全文获取类型
收费全文 | 3974篇 |
免费 | 98篇 |
国内免费 | 16篇 |
专业分类
化学 | 2463篇 |
晶体学 | 16篇 |
力学 | 288篇 |
数学 | 823篇 |
物理学 | 498篇 |
出版年
2023年 | 19篇 |
2022年 | 78篇 |
2021年 | 101篇 |
2020年 | 83篇 |
2019年 | 72篇 |
2018年 | 56篇 |
2017年 | 46篇 |
2016年 | 121篇 |
2015年 | 112篇 |
2014年 | 109篇 |
2013年 | 201篇 |
2012年 | 220篇 |
2011年 | 241篇 |
2010年 | 175篇 |
2009年 | 146篇 |
2008年 | 200篇 |
2007年 | 208篇 |
2006年 | 200篇 |
2005年 | 179篇 |
2004年 | 160篇 |
2003年 | 110篇 |
2002年 | 140篇 |
2001年 | 39篇 |
2000年 | 44篇 |
1999年 | 40篇 |
1998年 | 32篇 |
1997年 | 41篇 |
1996年 | 46篇 |
1995年 | 36篇 |
1994年 | 32篇 |
1993年 | 42篇 |
1992年 | 49篇 |
1991年 | 31篇 |
1990年 | 14篇 |
1989年 | 21篇 |
1988年 | 21篇 |
1987年 | 33篇 |
1986年 | 15篇 |
1985年 | 33篇 |
1984年 | 36篇 |
1983年 | 38篇 |
1982年 | 33篇 |
1981年 | 47篇 |
1980年 | 47篇 |
1979年 | 41篇 |
1978年 | 26篇 |
1977年 | 29篇 |
1976年 | 23篇 |
1975年 | 19篇 |
1967年 | 13篇 |
排序方式: 共有4088条查询结果,搜索用时 15 毫秒
31.
Graziano G 《The Journal of chemical physics》2004,121(4):1878-1882
It has been recently claimed that the large cohesive energy density of water is the ultimate cause of the poor solubility of nonpolar compounds in water. In order to test the validity of this idea, we analyze the difference in solubility between light water and heavy water of several nonpolar compounds. Even though the cohesive energy density of D(2)O is larger than that of H(2)O, nonpolar compounds are slightly more soluble in D(2)O than H(2)O. In such case experimental data do not support the correctness of the large cohesive energy density as the ultimate cause of hydrophobicity. We show that D(2)O is a slightly better solvent than H(2)O for nonpolar compounds because it is slightly less costly to create a cavity in the former liquid. This is because there is slightly more void volume in heavy water than in light water. 相似文献
32.
Cornelia Bohne Adelaide Faljoni-Alario Giuseppe Cilento 《Photochemistry and photobiology》1988,48(3):341-347
Abstract— The interaction of serum albumin-bound acceptors with enzyme-generated and protected triplet species was studied in two types of systems. Chlorophyll-a bound to bovine and human serum albumins is efficiently excited by enzymatically generated triplet acetone and acetaldehyde. When the Chl-a concentration is much lower than that of the albumin the interaction occurs with chlorophyll in an aggregate in which one Chl-a is surrounded by several protein molecules. When the Chl-a concentration is higher than that of the protein, the aggregate contains the proteins and fluorescent chlorophylls in a 1:1 ratio. The excess chlorophylls, although able to interact with the donors, are not fluorescent.
In another study, probes bound to various specific sites of serum albumins were used as quenchers of the enzymatically generated triplet acetone. The efficiency of quenching by all the bound probes is equal and in one case even stronger than for the free probes.
A model for the interaction of the excited species contained in the enzyme with the acceptor(s) located in the protein is proposed.
The present results provide further evidence that enzyme-generated and protected triplet carbonyl species can interact through a collisional process with acceptors bound to or constituents of macromolecules. 相似文献
In another study, probes bound to various specific sites of serum albumins were used as quenchers of the enzymatically generated triplet acetone. The efficiency of quenching by all the bound probes is equal and in one case even stronger than for the free probes.
A model for the interaction of the excited species contained in the enzyme with the acceptor(s) located in the protein is proposed.
The present results provide further evidence that enzyme-generated and protected triplet carbonyl species can interact through a collisional process with acceptors bound to or constituents of macromolecules. 相似文献
33.
