全文获取类型
收费全文 | 497篇 |
免费 | 16篇 |
专业分类
化学 | 342篇 |
晶体学 | 2篇 |
力学 | 20篇 |
数学 | 61篇 |
物理学 | 88篇 |
出版年
2022年 | 11篇 |
2021年 | 14篇 |
2020年 | 7篇 |
2019年 | 19篇 |
2018年 | 10篇 |
2017年 | 6篇 |
2016年 | 19篇 |
2015年 | 8篇 |
2014年 | 17篇 |
2013年 | 33篇 |
2012年 | 18篇 |
2011年 | 26篇 |
2010年 | 15篇 |
2009年 | 26篇 |
2008年 | 23篇 |
2007年 | 23篇 |
2006年 | 21篇 |
2005年 | 14篇 |
2004年 | 15篇 |
2003年 | 15篇 |
2002年 | 20篇 |
2001年 | 6篇 |
2000年 | 6篇 |
1999年 | 3篇 |
1998年 | 6篇 |
1996年 | 3篇 |
1995年 | 6篇 |
1994年 | 6篇 |
1993年 | 4篇 |
1988年 | 4篇 |
1985年 | 2篇 |
1984年 | 7篇 |
1983年 | 2篇 |
1981年 | 2篇 |
1980年 | 8篇 |
1979年 | 2篇 |
1978年 | 2篇 |
1977年 | 5篇 |
1975年 | 6篇 |
1974年 | 3篇 |
1973年 | 5篇 |
1972年 | 2篇 |
1971年 | 5篇 |
1970年 | 5篇 |
1969年 | 7篇 |
1968年 | 4篇 |
1967年 | 4篇 |
1966年 | 4篇 |
1911年 | 2篇 |
1891年 | 3篇 |
排序方式: 共有513条查询结果,搜索用时 0 毫秒
11.
G. Giraudi Claudio Baggiani Antonella Cosmaro Emilio Santià Adriano Vanni 《Fresenius' Journal of Analytical Chemistry》1998,360(2):235-240
A very selective polyclonal antiserum against 1,1,1-trichloro-2,2-bis-(4-chlorophenyl)-ethane (p,p′-DDT) was obtained by a careful choice of the haptenic structure (2,2-bis(4-chlorophenyl)-ethanol hemisuccinate). This hapten
was conjugated to BSA to prepare the immunogen. The effects of different types of solid phases on the equilibrium reaction
between the hapten on solid phase and the polyclonal antiserum were evaluated to obtain a fine tuning of the antiserum performances
in terms of specificity for p,p′-DDT and sensitivity to low levels of this pesticide. The calibration curves obtained show that it is possible to set up
a sensitive assay for p,p′-DDT, employing a p,p′-dichlorodiphenylacetic acid-based solid phase, with a detection limit of 0.12 ng/mL and a working range of about 0.21–40
ng/mL. Selectivity towards several p,p′-DDT-related substances was good (o,p-DDT 17%, p,p′-DDD 1.2% o,p-DDD 6.3%, p,p′-DDE 6.7%).
Received: 4 November 1996 / Revised: 9 June 1997 / Accepted: 16 June 1997 相似文献
12.
Abstract –The individual tryptophanyl contributions to the near-ultraviolet dichroic activity of apomyoglobin in its native conformation have been resolved. This was accomplished by comparing the spectra of two classes of apomyoglobin with different aromatic residue contents and observing the effect of a specific modification of indole residues. The circular dichroism (CD) spectra of apomyoglobins containing two tryptophanyl residues, i.e. Trp A-5 and A-12, show the presence of a positive peak centered at 292 nm, attributable to indolic chromophore, which is missing in the CD spectrum of tuna apomyoglobin possessing only Trp A-12. Moreover, the specific modification of Trp A-5 by 2-hydroxy-5-nitrobenzyl bromide is shown by the lack of the 292 nm peak and the appearance of a positive band at longer wavelength. The pH dependence of the position of this band suggests that it arises from the 2-hydroxy-5-nitrobenzyl moiety. The results suggest that Trp A-12 does not substantially contribute to the optical activity in the near ultraviolet. 相似文献
13.
Ettore Carletti 《Annali dell'Universita di Ferrara》1983,29(1):37-44
Riassunto Scopo di questo lavoro è dare una formula asintotica per il numero degli zeri di ReF
K(λ+it) e di ImF
K(λ+it), dove
eζ
K(8) è la funzione zeta di Dedekind associata al campo numericoK, con 0<t<T e λ numero reale fissato tale che 1−1/n<λ<1 doven è il grado diK.
