全文获取类型
收费全文 | 346篇 |
免费 | 10篇 |
国内免费 | 2篇 |
专业分类
化学 | 279篇 |
晶体学 | 3篇 |
力学 | 2篇 |
数学 | 20篇 |
物理学 | 54篇 |
出版年
2023年 | 3篇 |
2022年 | 5篇 |
2021年 | 6篇 |
2020年 | 5篇 |
2019年 | 8篇 |
2018年 | 3篇 |
2017年 | 3篇 |
2016年 | 7篇 |
2015年 | 11篇 |
2014年 | 8篇 |
2013年 | 21篇 |
2012年 | 24篇 |
2011年 | 25篇 |
2010年 | 17篇 |
2009年 | 12篇 |
2008年 | 30篇 |
2007年 | 36篇 |
2006年 | 23篇 |
2005年 | 14篇 |
2004年 | 18篇 |
2003年 | 14篇 |
2002年 | 9篇 |
2001年 | 3篇 |
2000年 | 3篇 |
1999年 | 1篇 |
1998年 | 2篇 |
1997年 | 4篇 |
1996年 | 3篇 |
1995年 | 3篇 |
1993年 | 1篇 |
1992年 | 1篇 |
1991年 | 1篇 |
1990年 | 2篇 |
1989年 | 1篇 |
1988年 | 2篇 |
1985年 | 2篇 |
1982年 | 4篇 |
1980年 | 2篇 |
1979年 | 6篇 |
1978年 | 2篇 |
1977年 | 2篇 |
1975年 | 3篇 |
1973年 | 1篇 |
1972年 | 1篇 |
1954年 | 1篇 |
1953年 | 1篇 |
1952年 | 1篇 |
1944年 | 1篇 |
1943年 | 1篇 |
1942年 | 1篇 |
排序方式: 共有358条查询结果,搜索用时 15 毫秒
1.
Juan Jos Berzas Nevado Rosa Carmen Rodríguez Martín-Doimeadis Francisco Javier Guzmn Bernardo Nuria Rodríguez Farias 《Microchemical Journal》2007,86(2):183-188
An analytical methodology was proposed and validated to be applied to the determination of p,p′-DDT and its metabolites p,p′-DDE and p,p′-DDD in fish oil. The analytical procedure presented in this paper involves a single-step clean up process prior to the analysis. A solution of 1,2,3,4-tetrachloronaphtalene was used as internal standard.The analytical technique used was gas chromatography coupled to an electron capture detector. Details on the validation process are provided.The limits of detection ranged from 2.6 to 4.7 pg μL− 1. The BCR 598 standard reference material (cod liver oil) was used to evaluate the performance of the methodology with satisfactory recoveries for all the compounds.The analytes were determined in three different fish oil pills sold in Spain as a supplementary vitamin support. The sum of p,p′-DDT and metabolites was from 13.2 to 51.3 ng g− 1, the dominant compound being p,p′-DDE. 相似文献
2.
Bayó N Jiménez JC Rivas L Nicolás E Albericio F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(5):1096-1103
An optimized solid-phase strategy for the preparation of the cyclic lipononadepsipeptide [N-Mst(L-Ser1), D-Ser4, L-Thr6, L-Asp8, L-Thr9]syringotoxin is reported. The strategy is based on the use of a mild orthogonal protection scheme and the incorporation of the nonproteinogenic amino acid (Z)-Dhb into the peptide chain as the dipeptide Fmoc-Thr(tBu)-(Z)-Dhb-OH. The didehydrodipeptide was synthesized by a water-soluble carbodiimide-induced beta-elimination of a protected dipeptide containing a residue of Thr with its free hydroxy side chain unprotected. 相似文献
3.
Stereoselective synthesis of trans-2,3-disubstituted pyrrolidines via addition to N-acyliminium ions
An efficient and stereoselective synthesis of trans-2,3-disubstituted pyrrolidines is described. The intermolecular alkylation of racemic N-acyliminium ions generated in situ from the corresponding 3-substituted lactams proceeds stereoselectively and in high yield. 相似文献
4.
Jean-Manuel Raimundo Philippe Blanchard Nuria Gallego-Planas Nicolas Mercier Isabelle Ledoux-Rak Rolland Hierle Jean Roncali 《The Journal of organic chemistry》2002,67(1):205-218
Two series of push-pull chromophores built around thiophene-based pi-conjugating spacers rigidified either by covalent bonds or by noncovalent intramolecular interactions have been synthesized and characterized by UV-vis spectroscopy, electric field induced second harmonic generation (EFISH) and differential scanning calorimetry. Comparison of the linear and second-order nonlinear optical properties of chromophores based on a covalently bridged dithienylethylene (DTE) spacer with those of their analogues based on open chain DTE shows that the rigidification of the spacer produces a considerable bathochromic shift of the absorption maximum together with a dramatic enhancement of the molecular quadratic hyperpolarizability (mu beta) which reaches values among the highest reported so far. A second series of NLO-phores has been derived from a 2,2'-bi(3,4-ethylenedioxythiophene) (BEDOT) pi-conjugating spacer. As indicated by X-ray and UV-vis data, rigidification of the spacer originates in that case, from noncovalent intramolecular interactions between sulfur and oxygen atoms. Again, comparison with the parent compounds based on an unsubstituted bithiophene spacer reveals a marked red shift of the absorption maximum and a large enhancement of mu beta. In an attempt to distinguish the contribution of the electronic and geometrical effects of the ethylenedioxy group, a third series of NLO-phores based on 3,4-ethylenedioxythiophene (EDOT) and 3,4-dihexyloxythiophene spacers has been synthesized. Comparison with compounds based on unsubstituted thiophene shows that, despite a red shift of lambda(max), introduction of alkoxy groups leads to a decrease of mu beta. Theoretical calculations indicate that this effect results from a decrease of the dipole moment (mu) caused by the auxiliary electron-donor alkoxy groups on the thiophene ring. In contrast, replacement of BT by BEDOT produces an increase of mu, which associated with the noncovalent rigidification of the BT system accounts for the observed enhancement of mu beta. 相似文献
5.
