4/propylene carbonate electrolyte. We classified the ex situ IR spectra of charged/discharged films according to their vibrational
band changes. The results reveal that, for small values of the intercalation coefficient, crystalline FeVO4, InVO4 and Fe2V4O13 films exhibit a simultaneous decrease in the intensity of all IR bands while the band frequencies remain unaffected. For
the higher intercalation levels, IR mode frequencies are shifted, signaling the presence of reduced vanadium. Further charging
leads to an amorphization of the film structure, which was established from the similarity of the IR spectra of charged films
with those of amorphous films prepared at lower annealing temperatures. The results confirm that ex situ IR spectroelectrochemical
measurement is an effective way to assess the structural changes in films with different levels of intercalation.
Electronic Publication 相似文献
102.
Alfred Schmidpeter Angela Willhalm Jürgen Kroner Roberta O. Day Joan M. Holmes Robert R. Holmes 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-2):495-498
Abstract Phosphamethincyanines prepared in 1964 by Dimroth and Hoffmann were among the first compounds with two-coordinate phosphorus. They are special cases of 2-phospha-allylic cations. Simple representatives of this type become available from the reaction of imidoyl chlorides with tris(trimethylsily1)phosphane. 相似文献
103.
Na9[FeO3][FeO4]a Mixed Valent Oxoferrat(II, III) with Isolated [FeO3]4— — and [FeO4]5— Anions Na9[FeO3][FeO4] has been formed and obtained from a redox reaction between CdO and iron metal (reaction container) and Na2O in the presence of NaOH at 450 °C as orange‐red transparent single crystals. The crystal structure determination (IPDS data: Pca21, a = 956.2(2) pm, b = 999.1(2) pm, c = 1032.3(2) pm, Z = 4, Rall = 0.0455) reveals the presence of isolated complex anions, [FeO3]4— and [FeO4]5—. 相似文献
104.
Bigoli F Deplano P Mercuri ML Pellinghelli MA Pilia L Pintus G Serpe A Trogu EF 《Inorganic chemistry》2002,41(20):5241-5248
New [M(R(2)pipdt)(2)](BF(4))(2) salts [R(2)pipdt = N,N'-dialkyl-piperazine-2,3-dithione; M = Pd(II), R = Me and M = Pt(II), R = Me, Et, Pr(i)] bearing redox-active cationic dithiolene complexes have been prepared and characterized. These cations react with the redox-active [M(mnt)(2)](2-) [M = Pd(II), Pt(II); mnt = maleonitrile-2,3-dithiolate] anionic dithiolenes to form salts describable as ion pair charge-transfer complexes. X-ray crystallographic studies have shown that [M(Me(2)pipdt)(2)][M(mnt)(2)] complexes, with M = Pd(II) and Pt(II), are isomorphous. Crystal data of the Pt salt (3a): triclinic, Ponemacr; (No. 2); Z = 1; T = 293(2) K; a = 6.784(7) A, b = 8.460(6) A, c = 13.510(5) A, alpha = 100.63(2) degrees, beta = 104.04(2) degrees, gamma = 96.90(2) degrees; R1 = 0.0691 [wR2 = 0.2187 (all data)]. Structural data show that approximately square-planar [Pt(Me(2)pipdt)(2)] dications and regular square-planar [Pt(mnt)(2)] dianions form an infinite anion-cation one-dimensional stack along axis a with a Pt...Pt a/2 distance of 3.392 A and a Pt...Pt...Pt angle of 180 degrees. Anions and cations arrange themselves face-to-face so as to take on a staggered arrangement. These salts exhibit strong absorptions in the visible-near-infrared region assigned to ion pair charge-transfer transitions. A relation between the optical and thermal electron transfer in the solid state is obtained using a "Marcus-Hush model", and a solid-state electrical conductivity in agreement with expectations is observed. Vibrational spectroscopy is in agreement with the existence of charge-transfer interactions between the cationic and anionic components of the salts. 相似文献
105.
A simple and rapid method for the preparation of a series of novel quinoxaline derivatives in the presence of Ag+ is reported. 相似文献
106.
