全文获取类型
收费全文 | 971篇 |
免费 | 27篇 |
国内免费 | 7篇 |
专业分类
化学 | 681篇 |
晶体学 | 3篇 |
力学 | 21篇 |
数学 | 154篇 |
物理学 | 146篇 |
出版年
2023年 | 7篇 |
2022年 | 33篇 |
2021年 | 42篇 |
2020年 | 29篇 |
2019年 | 27篇 |
2018年 | 13篇 |
2017年 | 14篇 |
2016年 | 43篇 |
2015年 | 20篇 |
2014年 | 45篇 |
2013年 | 68篇 |
2012年 | 60篇 |
2011年 | 87篇 |
2010年 | 50篇 |
2009年 | 37篇 |
2008年 | 48篇 |
2007年 | 55篇 |
2006年 | 47篇 |
2005年 | 43篇 |
2004年 | 41篇 |
2003年 | 23篇 |
2002年 | 26篇 |
2001年 | 13篇 |
2000年 | 7篇 |
1999年 | 6篇 |
1998年 | 7篇 |
1997年 | 3篇 |
1996年 | 7篇 |
1995年 | 4篇 |
1994年 | 3篇 |
1991年 | 3篇 |
1984年 | 2篇 |
1983年 | 2篇 |
1981年 | 3篇 |
1980年 | 2篇 |
1977年 | 5篇 |
1939年 | 2篇 |
1937年 | 5篇 |
1936年 | 4篇 |
1935年 | 2篇 |
1934年 | 9篇 |
1933年 | 6篇 |
1932年 | 4篇 |
1931年 | 4篇 |
1930年 | 2篇 |
1929年 | 5篇 |
1912年 | 3篇 |
1911年 | 2篇 |
1906年 | 3篇 |
1905年 | 2篇 |
排序方式: 共有1005条查询结果,搜索用时 15 毫秒
41.
Weiyu Qian Dr. Raffael C. Wende Prof. Dr. Peter R. Schreiner Dr. Artur Mardyukov 《Angewandte Chemie (International ed. in English)》2023,62(23):e202300761
The interstellar candidate phosphorus mononitride PN, a metastable species, was generated through high-vacuum flash pyrolysis of (o-phenyldioxyl)phosphinoazide in cryogenic matrices. Although the PN stretching band was not directly detected because of its low infrared intensity and possible overlaps with other strong bands, o-benzoquinone, carbon monoxide, and cyclopentadienone as additional fragmentation products were clearly identified. Moreover, an elusive o-benzoquinone-PN complex formed when (o-phenyldioxyl)phosphinoazide was exposed to UV irradiation at λ=254 nm. Its recombination to (o-phenyldioxyl)-λ5-phosphinonitrile was observed upon irradiation with the light at λ=523 nm, which demonstrates for the first time the reactivity of PN towards an organic molecule. Energy profile computations at the B3LYP/def2-TZVP density functional theory level reveal a concerted mechanism. To provide further evidence, UV/Vis spectra of the precursor and the irradiation products were recorded and agree well with time-dependent DFT computations. 相似文献
42.
Ana Ruas Angelica Graa Joana Marto Lídia Gonalves Ana Oliveira Alexandra Nogueira da Silva Madalena Pimentel Artur Mendes Moura Ana Teresa Serra Ana Cristina Figueiredo Helena M. Ribeiro 《Molecules (Basel, Switzerland)》2022,27(11)
Essential oils (EOs) and hydrolates (Hds) are natural sources of biologically active ingredients with broad applications in the cosmetic industry. In this study, nationally produced (mainland Portugal and Azores archipelago) EOs (11) and Hds (7) obtained from forest logging and thinning of Eucalyptus globulus, Pinus pinaster, Pinus pinea and Cryptomeria japonica, were chemically evaluated, and their bioactivity and sensorial properties were assessed. EOs and Hd volatiles (HdVs) were analyzed by GC-FID and GC-MS. 1,8-Cineole was dominant in E. globulus EOs and HdVs, and α- and β-pinene in P. pinaster EOs. Limonene and α-pinene led in P. pinea and C. japonica EOs, respectively. P. pinaster and C. japonica HVs were dominated by α-terpineol and terpinen-4-ol, respectively. The antioxidant activity was determined by DPPH, ORAC and ROS. C. japonica EO showed the highest antioxidant activity, whereas one of the E. globulus EOs showed the lowest. Antimicrobial activity results revealed different levels of efficacy for Eucalyptus and Pinus EOs while C. japonica EO showed no antimicrobial activity against the selected strains. The perception and applicability of emulsions with 0.5% of EOs were evaluated through an in vivo sensory study. C. japonica emulsion, which has a fresh and earthy odour, was chosen as the most pleasant fragrance (60%), followed by P. pinea emulsion (53%). In summary, some of the studied EOs and Hds showed antioxidant and antimicrobial activities and they are possible candidates to address the consumers demand for more sustainable and responsibly sourced ingredients. 相似文献
43.
