全文获取类型
收费全文 | 8534篇 |
免费 | 296篇 |
国内免费 | 3篇 |
专业分类
化学 | 5011篇 |
晶体学 | 177篇 |
力学 | 187篇 |
数学 | 1692篇 |
物理学 | 1766篇 |
出版年
2023年 | 41篇 |
2022年 | 55篇 |
2021年 | 71篇 |
2020年 | 128篇 |
2019年 | 181篇 |
2018年 | 210篇 |
2017年 | 238篇 |
2016年 | 436篇 |
2015年 | 321篇 |
2014年 | 406篇 |
2013年 | 763篇 |
2012年 | 463篇 |
2011年 | 495篇 |
2010年 | 366篇 |
2009年 | 321篇 |
2008年 | 508篇 |
2007年 | 453篇 |
2006年 | 376篇 |
2005年 | 302篇 |
2004年 | 258篇 |
2003年 | 203篇 |
2002年 | 171篇 |
2001年 | 129篇 |
2000年 | 120篇 |
1999年 | 85篇 |
1998年 | 91篇 |
1997年 | 58篇 |
1996年 | 76篇 |
1995年 | 72篇 |
1994年 | 47篇 |
1993年 | 36篇 |
1992年 | 44篇 |
1991年 | 67篇 |
1990年 | 51篇 |
1989年 | 57篇 |
1988年 | 55篇 |
1987年 | 51篇 |
1986年 | 56篇 |
1985年 | 118篇 |
1984年 | 113篇 |
1983年 | 70篇 |
1982年 | 71篇 |
1981年 | 74篇 |
1980年 | 73篇 |
1979年 | 55篇 |
1978年 | 46篇 |
1977年 | 38篇 |
1976年 | 49篇 |
1975年 | 42篇 |
1973年 | 32篇 |
排序方式: 共有8833条查询结果,搜索用时 15 毫秒
991.
Rajca A Shiraishi K Boratyński PJ Pink M Miyasaka M Rajca S 《The Journal of organic chemistry》2011,76(20):8447-8457
Oxidation of diaryldiamine 2, a tetrahydrodiazapentacene derivative, provides diarylnitroxide diradical 1 accompanied by an intermediate nitroxide monoradical and a multitude of isolable diamagnetic products. DFT-computed tensors for EPR spectra and paramagnetic (1)H NMR isotropic shifts for nitroxide diradical 1 show good agreement with the experimental EPR spectra in rigid matrices and paramagnetic (1)H NMR spectra in solution, respectively. Examination of the diamagnetic products elucidates their formation via distinct pathways involving C-O bond-forming reactions, including Baeyer-Villiger-type oxidations. An unusual diiminoketone structure and two spirocyclic structures of the predominant diamagnetic products are confirmed by either X-ray crystallography or correlations between DFT-computed and experimental spectroscopic data such as (1)H, (13)C, and (15)N NMR chemical shifts and electronic absorption spectra. 相似文献
992.
Woźnica M Butkiewicz A Grzywacz A Kowalska P Masnyk M Michalak K Luboradzki R Furche F Kruse H Grimme S Frelek J 《The Journal of organic chemistry》2011,76(9):3306-3319
In the present work, the validity of the helicity rule relating the absolute configuration of the bridgehead carbon atom in bicyclic β-lactams to the sign of the 220 nm band observed in their electronic circular dichroism (ECD) spectra is examined for ring-expanded cephalosporin analogues. To this end, a series of model compounds with a seven-membered ring condensed with the β-lactam unit was synthesized. A key step of their synthesis was either the ring-closing metathesis (RCM) or the free radical cyclization leading to the seven-membered ring with an S, O, or C atom at the 6 position in the bicyclic skeleton. To investigate the scope and limitations of the simple, empirically established helicity rule, a combination of ECD spectroscopy, variable-temperature ECD measurements, X-ray analysis, and time-dependent density functional theory (TD-DFT) calculations was used. A comparison of the experimental ECD spectra with the spectra simulated by TD-DFT calculations gives a reasonable interpretation of the Cotton effects observed in the 240-215 nm spectral range. The results suggest that the helicity rule does not apply to the investigated compounds because of the planarity of their amide chromophore. Thus, these compounds do not constitute an exception to the rule that was established for bi- and polycyclic β-lactams with the nonplanar amide chromophore only. 相似文献
993.