Roberto Grisorio Giuseppe Romanazzi Piero Mastrorilli Domenico Acierno Giuseppe Ciccarella 《Tetrahedron》2006,62(4):627-634
A series of novel bifluorene based systems was synthesised by a convergent approach by means of a Suzuki cross-coupling between 7,7′-bis-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-9,9,9′,9′-tetraoctyl-2,2′-bifluorene and suitable aryl-bromides. All the oligomers have been characterized by 1H, 13C NMR, FT-IR, UV-vis, PL spectroscopy and mass analyses. In particular, it has been demonstrated that the presence of strong electron donor (amines) or withdrawing (carboxylic esters) groups causes a bathochromic shift of the optical properties with respect to those of unsubstituted molecules. The effects of these functional groups on the HOMO-LUMO energy levels were investigated by cyclic voltammetry. Remarkably, the LUMO energy level of 7,7′-bis-[5′-carbodecaoxy-2,2′-bithiophen-5-yl]-9,9,9′,9′-tetraoctyl-2,2′-bifluorene (−3.07 eV) is strongly influenced by the presence of the ester functional group. 相似文献
34.
Pablo Ríos Javier Borge Francisco Fernndez de Crdova Giuseppe Sciortino Agustí Lleds Amor Rodríguez 《Chemical science》2021,12(7):2540
The concept of metal–ligand cooperation opens new avenues for the design of catalytic systems that may offer alternative reactivity patterns to the existing ones. Investigations of this concept with ligands bearing a boron center in their skeleton established mechanistic pathways for the activation of small molecules in which the boron atom usually performs as an electrophile. Here, we show how this electrophilic behavior can be modified by the ligand trans to the boron center, evincing its ambiphilic nature. Treatment of diphosphinoboryl (PBP) nickel–methyl complex 1 with bis(catecholato)diboron (B2Cat2) allows for the synthesis of nickel(ii) bis-boryl complex 3 that promotes the clean and reversible heterolytic cleavage of dihydrogen leading to the formation of dihydroborate nickel complex 4. Density functional theory analysis of this reaction revealed that the heterolytic activation of H2 is facilitated by the cooperation of both boryl moieties and the metal atom in a concerted mechanism that involves a Ni(ii)/Ni(0)/Ni(ii) process. Contrary to 1, the boron atom from the PBP ligand in 3 behaves as a nucleophile, accepting a formally protic hydrogen, whereas the catecholboryl moiety acts as an electrophile, receiving the attack from the hydride-like fragment. This manifests the dramatic change in the electronic properties of a ligand by tuning the substituent trans to it and constitutes an unprecedented cooperative mechanism that involves two boryl ligands in the same molecule operating differently, one as a Lewis acid and the other one as a Lewis base, in cooperation with the metal. In addition, reactivity towards different nucleophiles such as amines or ammonia confirmed the electrophilic nature of the Bcat moiety, allowing the formation of aminoboranes.A bis(boryl)nickel complex promotes the facile and reversible activation of H2 through a cooperative mechanism that involves the metal and both boryl moieties in a concerted five-center process. 相似文献
35.
Manetta AC Di Giuseppe L Giammarco M Fusaro I Simonella A Gramenzi A Formigoni A 《Journal of chromatography. A》2005,1083(1-2):219-222
A new HPLC method with fluorescence detection using pyridinium hydrobromide perbromide as a post-column derivatising agent has been developed to determine aflatoxin M1 in milk and cheese. The detection limits were 1 ng/kg for milk and 5 ng/kg for cheese. The calibration curve was linear from 0.001 to 0.1 ng injected. The method includes a preliminary C18-SPE clean-up and the average recoveries of Aflatoxin M1 from milk and cheese, spiked at levels of 25-75 ng/kg and 100-300 ng/kg, respectively, were 90 and 76%; the precision (RSDr) ranged from 1.7 to 2.6% for milk and from 3.5 to 6.5% for cheese. The method is rapid, easily automatable and therefore useful for accurate and precise screening of aflatoxin M1 in milk and cheese. 相似文献
36.
