全文获取类型
收费全文 | 441篇 |
免费 | 12篇 |
国内免费 | 1篇 |
专业分类
化学 | 292篇 |
晶体学 | 3篇 |
力学 | 7篇 |
数学 | 56篇 |
物理学 | 96篇 |
出版年
2023年 | 3篇 |
2022年 | 2篇 |
2021年 | 9篇 |
2020年 | 5篇 |
2019年 | 7篇 |
2018年 | 8篇 |
2017年 | 8篇 |
2016年 | 10篇 |
2015年 | 8篇 |
2014年 | 11篇 |
2013年 | 27篇 |
2012年 | 14篇 |
2011年 | 21篇 |
2010年 | 17篇 |
2009年 | 18篇 |
2008年 | 19篇 |
2007年 | 19篇 |
2006年 | 13篇 |
2005年 | 14篇 |
2004年 | 16篇 |
2003年 | 8篇 |
2002年 | 9篇 |
2001年 | 15篇 |
2000年 | 11篇 |
1999年 | 7篇 |
1998年 | 8篇 |
1997年 | 11篇 |
1996年 | 4篇 |
1995年 | 11篇 |
1994年 | 6篇 |
1993年 | 7篇 |
1992年 | 13篇 |
1991年 | 12篇 |
1990年 | 13篇 |
1989年 | 8篇 |
1988年 | 3篇 |
1987年 | 3篇 |
1986年 | 4篇 |
1985年 | 7篇 |
1984年 | 8篇 |
1983年 | 3篇 |
1982年 | 4篇 |
1981年 | 8篇 |
1980年 | 6篇 |
1979年 | 4篇 |
1978年 | 4篇 |
1977年 | 4篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1969年 | 1篇 |
排序方式: 共有454条查询结果,搜索用时 31 毫秒
441.
Contreras A 《Journal of colloid and interface science》2007,311(1):159-170
The wetting behavior and the interfacial reactions that occurred between molten Al-Cu alloys (1, 4, 8, 20, 33, and 100 wt% Cu) and solid TiC substrates were studied by the sessile drop technique in the temperature range of 800-1130 degrees C. The effect of wetting behavior on the interfacial reaction layer was studied. All the Al-Cu alloys react with TiC at the interface forming an extensive reaction layer. The interface thickness varied with the samples, and depends on the temperature, chemical composition of the alloy and the time of the test. Wetting increases with increasing concentration of copper in the Al-Cu alloy at 800 and 900 degrees C. In contrast, at higher temperature such as 1000 degrees C wetting decreases with increasing copper content. The spreading kinetics and the work of adhesion were evaluated. The high values of activation energies indicated that spreading is not a simple viscosity controlled phenomenon but is a chemical reaction process. The spreading of the aluminum drop is observed to occur according to the formation of Al4C3, CuAl2O4, CuAl2, TiCux mainly, leading to a decreases in the contact angle. As the contact angle decreases the work of adhesion increases with increasing temperature. Al-Cu/TiC assemblies showed cohesive fracture corresponding to a strong interface. However, using pure Cu the adhesion work is poor, and the percentage of cohesion work is also too low (27-34%). 相似文献
442.
In this work the partial molar volumes (V) of different anionic polyelectrolytes and hydrophobically modified polyelectrolytes (PHM) were measured. Polymers like polymaleic acid-co-styrene, polymaleic acid-co-1-olefin, polymaleic acid-co-vinyl-2-pyrrolidone, and polyacrylic acid (abbreviated as MAS-n, PA-n-K2, AMVP, and PAA, respectively) were employed. These materials were investigated by density measurements in highly dilute aqueous solutions. The molar volume results allow us to discuss the effect of the carboxylic groups and the contributions from the comonomeric principal chain. The PAA presents the smaller V, while the largest V value was for AMVP. The V of PHM shows a linear relationship with the number of methylene groups in the lateral chain. It is found that the magnitude of the contribution per methylene group decreases as the hydrophobic character of the environment increases. 相似文献
443.
444.
