全文获取类型
收费全文 | 129篇 |
免费 | 4篇 |
国内免费 | 2篇 |
专业分类
化学 | 106篇 |
数学 | 16篇 |
物理学 | 13篇 |
出版年
2023年 | 2篇 |
2022年 | 11篇 |
2021年 | 4篇 |
2020年 | 2篇 |
2019年 | 7篇 |
2018年 | 4篇 |
2017年 | 1篇 |
2016年 | 4篇 |
2015年 | 1篇 |
2014年 | 3篇 |
2013年 | 11篇 |
2012年 | 1篇 |
2011年 | 6篇 |
2010年 | 8篇 |
2009年 | 2篇 |
2008年 | 11篇 |
2007年 | 13篇 |
2006年 | 10篇 |
2005年 | 6篇 |
2004年 | 4篇 |
2003年 | 7篇 |
2002年 | 4篇 |
2001年 | 2篇 |
2000年 | 2篇 |
1999年 | 1篇 |
1997年 | 3篇 |
1993年 | 1篇 |
1989年 | 1篇 |
1981年 | 1篇 |
1974年 | 1篇 |
1973年 | 1篇 |
排序方式: 共有135条查询结果,搜索用时 15 毫秒
11.
[reaction: see text] The 2,2,2-trichloroethyl (TCE) group was utilized as the first protecting group for aryl sulfates. Aryl sulfates, protected with the TCE group, were prepared in high yield by reacting phenols with chlorosulfuric acid TCE ester. Deprotection was accomplished using Pd/C-ammonium formate or with Zn-ammonium formate to give aryl sulfate monoesters in high yield. This approach to aryl sulfate synthesis was successfully applied to the construction of estrone sulfate derivatives, which could not be prepared by previous methodologies. 相似文献
12.
Martin P. Seah Felicia M. Green Ian S. Gilmore 《Journal of the American Society for Mass Spectrometry》2010,21(3):370-377
Measurements are described to evaluate the constitution of secondary ion mass spectra for both monatomic and cluster primary
ions. Previous work shows that spectra for different primary ions may be accurately described as the product of three material-dependent
component spectra, two being raised to increasing powers as the cluster size increases. That work was for an organic material
and, here, this is extended to (SiO2)
t
OH− clusters from silicon oxide sputtered by 25 keV Bi
n
+ cluster primary ions for n = 1, 3, and 5 and 1 ≤ t ≤ 15. These results are described to a standard deviation of 2.4% over 6 decades of intensity by the product of a constant
with a spectrum, H
SiOH/*, and a power law spectrum in t. This evaluation is extended, using published data for Si
t
+ sputtered from Si by 9 and 18 keV Au− and Au3−, with confirmation that the spectra are closely described by the product of a constant with a spectrum, H
Si*, and a simple spectrum that is an exponential dependence on t, both being raised to appropriate powers. This is confirmed with further published data for 6, 9, 12, and 18 keV Al− and Al2− primary cluster ions. In all cases, the major effect of intensity is then related to the deposited energy of the primary
ion at the surface. The constitution of SIMS spectra, for monatomic and cluster primary ion sources, is shown, in all cases,
to be consistent with the product of a constant with two component spectra raised to given powers. 相似文献
13.
Pier Luigi Barili Maria Camilla Bergonzi Giancarlo Berti Giorgio Catelani Felicia D'Andrea Francesco De Rensis 《Journal of carbohydrate chemistry》2013,32(9):1037-1049
ABSTRACT The title compound, previously unreported in either enantioform, and its 2,6-di-O-benzyl derivative have been synthesized through a stereocontrolled epimerization at C-2 of 6-O-protected methyl 3,4-O-isopropylidene-5-C-methoxy-β-D-galactopyranosides. The epimerization, performed through a high yielding sequence of oxidation-reduction owing to the cooperative role of the equatorial C-1 aglycon and the steric hindrance of the isopropylidene group, turned out to be completely diastereoselective. Whereas the unprotected L-ribo-hexos-5-ulose exists, as proved by NMR in D2O, in five main tautomeric forms in a ratio of about 4:2:2:1:1, only two anomeric 1,4-furanosic forms are present at equilibrium in its 2,6-di-O-benzyl derivative, in ratios ranging from 10:1 to 7:3, depending on the prevalence of D2O or CD3CN in the solvent mixture. 相似文献
14.
