全文获取类型
收费全文 | 252篇 |
免费 | 5篇 |
专业分类
化学 | 160篇 |
晶体学 | 7篇 |
力学 | 4篇 |
数学 | 49篇 |
物理学 | 37篇 |
出版年
2023年 | 1篇 |
2022年 | 4篇 |
2021年 | 8篇 |
2020年 | 2篇 |
2019年 | 4篇 |
2018年 | 4篇 |
2017年 | 2篇 |
2016年 | 7篇 |
2015年 | 1篇 |
2014年 | 5篇 |
2013年 | 9篇 |
2012年 | 14篇 |
2011年 | 18篇 |
2010年 | 7篇 |
2009年 | 12篇 |
2008年 | 10篇 |
2007年 | 16篇 |
2006年 | 12篇 |
2005年 | 15篇 |
2004年 | 15篇 |
2003年 | 17篇 |
2002年 | 9篇 |
2001年 | 4篇 |
2000年 | 3篇 |
1999年 | 2篇 |
1998年 | 5篇 |
1997年 | 2篇 |
1996年 | 7篇 |
1995年 | 6篇 |
1994年 | 2篇 |
1993年 | 4篇 |
1992年 | 5篇 |
1991年 | 3篇 |
1990年 | 4篇 |
1988年 | 3篇 |
1987年 | 5篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 4篇 |
1971年 | 1篇 |
1968年 | 1篇 |
1954年 | 2篇 |
排序方式: 共有257条查询结果,搜索用时 281 毫秒
31.
Filippi A Roselli G Renzi G Grandinetti F Speranza M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(9):2072-2078
The kinetics and the stereochemistry of the protonation-induced unimolecular isomerization of (S)-(+)-1-D(1)-3-(p-tolyl)butane have been investigated in the gas phase in the 100-160 degrees C range. The process leads to the almost exclusive formation of the relevant meta isomer with complete racemization and partial 1,2-H shift in the migrating sec-butyl group. These results, together with the relevant activation parameters, point to the occurrence of low-energy, tightly bound isomeric sec-butyl cation/toluene complexes of defined structure and stability along the isomerization coordinate. The existence and the eta(1)-type structure of these low-energy intermediate species are confirmed by ab initio calculations on closely related systems at the MP2(full)/6-311++G**//HF/6-31+G** level of theory. Their role in the relevant energy surface clearly emerges from the comparison of the present results with those concerning sec-butylation of toluene carried out under comparable experimental conditions. 相似文献
32.
A family of enantiomerically pure oxonium ions, that is O-protonated 1-aryl-1-methoxyethanes, has been generated in the gas phase by the (CH(3))(2)Cl(+) methylation of the corresponding 1-arylethanols. Some information on their reaction dynamics was obtained from a detailed kinetic study of their inversion of configuration and dissociation. The activation parameters of the inversion reaction are found to obey two different isokinetic relationships depending upon the nature and the position of the substituents in the oxonium ions. In contrast, the activation parameters of the dissociation reaction obey a single isokinetic relationship. The inversion and dissociation rate constants do not follow simple linear free-energy relationships. This complicated kinetic picture has been rationalized in terms of different activation dynamics in gaseous CH(3)Cl, which, in turn, determine the reaction dynamics of the oxonium ion. When the predominant activation of the oxonium ion involves resonant energy exchange from the 1015 cm(-1) CH(3) rocking mode of unperturbed CH(3)Cl, the inversion reaction proceeds through the dynamically most favored TS, characterized by the unassisted C(alpha)bond;O bond elongation. When, instead, the activation of the oxonium ions requires the formation of an intimate encounter complex with CH(3)Cl, the inversion reaction takes place via the energetically most favored TS, characterized by multiple coordination of the CH(3)OH moiety with the H(alpha) and H(ortho) atoms of the benzylic residue. The activation dynamics operating in the intimate encounter complex with CH(3)Cl is also responsible for the dissociation of most selected oxonium ions. 相似文献
33.
34.
35.
Massimiliano Aschi Caterina Fraschetti Antonello Filippi Maurizio Speranza 《Journal of mass spectrometry : JMS》2009,44(7):1038-1046
The nature of the ionic species, formed by electrospray ionization (ESI) of Co(NO3)2/CH3OH solutions with a pair of aminoalcohols W and Y, has been investigated by mass spectrometric and computational methods. Collision induced dissociation (CID) of ions, formally corresponding to the [WYCoNO3]+ structures, yields fragmentation patterns which reflect not only the expected [WYCoNO3]+ connectivity but also that of other isomeric structures. Formation of these latter species is observed only in the presence of a tertiary aminoalcohol, like N‐methylpseudoephedrine. The CID patterns are found to be strongly dependent on the chemical form (whether the free aminoalcohol or its hydrochloride), the configuration, and the relative concentration of the W and Y aminoalcohols. This variability parallels the results of classical MD (molecular dynamics) simulations of the [WYCoNO3]+ adducts which show a drastic alteration of the mechanical–dynamical features of the adducts by simply changing the charge state of W and/or Y, their absolute configuration, or by removing the solvent. The present experimental and computational study confirms the observation of fast stereoselective reactions in ESI nanodroplets before their evaporation and warns against any automatic correlation between the ESI spectrum of an analyte and its structure in solution. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
36.
