全文获取类型
收费全文 | 1093篇 |
免费 | 26篇 |
国内免费 | 4篇 |
专业分类
化学 | 605篇 |
晶体学 | 3篇 |
力学 | 40篇 |
数学 | 316篇 |
物理学 | 159篇 |
出版年
2023年 | 10篇 |
2022年 | 28篇 |
2021年 | 33篇 |
2020年 | 40篇 |
2019年 | 23篇 |
2018年 | 26篇 |
2017年 | 19篇 |
2016年 | 40篇 |
2015年 | 28篇 |
2014年 | 36篇 |
2013年 | 61篇 |
2012年 | 79篇 |
2011年 | 95篇 |
2010年 | 70篇 |
2009年 | 52篇 |
2008年 | 54篇 |
2007年 | 62篇 |
2006年 | 56篇 |
2005年 | 55篇 |
2004年 | 50篇 |
2003年 | 24篇 |
2002年 | 26篇 |
2001年 | 21篇 |
2000年 | 12篇 |
1999年 | 16篇 |
1998年 | 10篇 |
1997年 | 5篇 |
1996年 | 13篇 |
1995年 | 10篇 |
1994年 | 4篇 |
1993年 | 6篇 |
1992年 | 8篇 |
1991年 | 4篇 |
1990年 | 9篇 |
1989年 | 2篇 |
1988年 | 4篇 |
1987年 | 2篇 |
1986年 | 2篇 |
1985年 | 8篇 |
1984年 | 1篇 |
1983年 | 3篇 |
1982年 | 5篇 |
1981年 | 4篇 |
1980年 | 1篇 |
1979年 | 3篇 |
1978年 | 1篇 |
1968年 | 1篇 |
1932年 | 1篇 |
排序方式: 共有1123条查询结果,搜索用时 15 毫秒
141.
Synthesis and characterization of chiral poly(alkyl isocyanates) by coordination polymerization using a chiral half‐titanocene complex 下载免费PDF全文
Ioannis Choinopoulos Spyros Koinis Marinos Pitsikalis 《Journal of polymer science. Part A, Polymer chemistry》2015,53(18):2141-2151
A new chiral half‐titanocene complex, [CpTiCl2(O‐(S)?2‐Bu)], is synthesized and characterized by 1H and 13C NMR spectroscopy. This complex is employed for the coordination polymerization of n‐butyl and n‐hexyl‐ isocyanate leading to chiral polymers, as revealed by their CD spectra. Only the left‐handed helix is produced, due to the chiral (S)?2‐butoxy group, which is bound to the polymer chain end. The polymerization of 3‐(triethoxysilyl)propyl isocyanate produces less soluble polymers. On the other hand, phenyl isocyanate reacts slowly with the complex leading quantitatively and selectively to triphenyl isocyanurate. 2‐Ethylhexyl isocyanate is slowly and selectively cyclotrimerized in the presence of the half‐titanocene complex. However, a statistical copolymer of 2‐ethylhexyl isocyanate and hexyl isocyanate is produced. The reaction of benzyl isocyanate with the complex leads to a mixture of low molecular weight polymer and cyclotrimer. The polymers are characterized using SEC, NMR, and CD spectroscopy and their thermal properties are investigated by TGA/DSC analysis. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2141–2151 相似文献
142.
Eman Al-Abbad Alakhras Fadi Anastopoulos Ioannis Das Debashis AL-Arfaj Ahlam Ouerfelli Noureddine Hosseini-Bandegharaei Ahmad 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2020,94(4):748-755
Russian Journal of Physical Chemistry A - Sorption of Ni(II) ions from liquid effluents utilizing chemically modified chitosan; (vanillin, polymer I) and (ortho-vanillin, polymer II) is studied... 相似文献
143.
Ioannis Haloulos Dimitrios Theodorou Ypatia Zannikou Fanourios Zannikos 《Accreditation and quality assurance》2016,21(3):203-210
Fuel adulteration and cross-contamination lead to low-quality fuel products, which may cause increased environmental pollution, loss of taxes and engine problems. An establishment of a quality monitoring mechanism based on laboratory measurements may reveal problematic areas of the fuel supply chain. For the purposes of this work, 97 unleaded petrol samples were measured in order to quantify mass concentration of quinizarin, a substance used in Greece to easily mark the presence of 95 Research Octane Number unleaded petrol in other types of automotive fuels. The samples were obtained from petroleum retail stations selling different brands of fuels and located in different geographic regions of Greece. Statistical analysis of the results revealed quinizarin mass concentrations below the 3 mg L?1 legislation specification limit and significant differences between brands and geographic regions, which may attributed to the structure of the fuel supply chain in Greece in combination with quinizarin properties and way of handling. Moreover, certain approaches were used for the calculation of decision limits for assessing compliance or non-compliance. These approaches take measurement reproducibility or estimated in-house uncertainty into account, in order to minimize the probability of false rejection. 相似文献
144.
