全文获取类型
收费全文 | 410篇 |
免费 | 14篇 |
国内免费 | 3篇 |
专业分类
化学 | 225篇 |
晶体学 | 1篇 |
力学 | 23篇 |
数学 | 15篇 |
物理学 | 163篇 |
出版年
2023年 | 3篇 |
2022年 | 4篇 |
2021年 | 8篇 |
2020年 | 3篇 |
2019年 | 5篇 |
2018年 | 2篇 |
2016年 | 10篇 |
2015年 | 9篇 |
2014年 | 8篇 |
2013年 | 23篇 |
2012年 | 28篇 |
2011年 | 28篇 |
2010年 | 13篇 |
2009年 | 8篇 |
2008年 | 23篇 |
2007年 | 30篇 |
2006年 | 22篇 |
2005年 | 20篇 |
2004年 | 11篇 |
2003年 | 15篇 |
2002年 | 9篇 |
2001年 | 9篇 |
2000年 | 7篇 |
1999年 | 5篇 |
1997年 | 4篇 |
1996年 | 6篇 |
1995年 | 9篇 |
1994年 | 9篇 |
1993年 | 9篇 |
1992年 | 9篇 |
1991年 | 10篇 |
1990年 | 11篇 |
1989年 | 10篇 |
1988年 | 2篇 |
1987年 | 4篇 |
1985年 | 6篇 |
1984年 | 5篇 |
1983年 | 3篇 |
1982年 | 4篇 |
1981年 | 3篇 |
1980年 | 1篇 |
1979年 | 2篇 |
1978年 | 2篇 |
1977年 | 3篇 |
1976年 | 2篇 |
1974年 | 2篇 |
1973年 | 2篇 |
1972年 | 1篇 |
1971年 | 1篇 |
1970年 | 1篇 |
排序方式: 共有427条查询结果,搜索用时 15 毫秒
21.
DNA interchain cross-links formed by acrolein and crotonaldehyde 总被引:1,自引:0,他引:1
Kozekov ID Nechev LV Moseley MS Harris CM Rizzo CJ Stone MP Harris TM 《Journal of the American Chemical Society》2003,125(1):50-61
Acrolein and higher alpha,beta-unsaturated aldehydes are bifunctional genotoxins. The deoxyguanosine adduct of acrolein, 3-(2-deoxy-beta-d-erythro-pentofuranosyl)-5,6,7,8-tetrahydro-8-hydroxypyrimido[1,2-a]purin-10(3H)-one (8-hydroxy-1,N(2)-propanodeoxyguanosine, 2a), is a major DNA adduct formed by acrolein. The potential for oligodeoxynucleotide duplexes containing 2a to form interchain cross-links was evaluated by HPLC, CZE, MALDI-TOF, and melting phenomena. Interchain cross-links represent one of the most serious types of damage in DNA since they are absolute blocks to replication. In oligodeoxynucleotides containing the sequence 5'-dC-2a, cross-linking occurred in a slow, reversible manner to the extent of approximately 50%. Enzymatic digestion to form 3-(2-deoxy-beta-d-erythro-pentofuranosyl)-5,6,7,8-tetrahydro-8-(N(2)-2'-deoxyguanosinyl)pyrimido[1,2-a]purin-10(3H)one (5a) and reduction with NaCNBH(3) followed by enzymatic digestion to give 1,3-bis(2'-deoxyguanosin-N(2)-yl)propane (6a) established that cross-linking had occurred with the exocyclic amino group of deoxyguanosine. It is concluded that the cross-link is a mixture of imine and carbinolamine structures. With oligodeoxynucleotide duplexes containing the sequence 5'-2a-dC, cross-links were not detected by the techniques enumerated above. In addition, (15)N-(1)H HSQC and HSQC-filtered NOESY spectra carried out with a duplex having (15)N-labeling of the target amino group established unambiguously that a carbinolamine cross-link was not formed. The potential for interchain cross-link formation by the analogous crotonaldehyde adduct (2b) was evaluated in a 5'-dC-2b sequence. Cross-link formation was strongly dependent on the configuration of the methyl group at C6 of 2b. The 6R diastereomer of 2b formed a cross-link to the extent of 38%, whereas the 6S diastereomer cross-linked only 5%. 相似文献
22.
Andrea Guerrini Greta Varchi Rizzo Daniele Cristian Samorì Arturo Battaglia 《Tetrahedron》2007,63(33):7949-7969
Reactions of chiral (2S)-enolates of dioxolan-4-ones, derived from lactic, mandelic, and phenyllactic acids, with aliphatic (SS)- and (SR)-tert-butylsulfinyl aldimines afforded conformationally restrained C2-disubstituted N,O-orthogonally protected 3-amino-2-hydroxyalkanoates in the form of N-sulfinyl protected 1′-aminodioxolan-4-ones. The product distribution showed that there is significant kinetic selectivity, due to the presence of ‘matched’ and ‘mismatched’ components, between the (S)- or (R)-tert-butylsulfinyl aldimines and the (2S)-enolates of the 1,3-dioxolan-4-ones. Selective methoxide-induced removal of the acetal group of the N-sulfinyl-1′-aminodioxolanones yielded the corresponding N-sulfinyl protected methyl alkanoates. In addition, the selective acid-induced removal of the sulfinyl group of the N-sulfinyl-1′-aminodioxolanones provided the corresponding N-unprotected 1′-aminodioxolanones, whose base-induced cyclization afforded the corresponding β-lactams. 相似文献
23.