Silva AM Filipe P Seixas RS Pinto DC Patterson LK Hug GL Cavaleiro JA Mazière JC Santus R Morlière P 《The journal of physical chemistry. B》2008,112(37):11456-11461
In micellar solutions, one-electron reduction of (*)O 2 (-) radical-anions by 3-alkylpolyhydroxyflavones (FnH) with alkyl chains of n = 1, 4, 6, 10 carbons produces phenoxyl radicals ( (*)Fn) identical to those obtained by one-electron oxidation by (*)Br 2 (-) radical-anions or by repair of tryptophan radicals. In cetyltrimethylammonium bromide (CTAB), F1H localizes in the Stern layer, and alkyl chains of other FnH solubilize in the hydrophobic interior, interacting with cetyl tails. This interaction produces more compact micelles with lower intramicellar fluidity, as suggested by the increase in the pseudo-first-order rate constant of (*)Fn formation ( k 1) from approximately 390 s (-1) for n = 1 to 610 s (-1) for n = 10, leading to an intramicellar bimolecular rate constant of 1 x 10 (5) M (-1) s (-1). Additionally, (*)F1 and (*)F4 decay by intermicellar bimolecular reaction (2 k = 20 and 2 x 10 (5) M (-1) s (-1), respectively) whereas other (*)Fn radicals are stable over seconds due to increased localization with regards to the Stern layer. In contrast, the thick uncharged hydrophilic palisade layer and the compact hydrophobic core of Triton X100 micelles are responsible for a much higher microviscosity resulting in a decrease in k 1 from approximately 15.6 s (-1) for n = 1 to 9.6 s (-1) for n = 10. 相似文献
44.
Experimental data of excess molar enthalpy of binary mixtures of acetonitrile + diethylamine or S-butylamine mixtures as a function of composition at 288.15, 293.15, 298.15 and 303.15 K at atmospheric pressure have been used to calculate excess partial molar enthalpy and partial molar enthalpy of each component as a function of composition as well as partial molar enthalpy properties at infinite dilution. The Flory and Prigogine–Flory–Patterson (PFP) theories were applied to correlate the data. The results of the calculations as well as the influence of temperature and isomers chain on the partial molar enthalpy properties are discussed. 相似文献
45.
Enhanced Photocatalytic Activity of MIL‐125 by Post‐Synthetic Modification with CrIII and Ag Nanoparticles 下载免费PDF全文
Reda M. Abdelhameed Prof. Dr. Mário M. Q. Simões Prof. Dr. Artur M. S. Silva Prof. Dr. João Rocha 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(31):11072-11081
NH2‐MIL‐125, [Ti8O8(OH)4(bdc‐NH2)6] (bdc2?=1,4‐benzene dicarboxylate) is a highly porous metal–organic framework (MOF) that has a band gap lying within the ultraviolet region at about 2.6 eV. The band gap may be reduced by a suitable post‐synthetic modification of the nanochannels using conventional organic chemistry methods. Here, it is shown that the photocatalytic activity of NH2‐MIL‐125 in the degradation of methylene blue under visible light is remarkably augmented by post‐synthetic modification with acetylacetone followed by CrIII complexation. The latter metal ion extends the absorption from the ultraviolet to the visible light region (band gap 2.21 eV). The photogenerated holes migrate from the MOF’s valence band to the CrIII valence band, promoting the separation of holes and electrons and increasing the recombination time. Moreover, it is shown that the MOF’s photocatalytic activity is also much improved by doping with Ag nanoparticles, formed in situ by the reduction of Ag+ with the acetylacetonate pendant groups (the resulting MOF band gap is 2.09 eV). Presumably, the Ag nanoparticles are able to accept the MOF’s photogenerated electrons, thus avoiding electron–hole recombination. Both, the Cr‐ and Ag‐bearing materials are stable under photocatalytic conditions. These findings open new avenues for improving the photocatalytic activity of MOFs. 相似文献
46.
Vladimir Strezov Artur Ziolkowski Tim J. Evans Peter F. Nelson 《Journal of Thermal Analysis and Calorimetry》2010,100(3):901-907
Ironmaking involves reduction of iron ores to metallic iron using coke, coal or gas as reductants. Although different iron ore reduction processes exist, prior to each reduction type, commonly, the hydroxyl and clay materials present in the iron ores undergo decomposition as a first stage. The mass loss during decomposition of these materials is termed as Loss on Ignition (LOI). The aim of this work is to apply a computer aided thermoanalytical technique to evaluate five different iron ore types during decomposition of the LOI matter and determine associated decomposition temperature ranges and heats of reactions. Fourier Transform Infrared (FTIR) spectroscopy and thermogravimetric analysis (TG) were also incorporated to support the analysis interpretation. Three distinctive temperature ranges of decomposition of iron ore LOI matter were detected. The first region was associated with dehydration of the hygroscopic moisture at a temperature range between 100 and 150 °C. The second region occurred at a temperature range between 260 and 425 °C during which strongly bonded water was released and the OH groups associated with primarily iron oxyhydroxides were fractured. The third range, which occurred at a temperature range of 530 and 605 °C, was related to decomposition of the aluminosilicate clay materials. 相似文献
47.