Ghiviriga I Zhang L Martinez H Contreras RH Tormena CF Nodin L Dolbier WR 《Magnetic resonance in chemistry : MRC》2011,49(3):93-105
In the process of studying the chemistry of perfluoro[2.2]paracyclophanes (PFPCs), a novel class of compounds, it became necessary to identify some disubstituted products. To achieve this goal, we characterize in this work some monosubstituted PFPCs, identifying their (19)F-(19) F coupling patterns, and establishing a methodology for the assignment of their (19)F chemical shifts. The pattern of coupling constants indicates a skewed geometry in which the upper deck moves towards or away from the substituent, depending on the substituent electron-donor character and size. Quantum chemical calculations, performed at the HF/6-311 + G(d,p)//B3LYP/EPR-III level of theory, confirmed the conformations inferred from coupling constants and reproduced well the values of the couplings. Transmission mechanisms for the FC term of four- and five-bond (19)F-(19) F couplings are discussed in detail. Understanding the conformational preferences of PFPCs and how they are reflected by the coupling constants facilitates the assignment of (19)F chemical shifts in monosubstituted PFPCs and the identification of the disubstituted products. 相似文献
445.
446.
E. Contreras Aguilar G. A. Echeverría O. E. Piro S. E. Ulic M. E. Tuttolomondo 《Molecular physics》2018,116(3):399-413
A detailed structural and spectroscopic study of a new thiourea derivative 1-butyl-3-(1-naphthoyl)thiourea (1) is presented with the assistance of theoretical calculations. The X-ray diffraction structure analysis reveals a planar carbonylthiourea group, favoured by intra-molecular NH···O bond. The compound is arranged in the lattice as NH···O and NH···S bonded polymeric ribbons, that extend along the crystal b-axis. Molecular pairs involving N–H···S hydrogen bonds are a dominant contribution to packing stabilisation coming from coulombic component. Hirshfeld surfaces and two-dimensional-fingerprint plots show different intermolecular contacts and its relative contributions to total surface in each compound. The AIM approach shows the nature and strength of the strong and weak intramolecular interactions and the solvent effect, while NBO analysis reveals that the sulphur atom is responsible for the higher hyperconjugative stabilising energy. 相似文献
447.
Rosalinda Contreras Jean Michel Grevy Zureima García‐Hernndez Marisol Gizado‐Rodriguez Bernd Wrackmeyer 《Heteroatom Chemistry》2001,12(6):542-550
A series of aminodiphenylphosphanes 1 [Ph2P‐N(H)tBu ( a ), ‐NEt2 ( b ), ‐NiPr2 ( c )], 2 [Ph2P‐NHPh ( a ), ‐NH‐2‐pyridine ( b ), ‐NH‐3‐pyridine ( c ), ‐NH‐4‐pyridine ( d ), NH‐pyrimidine ( e ), NH‐2,6‐Me2‐C6H3 ( f ), NH‐3‐Me‐2‐pyridine ( g )], 3 [Ph2P‐N(Me)Ph ( a ), ‐NPh2 ( b )], and N‐pyrrolyldiphenylphosphane 4 (Ph2P‐NC4H4) was prepared and studied by NMR (1H, 13C, 31P, 15N NMR) spectroscopy. The isotope‐induced chemical shifts 1Δ14/15N(31P) were determined at natural abundance of 15N by using HEED INEPT experiments. A dependence of 1Δ14/15N(31P) on the substituents at nitrogen was found (alkyl < H < aryl; increasingly negative values). The magnitude and sign of the coupling constants 1J(31P,15N) (positive sign) are dominated by the presence of the lone pair of electrons at the phosphorus atom. The X‐ray structural analysis of 2b is reported, showing the presence of dimers owing to intermolecular hydrogen bridges in the solid state. © 2001 John Wiley & Sons, Inc. Heteroatom Chem 12:542–550, 2001 相似文献
448.