Prediction of 195Pt NMR chemical shifts of dissolution products of H2[Pt(OH)6] in nitric acid solutions by DFT methods: how important are the counter‐ion effects? 下载免费PDF全文
Athanassios C. Tsipis Ioannis N. Karapetsas 《Magnetic resonance in chemistry : MRC》2016,54(8):656-664
195Pt NMR chemical shifts of octahedral Pt(IV) complexes with general formula [Pt(NO3)n(OH)6 ? n]2?, [Pt(NO3)n(OH2)6 ? n]4 ? n (n = 1–6), and [Pt(NO3)6 ? n ? m(OH)m(OH2)n]?2 + n ? m formed by dissolution of platinic acid, H2[Pt(OH)6], in aqueous nitric acid solutions are calculated employing density functional theory methods. Particularly, the gauge‐including atomic orbitals (GIAO)‐PBE0/segmented all‐electron relativistically contracted–zeroth‐order regular approximation (SARC–ZORA)(Pt) ∪ 6–31G(d,p)(E)/Polarizable Continuum Model computational protocol performs the best. Excellent second‐order polynomial plots of δcalcd(195Pt) versus δexptl(195Pt) chemical shifts and δcalcd(195Pt) versus the natural atomic charge QPt are obtained. Despite of neglecting relativistic and spin orbit effects the good agreement of the calculated δ 195Pt chemical shifts with experimental values is probably because of the fact that the contribution of relativistic and spin orbit effects to computed σiso 195Pt magnetic shielding of Pt(IV) coordination compounds is effectively cancelled in the computed δ 195Pt chemical shifts, because the relativistic corrections are expected to be similar in the complexes and the proper reference standard used. To probe the counter‐ion effects on the 195Pt NMR chemical shifts of the anionic [Pt(NO3)n(OH)6 ? n]2? and cationic [Pt(NO3)n(OH2)6 ? n]4 ? n (n = 0–3) complexes we calculated the 195Pt NMR chemical shifts of the neutral (PyH)2[Pt(NO3)n(OH)6 ? n] (n = 1–6; PyH = pyridinium cation, C5H5NH+) and [Pt(NO3)n(H2O)6 ? n](NO3)4 ? n (n = 0–3) complexes. Counter‐anion effects are very important for the accurate prediction of the 195Pt NMR chemical shifts of the cationic [Pt(NO3)n(OH2)6 ? n]4 ? n complexes, while counter‐cation effects are less important for the anionic [Pt(NO3)n(OH)6 ? n]2? complexes. The simple computational protocol is easily implemented even by synthetic chemists in platinum coordination chemistry that dispose limited software availability, or locally existing routines and knowhow. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
145.
DFT calculations of 1H NMR chemical shifts, using various functionals and basis sets, the conductor-like polarizable continuum model and discrete solute-solvent hydrogen bond interactions have been used to derive the solution structures of methyl salicylate and methyl 2,5-dihydroxybenzoate. We demonstrate that very good agreement between experimental and computed 1H NMR chemical shifts can be obtained for various basis sets. The DFT structures in solution were compared with the recently reported X-ray structure, solved by the crystalline-sponge method, of the methyl salicylate and the single-crystal X-ray structure of methyl 2,5-dihydroxybenzoate. It is demonstrated that the information provided by 1H NMR chemical shifts about the solution structure is significantly more precise than that obtained by the single-crystal X-ray and the crystalline-sponge methods. 相似文献
146.
Ioannis Kontoyiannis 《Journal of Theoretical Probability》1998,11(3):795-811
Let
be a discrete-valued stationary ergodic process distributed according to P and let x=(..., x
–1, x
0, x
1,...) denote a realization from X. We investigate the asymptotic behavior of the recurrence time R
n defined as the first time that the initial n-block
reappears in the past of x. We identify an associated random walk,
on the same probability space as X, and we prove a strong approximation theorem between log R
n and
. From this we deduce an almost sure invariance principle for log R
n. As a byproduct of our analysis we get unified proofs for several recent results that were previously established using methods from ergodic theory, the theory of Poisson approximation and the analysis of random trees. Similar results are proved for the waiting time W
n defined as the first time until the initial n-block from one realization first appears in an independent realization generated by the same (or by a different) process. 相似文献
147.