Particle-vibration coupling: Recent advances in microscopic calculations with the Skyrme Hamiltonian
In this contribution, we report some recent progress in our understanding of particle-vibration coupling (PVC) in nuclei. In particular, we first review the formal development that has allowed some of us to deduce the PVC equations within the Green’s functionmethod. Applications are then discussed, both in the case of single-particle states and giant resonances in magic nuclei. We also present a new model that extends the PVC ansatz and is meant to account for the complete low-lying spectra of odd nuclei. 相似文献
24.
Allostatic load as a complex clinical construct: A case‐based computational modeling approach
下载免费PDF全文
![点击此处可从《Complexity》网站下载免费的PDF全文](/ch/ext_images/free.gif)
J. Galen Buckwalter Brian Castellani Bruce Mcewen Arun S. Karlamangla Albert A. Rizzo Bruce John Kyle O'donnell Teresa Seeman 《Complexity》2016,21(Z1):291-306
Allostatic load (AL) is a complex clinical construct, providing a unique window into the cumulative impact of stress. However, due to its inherent complexity, AL presents two major measurement challenges to conventional statistical modeling (the field's dominant methodology): it is comprised of a complex causal network of bioallostatic systems, represented by an even larger set of dynamic biomarkers; and, it is situated within a web of antecedent socioecological systems, linking AL to differences in health outcomes and disparities. To address these challenges, we employed case‐based computational modeling (CBM), which allowed us to make four advances: (1) we developed a multisystem, 7‐factor (20 biomarker) model of AL's network of allostatic systems; (2) used it to create a catalog of nine different clinical AL profiles (causal pathways); (3) linked each clinical profile to a typology of 23 health outcomes; and (4) explored our results (post hoc) as a function of gender, a key socioecological factor. In terms of highlights, (a) the Healthy clinical profile had few health risks; (b) the pro‐inflammatory profile linked to high blood pressure and diabetes; (c) Low Stress Hormones linked to heart disease, TIA/Stroke, diabetes, and circulation problems; and (d) high stress hormones linked to heart disease and high blood pressure. Post hoc analyses also found that males were overrepresented on the High Blood Pressure (61.2%), Metabolic Syndrome (63.2%), High Stress Hormones (66.4%), and High Blood Sugar (57.1%); while females were overrepresented on the Healthy (81.9%), Low Stress Hormones (66.3%), and Low Stress Antagonists (stress buffers) (95.4%) profiles. © 2015 Wiley Periodicals, Inc. Complexity 21: 291–306, 2016 相似文献
25.
Angelika Baranowska-Łączkowska Berta Fernández Antonio Rizzo Filip Pawłowski 《Molecular physics》2015,113(13-14):1786-1793
Static and dynamic average polarisabilities and polarisability anisotropies of seven linear non-polar and polar molecules are calculated within the CCS, CC2, and CC3 approximations using a range of medium-sized basis sets: the polarised LPol-n (n = ds, dl, fs, fl), the aug-pc-n (n = 1, 2), the def2-SVPD, and -TZVPD basis sets. Reference values are obtained using a hierarchy of Dunning's (d-)aug-cc-pVXZ (X = D, T, Q, 5) basis sets. The results are discussed together with the available CCSD values in terms of basis set and correlation method errors, and their ratio. Detailed analysis shows that already the def2-SVPD basis set can be used in CCS polarisability calculations. When affordable, the slightly larger aug-pc-1 basis set is recommended, as it leads to significant reduction of basis set error. The def2-TZVPD, LPol-ds, and aug-pc-2 basis sets are optimal choice within the CC2 approximation, with the latter allowing to approach the CC2 basis set limit. The LPol-ds, -dl, and def2-TZVPD sets outperform the aug-cc-pVTZ set in average polarisability CCSD calculations, with the def2-TZVPD being competitive to other reduced-size sets also in determination of polarisability anisotropy. The aug-pc-2 basis is a particularly attractive choice for CCSD, giving the accuracy of aug-cc-pVQZ at a significantly reduced computational cost. The polarisability anisotropy is shown to be more computationally demanding than the average polarisability, in particular with respect to the accuracy of the correlation method and an accurate evaluation of this property requires at least the CCSD model. 相似文献
26.