Summary The aim of this paper is to give an asymptotic formula for the number of zeros of ReF K(λ+it) and ImF K(λ+it), where andζ K(8) is the Dedekind zeta function for a number fieldK, with 0<t<T and λ fixed real number such that 1−1/n<λ<1, wheren is the degree ofK.相似文献
14.
Valeria Di Bussolo Giorgio Catelani Ettore Mastrorilli Cristina Di Bugno Raffaello Giorgi 《Tetrahedron: Asymmetry》1996,7(12):3585-3592
(±)-1-Cyclohexyl-c-2-hydroxymethyl-r-1-cyclohexanol 3, a precursor of the antimuscarinic drug Rociverine 1, was obtained diastereospecifically in very high yield, from the Grignard reaction between C6H11MgCl and an appropriately protected 2-(hydroxymethyl)cyclohexanone. The preparation of enantiomerically enriched cis diol (+)-(1R,2S)-3 and the corresponding 2-acetoxymethyl derivative (+)-(1S,2R)-12 was achieved by lipase PPL-catalyzed transesterification of racemic diol (±)-3. 相似文献
15.
ClaudiaG. Martínez Annette Neuner Cristina Martí Santi Nonell AndrM. Braun Esther Oliveros 《Helvetica chimica acta》2003,86(2):384-397
We have investigated the effect of a series of 18 solvents and mixtures of solvents on the production of singlet molecular oxygen (O2(1Δg), denoted as 1O2) by 9H‐fluoren‐9‐one (FLU). The normalized empirical parameter E derived from ET(30) has been chosen as a measure of solvent polarity using Reichardt's betaine dyes. Quantum yields of 1O2 production (ΦΔ) decrease with increasing solvent polarity and protic character as a consequence of the decrease of the quantum yield of intersystem crossing (ΦISC). Values of ΦΔ of unity have been found in alkanes. In nonprotic solvents of increasing polarity, ΦISC and, therefore, ΦΔ decrease due to solvent‐induced changes in the energy levels of singlet and triplet excited states of FLU. This compound is a poor 1O2 sensitizer in protic solvents, because hydrogen bonding considerably increases the rate of internal conversion from the singlet excited state, thus diminishing ΦΔ to values much lower than those in nonprotic solvents of similar polarity. In mixtures of cyclohexane and alcohols, preferential solvation of FLU by the protic solvent leads to a fast decrease of ΦΔ upon addition of increasing amounts of the latter. 相似文献
16.
Davide Barreca Ettore Fois Alberto Gasparotto Chiara Maccato Mario Oriani Gloria Tabacchi 《Molecules (Basel, Switzerland)》2021,26(7)
Transition metal complexes with β-diketonate and diamine ligands are valuable precursors for chemical vapor deposition (CVD) of metal oxide nanomaterials, but the metal-ligand bond dissociation mechanism on the growth surface is not yet clarified in detail. We address this question by density functional theory (DFT) and ab initio molecular dynamics (AIMD) in combination with the Blue Moon (BM) statistical sampling approach. AIMD simulations of the Zn β-diketonate-diamine complex Zn(hfa)2TMEDA (hfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate; TMEDA = N,N,N′,N′-tetramethylethylenediamine), an amenable precursor for the CVD of ZnO nanosystems, show that rolling diffusion of this precursor at 500 K on a hydroxylated silica slab leads to an octahedral-to-square pyramidal rearrangement of its molecular geometry. The free energy profile of the octahedral-to-square pyramidal conversion indicates that the process barrier (5.8 kcal/mol) is of the order of magnitude of the thermal energy at the operating temperature. The formation of hydrogen bonds with surface hydroxyl groups plays a key role in aiding the dissociation of a Zn-O bond. In the square-pyramidal complex, the Zn center has a free coordination position, which might promote the interaction with incoming reagents on the deposition surface. These results provide a valuable atomistic insight on the molecule-to-material conversion process which, in perspective, might help to tailor by design the first nucleation stages of the target ZnO-based nanostructures. 相似文献
17.
18.
C. Santi M. Tiecco L. Testaferri C. Tomassini F. Marini L. Bagnoli 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3-4):1071-1075
Abstract The first example of a kinetic resolution process promoted by an electrophilic selenium reagent is reported. Racemic allylic alcohols react with half equivalents of a selenenylating agent in methanol leading to the regiospecific formation of the corresponding addition products with a very high level of facial selectivity (98% de). The unreacted alcohol can be recovered in a optically enriched form (92% ee). 相似文献
19.
20.
Facile synthesis of novel ibuprofen bearing polyurethane 1 has been achieved for the first time and found to display the release pattern of ibuprofen based on the easy cleavage of ester linkages. Thorough characterizations (FT‐IR, UV‐Vis, NMR, and elemental analysis) were performed to ascertain the structure of polyurethane 1. 相似文献