Racemic 1-acetyl-2-methoxymethylferrocene, (±)-1 was subjected to asymmetric reduction with two different methodologies and complementary results were obtained. When the reduction of (±)-1 was carried out in the presence of CBS-oxazaborolidine catalyst and BH3·Me2S as the hydrogen source, both enantiomers of the substrate were converted with comparable reaction rates and selectivities. The corresponding diastereoisomeric ferrocenylalcohols 3a and 3b were obtained in a 1:1 ratio and >90% enantiomeric excess; this reaction profile being related with a parallel kinetic resolution with high ds1 and ds2 diastereofacial selectivities. On the contrary, the transfer hydrogenation of (±)-1 with HCOOH/triethylamine in the presence of (R,R)-Noyori’s catalyst proceeded via classical kinetic resolution, so that the formed (?)-3b or unreacted (+)-1 could be obtained in highly enantiopure form before or beyond 50% of the substrate conversion, respectively. Alcohol 3b with an (1Rp,S)- or (1Sp,R)-configuration is not easily accessible by the diastereoselective metallation/electrophilic quenching sequence routinely applied in the synthesis of planar chiral ferrocenes. As a result, the described procedures provide a valuable access to this useful starting material for the synthesis of homochiral related derivatives. 相似文献
107.
Andrea Petrella Pinalysa Cosma M. Lucia Curri Sergio Rochira Angela Agostiano 《Journal of nanoparticle research》2011,13(12):6467-6481
Heterostructures formed of films of organic-capped ZnO and TiO2 nanocrystals (both with the size of ca. 6 nm) and photosynthetic pigments were prepared and characterized. The surface of
optically transparent electrodes (Indium Tin Oxide) was modified with nanocrystals and prepared by colloidal synthetic routes.
The nanostructured electrodes were sensitized by a mixture of chlorophyll a and carotenoids. The characterization of the hybrid
structures, carried out by means of steady-state optical measurements, demonstrated such class of dyes able to extend the
photoresponse of the large band-gap semiconductors. The charge-transfer processes between the components of the heterojunction
were investigated, and photoelectrochemical measurements taken on the sensitized ZnO and TiO2 nanocrystals electrodes elucidated the photoactivity of the heterojunctions as a function of the dyes and of the red–ox mediator
used in solution. The effect of methyl viologen as different red–ox mediator was also evaluated in order to show its effect
on the heterojunction photoactivity. The overall results contributed to describe the photoelectrochemical potential of the
investigated heterojunctions, highlighting a higher response of the dye-sensitized ZnO nanocrystals, and then provided the
TiO2-modified counterparts. 相似文献
108.
The pKa of 3',3",5',5"tetrabromo-m-cresolsulfonephtalein (Bromocresol Green) and o-cresolsulphonephtalein (Cresol Red) was spectrophotometrically measured in a water/AOT/isooctane microemulsion in the presence of a series of buffers carrying different charges at different water/surfactant ratios. Extended Principal Component Analysis was used for a precise determination of the apparent pKa and of the spectra of the acid and base forms of the dye. The apparent pKa of dyes in water-in-oil microemulsions depends on the charge of the acid and base forms of the buffers present in the water pool. Combination with multiple linear regression increases the precision. Results are discussed taking into account the profile of the electrostatic potential in the water pool and the possible partition of the indicator between the aqueous core and the surfactant. The pKa corrected for these effects are independent of w0 and are close to the value of the pKa in bulk water. On the basis of a tentative hypothesis it is possible to calculate the true pKa of the buffer in the pool. 相似文献
109.
Andrew V. Chapman Michael J. Cook Alan R. Katritzky Michael H. Aabraham Angela F. Danil De Namor Lilane Dumont Jacques Reisse 《Tetrahedron》1978,34(10):1571-1575
The dehydration of various 4,5-dihydro-4- and -5-hydroxy derivatives of pyrazole and isoxazole has been investigated. Heats of dehydration of 4,5-duiydro-4-hydroxy-1,3,5-tripbenylpyrazole and 4,5-dihydro-5-hydroxy-isoxazole are evaluated and used to assess the empirical resonance energy and conjugation energy of pyrazole and isoxazole. The former possesses resonance stabilisation comparable to pyrrole but that of the latter is low. 相似文献
110.
[reactions: see text] Regioselective synthesis of 2,4,5- or 3,4,5-trisubstituted 2,3-dihydrofurans has been realized by using donor-acceptor cyclopropanes or by a Corey ylide reaction with alpha-sulfenyl-, alpha-sulfinyl-, or alpha-sulfonylenones. The method allowed a straightforward synthesis of the natural product calyxolane B. 相似文献