Pier Luigi Barili Giancarlo Berti Giorgio Catelani Felicia D'Andrea Francesco De Rensis Giampaolo Goracci 《Journal of carbohydrate chemistry》2013,32(8):1167-1180
Abstract The unreported title compound and its 2,6-di-O-benzyl derivative have been prepared from methyl β-D-galactopyranoside through a sequence involving the bisglycoside methyl 2,6-di-O-benzyl-5-O-methoxv-β-D-galactopyranoside 8, the precursor of L-orabino-hexos-5-ulose, that was converted to the L-lyxo series by inversion at C-3. The inversion was achieved in acceptable yields by selective triflation, followed by displacement with benzoate, and by an oxidation/reduction sequence. Whereas 2,5-di-O-benzyl-L-lyxo-hexos-5-ulose exists entirely as a mixture of the two anomeric 1,4-furanosic forms, the unprotected hexos-5-ulose involves at equilibrium in CD3CN/D2O at least eight tautomers, one of which is predominant. 相似文献
15.
Mihaela Badea Rodica Olar Valentina Uivarosi Dana Marinescu Victoria Aldea Stefania Felicia Barbuceanu George Mihai Nitulescu 《Journal of Thermal Analysis and Calorimetry》2011,105(2):559-564
Two new complexes having general formula VOL2·nH2O [(1) L: 5-hydroxyflavone, n = 1; (2) L: chrysin, n = 4] were synthesized and characterized. Based on IR and electronic data we concluded that studied flavones act as bidentate
ligands in complexes with metallic ion coordinated in a square-pyramidal stereochemistry. The thermal analysis (TG, DTA) elucidated
the composition and also the number and nature of the water molecules. The thermal behavior also indicated strong interactions
between oxovanadium (IV) and these oxygen donor ligands. 相似文献
16.
Laura Felicia Matusevich Ezra Miller 《Proceedings of the American Mathematical Society》2006,134(5):1375-1381
Let be an integer matrix, and assume that the convex hull of its columns is a simplex of dimension not containing the origin. It is known that the semigroup ring is Cohen-Macaulay if and only if the rank of the GKZ hypergeometric system equals the normalized volume of for all complex parameters (Saito, 2002). Our refinement here shows that has rank strictly larger than the volume of if and only if lies in the Zariski closure (in ) of all -graded degrees where the local cohomology is nonzero. We conjecture that the same statement holds even when is not a simplex.
17.
Jaganyi D Tiba F Munro OQ Petrović B Bugarcić ZD 《Dalton transactions (Cambridge, England : 2003)》2006,(24):2943-2949
Substitution reactions of the complexes [Pd(bpma)(H2O)]2+ and [Pt(bpma)(H2O)]2+, where bpma = bis(2-pyridylmethyl)amine, with TU, DMTU and TMTU for both complexes and Cl-, Br-, I- and SCN- for the platinum complex, were studied in aqueous 0.10 M NaClO4 at pH 2.5 using a variable-temperature stopped-flow spectrophotometer. The pKa value for the coordinated water molecule in [Pd(bpma)(H2O)]2+ (6.67) is a unit higher than that of [Pt(bpma)(H2O)]2+. The observed pseudo-first-order rate constants k(obs) (s(-1)) obeyed the equation k(obs) = k2[Nu] (Nu = nucleophile). The second-order rate constants indicate that the Pd(II) complex is a factor of 10(3) more reactive than Pt(II) complex. The nucleophile reactivity attributed to the steric hindrance in case of TMTU and the inductive effect for DMTU was found to be DMTU > TU > TMTU for [Pt(bpma)(H2O)]2+ and DMTU approximately TU > TMTU for [Pd(bpma)(H2O)]2+. The trend for ionic nucleophile was I- > SCN- > Br- > Cl-, an order linked to their polarizability and the softness or hardness of the metal. Activation parameters were determined for all reactions and the negative entropies of activation (Delta S++) support an associative ligand substitution mechanism. The X-ray crystal structure of [Pd(bpma)(py)](ClO4)2 was determined; it belongs to the triclinic space group P1 and has one formula unit in the unit cell. The unit cell dimensions are a = 8.522(2), b = 8.627(2), c = 16.730(4) A; alpha = 89.20(2), beta = 81.03(2), gamma = 60.61(2) degrees ; V = 1055.7(5) A3. The structure was solved using direct methods in WinGX's implementation of SHELXS-97 and refined to R = 0.054. The coordination geometry of [Pd(bpma)(py)]2+ is distorted square-planar. The Pd-N(central) bond distance, 1.996(3) A, is shorter than the other two Pd-N distances, 2.017(3) and 2.019(3) A. The Pd-N(pyridine) distance is 2.037(3) A. 相似文献
18.