Ali Azmy Shunran Li Giasemi K. Angeli Claire Welton Parth Raval Min Li Nourdine Zibouche Lukasz Wojtas G. N. Manjunatha Reddy Peijun Guo Pantelis N. Trikalitis Ioannis Spanopoulos 《Angewandte Chemie (International ed. in English)》2023,62(12):e202218429
In this work we report a strategy for generating porosity in hybrid metal halide materials using molecular cages that serve as both structure-directing agents and counter-cations. Reaction of the [2.2.2] cryptand (DHS) linker with PbII in acidic media gave rise to the first porous and water-stable 2D metal halide semiconductor (DHS)2Pb5Br14. The corresponding material is stable in water for a year, while gas and vapor-sorption studies revealed that it can selectively and reversibly adsorb H2O and D2O at room temperature (RT). Solid-state NMR measurements and DFT calculations verified the incorporation of H2O and D2O in the organic linker cavities and shed light on their molecular configuration. In addition to porosity, the material exhibits broad light emission centered at 617 nm with a full width at half-maximum (FWHM) of 284 nm (0.96 eV). The recorded water stability is unparalleled for hybrid metal halide and perovskite materials, while the generation of porosity opens new pathways towards unexplored applications (e.g. solid-state batteries) for this class of hybrid semiconductors. 相似文献
148.
Tzeli D Theodorakopoulos G Petsalakis ID 《The journal of physical chemistry. A》2008,112(37):8858-8867
The electronic and geometric structures of gallium dinitride GaN 2, and gallium tetranitride molecules, GaN 4, were systematically studied by employing density functional theory and perturbation theory (MP2, MP4) in conjunction with the aug-cc-pVTZ basis set. In addition, for the ground-state of GaN 4( (2)B 1) a density functional theory study was carried out combining different functionals with different basis sets. A total of 7 minima have been identified for GaN 2, while 37 structures were identified for GaN 4 corresponding to minima, transition states, and saddle points. We report geometries and dissociation energies for all the above structures as well as potential energy profiles, potential energy surfaces and bonding mechanisms for some low-lying electronic states of GaN 4. The dissociation energy of the ground-state GaN 2 ( X (2)Pi) is 1.1 kcal/mol with respect to Ga( (2)P) + N 2( X (1)Sigma g (+)). The ground-state and the first two excited minima of GaN 4 are of (2)B 1( C 2 v ), (2)A 1( C 2 v , five member ring), and (4)Sigma g (-)( D infinityh ) symmetry, respectively. The dissociation energy ( D e) of the ground-state of GaN 4, X (2)B 1, with respect to Ga( (2)P) + 2 N 2( X (1)Sigma g (+)), is 2.4 kcal/mol, whereas the D e of (4)Sigma g (-) with respect to Ga( (4)P) + 2 N 2( X (1)Sigma g (+)) is 17.6 kcal/mol. 相似文献
149.
Ioannis K. Argyros 《Journal of Applied Mathematics and Computing》2008,27(1-2):339-344
The semilocal convergence of a numerical algorithm for solving the algebraic Ricatti equation with multiparameter singularly perturbed systems is investigated here. We show that under weaker hypotheses and the some computational cost than in Mukaidani et al. (J. Math. Anal. Appl. 267:209–234, [2002]) finer estimates on the distances involved and a more precise information on the location of the solution can be obtained. 相似文献
150.
Daniilia S Minopoulou E Andrikopoulos KS Karapanagiotis I Kourouklis GA 《Analytica chimica acta》2008,611(2):239-249
The purpose of this study is to clarify important details about a Cumaean Sibyl painting that is preserved in a private collection. This work, bearing neither signature nor date, has never undergone conservation. It was executed after Domenichino's Cumaean Sibyl, a work known to have been used as a model by many 18th century painters.Investigation of the anonymous artist's painting technique and identification of its constituent materials were facilitated by employing optical microscopy (OM), scanning electron microscopy (SEM/EDS), FTIR and microRaman spectroscopies and high performance liquid chromatography with diode array detection (HPLC-DAD). The painter's palette comprised lead white, yellow ochre, lead-antimonate yellow (Naples yellow), cinnabar, cochineal lake, madder lake, haematite, Prussian blue and carbon black.The detection of Prussian blue (synthesized in 1704 and widely used as artist's pigment after 1750) was decisive in establishing the work's authenticity for, as such, it cannot be attributed either to Domenico Zampieri (1581-1641) or to his apprentices. In addition, the identification of Naples yellow, which prevailed in the period from 1750 to 1850, supports this statement. Nevertheless, its elaborate painting technique strongly suggests an artist greatly influenced by the Renaissance masters. A comparison of its stylistic features with those of the Cumaean Sibyl of Angelica Kauffmann (1741-1807), a prolific 18th century artist known to have studied and to have copied Domenichino's Sibyl, reveals significant similarities between the two in composition and palette. The unsigned Sibyl, therefore, could well be by Kauffmann. 相似文献