Deperasińska I Gryko DT Karpiuk E Kozankiewicz B Makarewicz A Piechowska J 《The journal of physical chemistry. A》2012,116(9):2109-2116
Absorption, fluorescence, and fluorescence excitation spectra of 12-hydroxy-1-azaperylene (HAP) and 1-azaperylene were studied in n-alkane matrices at 5 K. Two stable tautomers of HAP, each of them in n-nonane embedded in two sites, were identified and attributed to the enol and keto forms. Theoretical calculations of the energy and vibrational structure of the spectra suggest that tautomer A, with the (0, 0) transition energy at 18,980 ± 10 cm(-1) (and 19,060 ± 10 cm(-1) in the high energy site), should be identified as the keto form, whereas tautomer B, with the (0, 0) energy at 19,200 ± 20 cm(-1) (19,290 ± 20 cm(-1)), as the enol form. Observation of absorption and fluorescence of both tautomeric forms and lack of large Stokes shift of fluorescence of the keto form classify HAP as the limiting case of the excited-state intramolecular proton transfer system. 相似文献
48.
Relativistic density functional theory (DFT) calculations of nuclear spin-spin coupling constants and shielding constants have been performed for selected transition metal (11th and 12th group of periodic table) and thallium cyanides. The calculations have been carried out using zeroth-order regular approximation (ZORA) Hamiltonian and four-component Dirac-Kohn-Sham (DKS) theory with different nonrelativistic exchange-correlation functionals. Two recent approaches for representing the magnetic balance (MB) between the large and small components of four-component spinors, namely, mDKS-RMB and sMB, have been employed for shielding tensor calculations and their results have been compared. Relativistic effects have also been analysed in terms of scalar and spin-orbit contributions at the two-component level of theory, including discussion of heavy-atom-on-light-atom effects for (1)J(CN), σ(C), and σ(N). The results for molecules containing metals from 4th row of periodic table show that relativistic effects for them are small (especially for spin-spin coupling constants). The biggest effects are observed for the 6th row where nonrelativistic theory reproduces only about 50%-70% of the two-component ZORA results for (1)J(MeC) and about 75% for heavy metal shielding constants. It is important to employ a full Dirac picture for calculations of heavy metal shielding constants, since ZORA reproduces only 75%-90% of the DKS results. Smaller discrepancies between ZORA-DFT and DKS are observed for nuclear spin-spin coupling constants. No significant differences are observed between the results obtained using mDKS-RMB and sMB approaches for magnetic balance in four-component calculations of the shielding constants. 相似文献
49.
Garrido JM Marques MP Silva AM Macedo TR Oliveira-Brett AM Borges F 《Analytical and bioanalytical chemistry》2007,388(8):1799-1808
The drugs of abuse cocaine (C), heroin (H), and morphine (M) have been studied to enable understanding of the occurrence of
cocaine–opioid interactions at a molecular level. Electrochemical, Raman, and NMR studies of the free drugs and their mixtures
were used to study drug–drug interactions. The results were analyzed using data obtained from quantum-mechanical calculations.
For the cocaine–morphine mixture (C–MH), formation of a binary complex was detected; this involved the 3-phenolic group and
the heterocyclic oxygen of morphine and the carbonyl oxygen and the methyl protons of cocaine’s methyl ester group. NMR studies
conducted simultaneously also revealed C–MH binding geometry consistent with theoretical predictions and with electrochemical
and vibrational spectroscopy results. These results provide evidence for the occurrence of a cocaine–morphine interaction,
both in the solid state and in solution, particularly for the hydrochloride form. A slight interaction, in solution, was also
detected by NMR for the cocaine–heroin mixture.
Figure "Schematic representation of the proposed model for cocaine:morphine salt interaction" 相似文献
50.
Artur R. Stefankiewicz Jean‐Marie Lehn Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(11):2500-2503
A sensitive magnetic nanoprobe : Hydrogen‐bonding interactions are reflected with great sensitivity in the 1H NMR spectra of a high‐spin multinuclear Fe4II [2×2] grid‐type complex (see scheme) and the measured shifts can be used to evaluate the hydrogen‐bond donating ability. The grid complex also represents a prototype of a very sensitive magnetic nanoreceptor for the detection of very small changes around a magnetic center.