Stefania‐Felicia Barbuceanu Gabriela Bancescu Gabriel Saramet Florica Barbuceanu Constantin Draghici Flavian Stefan Radulescu Aura Ionescu Simona Negres 《Heteroatom Chemistry》2013,24(4):309-321
In the present study, new 1,2,4‐triazoles, 1,3,4‐thiadiazoles, and acylthiosemicarbaz‐ides derived from 4‐(4‐chlorophenylsulfonyl)benzoic acid hydrazide were synthesized and screened for their antimicrobial and analgesic activities. Acylthiosemicarbazides 2–4 were synthesized by a reaction of 4‐(4‐chlorophenyl‐sulfonyl)benzoic acid hydrazide 1 with different arylisothiocyanates.4,5‐Disubstituted‐2,4‐dihydro‐3H‐1,2,4‐triazol‐3‐thiones 5–7 and 2,5‐disubstituted‐1,3,4‐thiadiazoles 8–10 were obtained by dehydrative cyclization of corresponding acylthiosemicarbazide derivatives 2–4 in basic media (8% aqueous sodium hydroxide) and in acidic media (sulfuric acid or phosphorous oxychloride), respectively. The structures of the newly synthesized compounds have been confirmed on the basis of elemental analysis and spectral studies (IR, 1H NMR, 13C NMR, MS). Their antimicrobial activities against some bacteria and yeasts were investigated. The analgesic activity of all compounds was performed with two pharmacological tests: the writhing test induced with acetic acid and hot‐plate test. The results showed that triazole 7 had the best antimicrobial activity against Bacillus cereus. In the chemical stimulus test, triazoles 6 and 7 were the most active compounds whereas in the hot‐plate test thiadiazoles 9 and 10 exhibited the highest analgesic activity. 相似文献
19.
Carmen Felicia Dascălu Beatrice Carmen Zelinschi Dana Ortansa Dorohoi Alexandru Ioan Cuza 《光谱学快报》2013,46(6):378-382
The transmission factor of multilayer Wood filters containing quartz and rutile layers was simulated in order to avoid the experimental trials for obtaining optical filters with predicted transmission. The main refractive indices of uniaxial crystals—quartz and rutile—were interferometrically determined and Cauchy constants were obtained by simulation. The transmission factor of optical devices consisting of quartz and rutile layers was simulated using the Maple Program. 相似文献
20.
Felicia Phei Lin Lim Lee Ming Hu Edward R.T. Tiekink Anton V. Dolzhenko 《Tetrahedron letters》2018,59(42):3792-3796
A highly selective and efficient method for the synthesis of 3,3′(5,5′)-polymethylene-bis(1H-1,2,4-triazol-5(3)-amines) was developed using the reaction of dicarboxylic acids and aminoguanidine in an aqueous medium. This one-pot, microwave-promoted method was proved to be scalable affording the desired products in good yields and purity. The scope of the method was successfully explored by the preparation of a small library of polymethylene-bis(1H-1,2,4-triazol-5(3)-amines) with different alkyl chain linkers. The annular prototropic tautomerism in the prepared compounds was studied using NMR spectroscopy and X-ray crystallography. 相似文献