Torres D Lopez N Illas F Lambert RM 《Journal of the American Chemical Society》2005,127(31):10774-10775
The heterogeneously catalyzed epoxidation of alkenes is experimentally challenging, theoretically interesting, and technologically important. Although large-scale ethylene epoxidation is universally carried out with Ag catalysts, recent laboratory studies on single crystal surfaces show that Cu is intrinsically much more selective than Ag in the epoxidation of a variety of terminal alkenes. The reasons for this striking difference between Ag and Cu have been investigated by means of density functional theory. It is found that the fundamental cause is the inversion in the ordering of activation barriers for the competing pathways to epoxide formation versus acetaldehyde formation (the latter being the first step on the route to combustion). On Cu, epoxide formation is less activated than aldehyde formation; the opposite is true on Ag. This behavior is associated with a late transition state to epoxidation on Cu (i.e., product-like) compared to an early (reactant-like) transition state to epoxidation on Ag. 相似文献
6.
C. Kourkoumelis L. K. Resvanis T. A. Filippas E. Fokitis A. M. Chops S. Iwata R. B. Palmer D. C. Rahm P. Rehak I. Stumer C. W. Fabjan T. Fields D. Lissauer I. Mannelli P. Mouzourakis A. Nappi W. J. Willis 《Zeitschrift fur Physik C Particles and Fields》1980,5(2):95-104
The inclusive cross-section for π0 production near 90° inpp collisions at the CERN Intersecting Storage Rings has been studied for thep T range 3<p T <16GeV/c at four different centre-of-mass energies ( \(\sqrt s = 30.6\) , 44.8, 52.7, and 62.8 GeV). In this experiment the two photons from the π0→yy decay were resolved and measured separately forp T values up to 10 GeV/c. Results indicate an agreement with thep T ?8 behaviour for the lower values ofp T and a slower decrease of the cross-section for the higher values ofp T . The high-p T data deviate from the scaling expressionp T ?n F(x T ), which holds for the lowerp T values (p T <8GeV/c). 相似文献
7.
C. Kourkoumelis L. K. Resvanis T. A. Filippas E. Fokitis R. B. Palmer D. C. Rahm P. Rehak I. Stumer C. W. Fabjan T. Fields D. Lissauer I. Mannelli P. Mouzourakis A. Nappi W. J. Willis M. Goldberg 《Zeitschrift fur Physik C Particles and Fields》1982,16(2):101-109
A search for massive photon pair production at \(\sqrt s = 63 GeV\) has been carried out on the data sample previously employed for the electron pair production study. Positive evidence is reported form γγ>6GeV, with a production cross-section similar to Drell-Yan electron pairs. The ratio γγ/π0π0 was measured to be ~10?3 for ap T of each γ or γ or π0 above 3 GeV/c. 相似文献
8.
Rodríguez-Calvillo Pablo Ferrer Nuria Cabrera José-María 《Journal of Thermal Analysis and Calorimetry》2021,146(3):1393-1403
Journal of Thermal Analysis and Calorimetry - The thermal behavior of two copper alloys, with 0.2 and 0.5 mass % of Mg, was analyzed after severe plastic deformation processing by Equal Channel... 相似文献
9.
10.
Ridi F Fratini E Mannelli F Baglioni P 《The journal of physical chemistry. B》2005,109(30):14727-14734
In the cement industry, the extrusion technique is used to produce flat shapes with improved resistance to compression. Extrusion is a plastic-forming process that consists of forcing a highly viscous plastic mixture through a shaped die. The material should be fluid enough to be mixed and to pass through the die, and on the other hand, the extruded specimen should be stiff enough to be handled without changing in shape or cracking. These characteristics are industrially obtained by adding cellulosic polymers to the mixture. The aim of this work is to understand the action mechanism of these additives on the major pure phases constituting a typical Portland cement: tricalcium silicate (C(3)S), dicalcium silicate (C(2)S), tricalcium aluminate (C(3)A), and tetracalcium iron-aluminate (C(4)AF). In particular, a methylhydroxyethyl cellulose (MHEC) was selected from the best-performing polymers for further study. The effect of this additive on the hydration kinetics (rate constants, activation energies, and diffusional constants) was evaluated by means of differential scanning calorimetry (DSC) while the hydration products were studied by using thermogravimetry-differential thermal analysis (TG-DTA), X-ray diffraction (XRD), and scanning electron microscopy (SEM). MHEC addition in calcium silicate pastes produces an increase in the induction time without affecting the nucleation-and-growth period. A less dense CSH gel was deduced from the diffusional constants in the presence of MHEC. Moreover, CSH laminar features and poorly structured hydrates were noted during the first hours of hydration. In the case of the aluminous phases, the additive inhibits the growth of stable cubic hydrated phases (C(3)AH(6)), with the advantage of the metastable hexagonal phases being formed in the earliest minutes of hydration. 相似文献