Depending on their relative orientation, coupled oscillating carbonyl groups provide a VCD spectrum with a characteristic CO bond stretching region showing a strong bisignate VCD feature, which can be readily predicted adopting long available semiempirical methods. The extended coupled oscillator (ECO) formalism has been used to assign the absolute configuration of a recently synthesized chiral 3-substituted isoindolinone. The prediction of (S) configuration for the (−) enantiomer has been confirmed by quantum mechanical calculations. 相似文献
27.
E. Nava A. Rizzo R. Lorenzelli S. Salvi P. Bartolomei F. Padoani 《Journal of Radioanalytical and Nuclear Chemistry》2013,296(2):1163-1167
The strategic value of noble gas capability has been recently recognized by ENEA for the acquisition of data about anthropogenic activities. Within the framework of institutional agreements, a laboratory for measurement of radioactive noble gases is under construction for environmental analysis and for monitoring studies in connection with issues related to the nuclear fuel cycle to distinguish the anthropogenic contributions to the environment. This research is intended to contribute also to the international effort to support the comprehensive nuclear-test-ban treaty verification capability. The present work summarizes the status of implementation of the noble gas laboratory at the ENEA Brasimone research centre that is located in the north-centre part of Italy by the Brasimone lake at about 850 m altitude. The radionuclides of interest are the following four xenon radioisotopes: 131mXe, 133mXe, 133Xe and 135Xe. The noble gas system under development at ENEA has three separate components: air collection (sampling and adsorption), processing (gas extraction and purification) and measurement (gamma-ray spectrometry analysis). The separation of the sampling equipment from the analysis is seen as necessary for the effectiveness of extensive sampling campaigns, as required in monitoring programs. Refurbishment is currently under way to accommodate a more sensitive acquisition system. 相似文献
28.
Prof. Tiziana Benincori Dr. Valentina Bonometti Dr. Roberto Cirilli Prof. Patrizia R. Mussini Dr. Andrea Marchesi Prof. Marco Pierini Dr. Tullio Pilati Dr. Simona Rizzo Prof. Francesco Sannicolò 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(1):165-181
A series of tris‐aryl phosphane oxides existing as residual enantiomers or diastereoisomers with substituents on the aryl rings differing in size and electronic properties were synthesized and characterized. Their electronic properties were evaluated on the basis of their electrochemical oxidation and reduction potentials together with those of the corresponding “blade bromides” (i.e., the naphthalene derivatives displaying the same substitution pattern of the tris‐naphthyl phosphane oxide blades, with a bromo substituent where the phosphorus atom is located) determined by CV. The residual stereoisomeric phosphane oxides were isolated in a stereochemically pure state and were found to be highly configurationally stable at room temperature (stereoisomerization barriers of about 27 kcal mol?1). The chiroptical properties of the residual stereoisomers and the assignments of absolute configuration are discussed. The configurational stability of residual tris‐aryl phosphane oxides was found to be scarcely influenced by the electronic properties of the substituents present on the aromatic rings constituting the blades, while steric effects play the most relevant role. Detailed theoretical calculations are in agreement with the experimental results and also contribute to a rational interpretation of the stereodynamics of these systems. 相似文献
29.
A particle phi coupling to two photons couples also radiatively to charged particles, like protons. If the particle is a light scalar, this induced coupling leads to spin-independent non-Newtonian forces. We show that the experimental constraints on exotic, fifth-type forces lead to stringent constraints on the phigammagamma coupling. We discuss the impact on the recent PVLAS results and the role of paraphoton models introduced to solve the PVLAS-CAST puzzle. 相似文献
30.
Inherently Chiral Macrocyclic Oligothiophenes: Easily Accessible Electrosensitive Cavities with Outstanding Enantioselection Performances
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Prof. Francesco Sannicolò Prof. Patrizia R. Mussini Prof. Tiziana Benincori Dr. Roberto Cirilli Prof. Sergio Abbate Serena Arnaboldi Simone Casolo Dr. Ettore Castiglioni Prof. Giovanna Longhi Dr. Rocco Martinazzo Dr. Monica Panigati Dr. Marco Pappini Dr. Elsa Quartapelle Procopio Dr. Simona Rizzo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(47):15298-15302
Linear conjugated oligothiophenes of variable length and different substitution pattern are ubiquitous in technologically advanced optoelectronic devices, though limitations in application derive from insolubility, scarce processability and chain‐end effects. This study describes an easy access to chiral cyclic oligothiophenes constituted by 12 and 18 fully conjugated thiophene units. Chemical oxidation of an “inherently chiral” sexithiophene monomer, synthesized in two steps from commercially available materials, induces the formation of an elliptical dimer and a triangular trimer endowed with electrosensitive cavities of different tunable sizes. Combination of chirality with electroactivity makes these molecules unique in the current oligothiophenes literature. These macrocycles, which are stable and soluble in most organic solvents, show outstanding chiroptical properties, high circularly polarized luminescence effects and an exceptional enantiorecognition ability. 相似文献