Ekaterina V. Bakhmutova Heinrich Nth Rosalinda Contreras Bernd Wrackmeyer 《无机化学与普通化学杂志》2001,627(8):1846-1854
Pseudo‐ephedrine derived 2‐imino‐1,3‐thiazolidine 1 reacts with tris(diethylamino)phosphane by stepwise replacement of the diethylamino group to give the mono‐, bis‐ and tris(imino)phosphanes 2 , 3 and 4 , respectively, of which 4 could be isolated in pure state. The analogous reaction with diethylamino‐diphenylphosphane affords the imino‐diphenylphosphane 5 . The iminophosphanes react with sulfur or selenium to give the corresponding phosphorus(V) compounds. In contrast, the reaction of the iminophosphanes with oxygen is very slow; anhydrous trimethylamine N‐oxide reacts in the melt with the phosphanes to give the oxides 4(O) and 5(O) . The molecular structures of 4(O) (in mixture with 4 ), 4(Se) , 5(S) and 5(Se) were determined by X‐ray analysis. In all cases the ring‐sulfur and the phosphorus atoms are in cis‐positions at the C=N bonds. The analogous solution structures were determined by 1H, 13C, 15N, 31P and 77Se NMR spectroscopy. In the case of the compounds 5 , 5(O) , 5(S) and 5(Se) the isotope‐induced chemical shifts 1δ14/15N(31P) were determined, using INEPT‐HEED experiments. 相似文献
449.
J. C. Cesco C. C. Denner G. O. Giubergia A. E. Rosso J. E. Prez F. S. Ortiz O. E. Taurian R. H. Contreras 《Journal of computational chemistry》1999,20(6):604-609
A mixed atomic basis set formed with ls Slater-type orbitals and 1s floating spherical Gaussian orbitals is implemented. Evaluation of multicenter integrals is carried out using a method based on expansion of binary products of atomic basis functions in terms of a complete basis set, and a systematic analysis is performed. The proposed algorithm is very stable and furnishes fairly good results for total energy and geometry. An LCAO-SCF test calculation is carried out on LiH. The trends observed show that there are some combinations of mixed orbitals that are appropriate to describe the system. ©1999 John Wiley & Sons, Inc. J Comput Chem 20: 604–609, 1999 相似文献
450.
Noemí Andrade-Lpez Armando Ariza-Castolo Rosalinda Contreras Amrica Vzquez-Olmos Norh Barba Behrens Hugo Tlahuext 《Heteroatom Chemistry》1997,8(5):397-410
The structure, dynamic behavior, protonation, methylation, and coordination sites of 2-guanidinobenzimidazole 1a were investigated. Structures of compounds [2-guanidinium-1,3,10-trihydrobenzimidazole]sulfate 1b , [2-guanidinium-1,3-dihydro-benzimidazole]sulfate 1c–1d , [2-guanidinium-1,3-dihydro-benzimidazole]tetrafluoroborate 1e , [2-guanidinium-1,3-dihydro-benzimidazole]chloride 1f , [2-guanidinium-1,3-dihydro-benzimidazole] perchlorate 1g , 2-guanidino-1-methyl-benzimidazole 2a , [2-guanidinium-1,3-dimethyl-benzimidazole]iodide 2b , [2-guanidinium-1-methyl-3-hydro-benzimidazole]chloride 2c , [2-guanidinium-1,10-dihydro-benzimidazole]acetate 3 , 2-guanidino-1-hydro-3-borane-benzimidazole 4a , 2-guanidino-1-methyl-3-borane-benzimidazole 4b , (2-guanidino-benzimidazole)dimethyltin 5 , [bis(2-guanidino-10-hydro-benzimidazole)nickel(II)] 6 , and [bis(2-guanidino-1,10-dihydro-benzimidazole)zinc(II)]nitrate 7 were determined based on 1H, 13C, and 15N NMR spectroscopy. The X-ray diffraction structures of 2a, 2b, 3, 6 , and 7 were obtained. The results show that 1a has an open structure without an intramolecular hydrogen bond in DMSO or DMF. The imidazolic N-3 is the preferred basic site in solution for protonation, methylation, and coordination and not N-10 as was suggested from semiempirical calculations. Under strong acidic conditions, diprotonation occurs at N-3 and N-10. In the solid state, 3 and 6 were protonated preferently at N10 rather than at N-1. © 1997 John Wiley & Sons, Inc. Heteroatom Chem 8: 397–410, 1997 相似文献