Salen-complex-mediated formation of cyclic carbonates by cycloaddition of CO2 to epoxides 总被引:1,自引:0,他引:1
Decortes A Castilla AM Kleij AW 《Angewandte Chemie (International ed. in English)》2010,49(51):9822-9837
Metal complexes of salen ligands are an important class of compounds, and they have been widely studied in the past. Among their successful catalytic applications, the synthesis of cyclic carbonates by the coupling reaction of epoxides with CO(2) has received increased attention; this is mostly due to the importance of using a greenhouse gas as a feedstock for the synthesis of useful molecules. Herein the most relevant past and present research surrounding this topic is presented. 相似文献
37.
Amol Date Patrizia Pasini Sylvia Daunert 《Analytical and bioanalytical chemistry》2010,398(1):349-356
Bacterial whole-cell biosensing systems provide important information about the bioavailable amount of target analytes. They
are characterized by high sensitivity and specificity/selectivity along with rapid response times and amenability to miniaturization
as well as high-throughput analysis. Accordingly, they have been employed in various environmental and clinical applications.
The use of spore-based sensing systems offers the unique advantage of long-term preservation of the sensing cells by taking
advantage of the environmental resistance and ruggedness of bacterial spores. In this work, we have incorporated spore-based
whole-cell sensing systems into centrifugal compact disk (CD) microfluidic platforms in order to develop a portable sensing
system, which should enable the use of these hardy sensors for fast on-field analysis of compounds of interest. For that,
we have employed two spore-based sensing systems for the detection of arsenite and zinc, respectively, and evaluated their
analytical performance in the miniaturized microfluidic format. Furthermore, we have tested environmental and clinical samples
on the CD microfluidic platforms using the spore-based sensors. Germination of spores and quantitative response to the analyte
could be obtained in 2.5–3 h, depending on the sensing system, with detection limits of 1 × 10−7 M for arsenite and 1 × 10−6 M for zinc in both serum and fresh water samples. Incorporation of spore-based whole-cell biosensing systems on microfluidic
platforms enabled the rapid and sensitive detection of the analytes and is expected to facilitate the on-site use of such
sensing systems. 相似文献
38.
Antonio Pasini 《Geometriae Dedicata》1990,34(1):35-56
We give some contributions to the classification of geometries belonging to the following diagram: (Af. Cn) 相似文献
39.
[2.2]Paracyclophanes, incorporating functional groups in the aliphatic bridges, suitable for elimination to give [2.2]paracyclophanedienes, are synthesized through a novel approach. It relies on a double Pummerer rearrangement on dithiacyclophane precursors, followed by ring contraction through a photochemical sulfur extrusion, and it is compatible with aryl moieties possessing very different electronic properties. 相似文献
40.
Rigamonti L Rusconi M Forni A Pasini A 《Dalton transactions (Cambridge, England : 2003)》2011,40(39):10162-10173
One bond Pt-P coupling constants (1)J(PtP) of a series of cationic complexes [PtXL(PPh(3))(2)](+) (X = NO(3), Cl, Br, I; L = 4-Z-pyridines, Z = electron withdrawing or releasing groups, 4a-k; or X = Cl, L = NH(3), PhCH(2)NH(2) and (i)PrNH(2), 5a-c) have been used to establish the trans and cis influence sequences of X and pyridines. The crystal structure of compound 4f(BF(4)) with Z = (t)Bu has been resolved. In the pyridine complexes 4a-d (Z = H, variable X), both the trans and cis influence series of the anionic ligands X decrease along the same sequence I > Br > Cl > NO(3), as previously found for [PtX(PPh(3))(3)](+) (X = NO(3), Cl, Br, I, 3a-d), however in 4a-d the cis influence turns out to be more important than the trans. On the contrary, in [PtCl(4-Z-py)(PPh(3))(2)](+) (4b,e-k) the sequence of the trans influence of the 4-Z-pyridines is opposite to that of the cis, the latter being Z = CN > CHO > Br > PhCO > H > Me > (t)Bu > NH(2), i.e. the most basic pyridine gives rise to the lowest cis influence. This correlation was found to hold also for complexes 5a-c (L = amines). All the observed trends have been fully reproduced by B3LYP/def2-SVP DFT calculations, by looking at the relevant optimized bond lengths of selected complexes of type 3, 4 and 5. Subsequent evaluation of the atomic charges, by resorting to two independent methods, i.e., the Natural Bond Order analysis of the wavefunction and the Bader's Quantum Theory of Atoms in Molecules, allowed for rationalization of the origin of the cis and trans influences. The negative charge on the nitrogen atoms of free pyridines becomes more negative upon protonation and even more so when coordinated to the [PtCl(PPh(3))(2)](+) moiety. The least negatively charged nitrogen atom of coordinated pyridines is that of 4-CN-py (the highest cis influencing pyridine derivative), which gives rise to the lowest positive charge on Pt, confirming the relationship between the lowering of the charge on the metal ion and a high cis influence. The trans influence can be described in terms of competition between the charges on the two trans donor atoms. In contrast with the behaviour of pyridines, the positive charge on the phosphorous atom of free PPh(3) increases upon coordination to Pt(II), moreover the PPh(3) ligands acquire a substantial positive charge, thus efficiently delocalising the charge of the cationic complex. 相似文献