Spoto G Gribov E Bordiga S Lamberti C Ricchiardi G Scarano D Zecchina A 《Chemical communications (Cambridge, England)》2004,(23):2768-2769
Cu(I) ions in Cu-ZSM-5 form Cu+(H2) complexes, stable at room temperature and sub-atmospheric H2 pressure, which do not have any homogeneous analogue except for matrix-isolated [Cu(eta2-H2)Cl]. Comparison with the unstable Na+(H2) adducts formed in the parent Na-ZSM-5 zeolite allow the conclusion that the Cu(I)/H2 bond is governed by sigma-pi overlap forces. 相似文献
37.
Celebre G De Luca G Longeri M Pileio G Emsley JW 《The Journal of chemical physics》2004,120(15):7075-7084
The proton NMR spectra of two (13)C-labeled isotopomers of styrene dissolved in two liquid crystalline solvents have been obtained and analyzed to yield four sets each of 24 dipolar couplings. These couplings were then used to investigate the structure of the ring and the ene fragments of the molecule, and the position of the maximum, phi(0), in the ring-ene bond rotational probability distribution. To do this, the effect on the dipolar couplings of small-amplitude vibrational motion was taken into account using vibrational wave functions calculated by molecular orbital and density functional methods. It is concluded that the NMR data are consistent with the ring fragment, averaged over the ring-ene rotation, planar, while the ene fragment is not. The value of phi(0) is found to be 18.0 degrees +/-0.2 degrees for the two solutions, compared with a value of 27 degrees calculated by the molecular method MP2/6-31G(*). 相似文献
38.
Cappelletti G Ricci C Ardizzone S Parola C Anedda A 《The journal of physical chemistry. B》2005,109(10):4448-4454
TiO(2) nanoparticles are obtained by combining a sol-gel preparative route with hydrothermal aging steps, performed in mild conditions, of varying time lengths. Both aged and un-aged samples are thermally treated at 300 and 600 degrees C, for the same length of time. The crystal structures, the phase composition, and crystallite sizes are analyzed by powder X-ray diffraction. Raman spectra of anatase nanocrystals with average sizes of 7-10 nm are reported and the correlation between the Raman band shape of the main feature at 144 cm(-1) and the crystallite size is discussed. Nitrogen physisorption by Brunauer-Emmett-Teller (BET) method is adopted to evaluate the particles surface area and mesopore size and size distribution. The role played by the hydrothermal step in affecting the physicochemical properties of the powders is discussed also with respect to the H(2)O/TiO(2) interactions as apparent from Raman spectroscopy investigations of the O-H stretching range (3000-3800 cm(-1)). 相似文献
39.
Giuseppe Werber Francesco Buccheri Nicol Vivona Manlio Gentile 《Journal of heterocyclic chemistry》1978,15(8):1393-1398
The factors influencing the reactivity of α-thienylglyoxal monosemicarbazones when treated with cyclizing reagents (bromine/sodium acetate and hydrobromic acid in acetic acid) were investigated. Depending on the experimental conditions, on the position of the substituent on the semicarbazide residue, and on the cyclizing agent, the substrates 1a-e give the semicarbazone bromides 2a-b, 5 , the 1,3,4-oxadiazoles 3a-c , the 1,2,4-triazine 11 and the 2,3,4,5-tetrahydro-1,2,4-triazine-3-ones 6, 8 and 9 . Compound 6 by thermolysis undergoes ring contraction in the Δ2-1,3,4-oxadiazoline 12 , while treatment with base involves the conversion of 6 into 1,2,4-triazol-5-one 13 . Ir, nmr and mass spectra support the reported structures. 相似文献
40.
Coppola L Gianferri R Oliviero C Ranieri GA 《Journal of colloid and interface science》2003,264(2):554-557
We report on the first rheological study of the structural relaxations in a nematic liquid crystalline phase. Linear dynamic and transient shear experiments were applied to a polydomain nematic phase of the CTAB/water system: a liquid crystalline mixture composed of 28 wt% CTAB at 35 degrees C. The decay of the shear modulus, G(t), was analyzed using the CONTIN inverse Laplace transform to obtain a distribution of relaxation times which were compared with ones from the usual fitting procedure based on a generalized Maxwell model. The behavior of the nematic lyotropic structure of the CTAB/water system is characterized by the presence of both slow and fast relaxation times. These were interpreted as being due to a progressive loss of the lyotropic domain orientation and to the breaking/reforming process of the cylindrical aggregates, respectively. 相似文献