Ohta K Yamada S Kamada K Slepkov AD Hegmann FA Tykwinski RR Shirtcliff LD Haley MM Sałek P Gel'mukhanov F Ågren H 《The journal of physical chemistry. A》2011,115(2):105-117
The two-photon absorption (TPA) properties of four TPEB [tetrakis(phenylethynyl)benzene] derivatives (TD, para, ortho, and meta) with different donor/acceptor substitution patterns have been investigated experimentally by the femtosecond open-aperture Z-scan method and theoretically by the time-dependent density-functional theory (TDDFT) method. The four compounds show relatively large TPA cross sections, and the all-donor substituted species (TD) displays the largest TPA cross-section σ(2) = 520 ± 30 GM. On the basis of the calculated electronic structure, TD shows no TPA band in the lower energy region of the spectrum because the transition density is concentrated on particular transitions due to the high symmetry of the molecular structure. The centrosymmetric donor-acceptor TPEB para shows excitations resulting from transitions centered on D-π-D and A-π-A moieties, as well as transition between the D-π-D and A-π-A moieties; this accounts for the broad nature of the TPA bands for this compound. Calculations for two noncentrosymmetric TPEBs (ortho and meta) reveal that the diminished TPA intensities of higher-energy bands result from destructive interference between the dipolar and three-state terms. The molecular orbitals (MOs) of the TPEBs are derivable with linear combinations of the MOs of the two crossing BPEB [bis(phenylethynyl)benzene] derivatives. Overall, the characteristics of the experimental spectra are well-described based on the theoretical analysis. 相似文献
994.
Grabowski SJ 《The journal of physical chemistry. A》2011,115(45):12789-12799
MP2/6-311++G(3pd,3df) calculations were performed on complexes of acetylene and fluoroform acting as the proton donating systems and different Lewis bases being the proton acceptors since these complexes are linked through C-H···Y hydrogen bonds. Quantum Theory of Atoms in Molecules (QTAIM) is applied to explain the nature of these interactions. The characteristics of bond critical points are presented for these complexes. The inter-relations between energetic and geometrical parameters as well as the parameters derived from the Natural Bond Orbital (NBO) theory are analyzed here. Red- and blue-shifted hydrogen bonds are detected for the complexes investigated and the differences between those interactions are analyzed from the QTAIM perspective. It is shown that such differences are in agreement with the Bent rule. The position of the bond critical point of the proton donating bond is connected with the nature of hydrogen bonding, that is, if it is blue- or red-shifted. 相似文献
995.
Szcześ A Chibowski E Hołysz L Rafalski P 《The journal of physical chemistry. A》2011,115(21):5449-5452
Electrolyte solutions were exposed for different time to weak static magnetic field (MF) generated from a stack of magnets (B = 15 mT) at the flow rate of 1.4 mL/s. The conductivity was measured as a function of time following the application of MF. It was found that the changes in conductivity depend on the kind of electrolyte and the magnetic exposure time and are related to the thermodynamic function of hydration. 相似文献
996.
Połomska M Pogorzelec-Glaser K Pawlaczyk C Pietraszko A 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2011,79(4):797-800
New bio-inspired polymer composites of alginic acid and benzimidazole were created and characterized by FT NIR Raman spectroscopy. The obtained films with 1:0.5, 1:1 and 1:1.5 molar ratio are homogeneous, with good mechanical properties. Raman spectra recorded at room temperature revealed that the obtained films are a new compound with a different molecular structure and physical properties compared with pure substrates: alginic acid and benzimidazole. Raman band related to vibration of COOH entity at 1740 cm(-1) of alginic acid disappears in the alginic acid:benzimidazole composites, in which new Raman band related to COO(-) was found. Additionally, characteristic lines observed in polymer composites which may be associated with vibrations of NH groups, can be attributed to the linking of proton to deprotonated N atom in benzimidazole group. Possibility of such proton exchange is a promising property which might facilitate the application of obtained composites to anhydrous proton conducting electrolytes in fuel cells. 相似文献
997.
Simeonika Rangełowa‐Jankowska Dawid Jankowski Dr. Beata Grobelna Prof. Ignacy Gryczyński Prof. Zygmunt Gryczyński Dr. Robert Bogdanowicz Prof. Piotr Bojarski 《Chemphyschem》2011,12(13):2449-2452
The first observation of strong directional surface‐plasmon‐coupled emission (SPCE) of Rhodamine 110 in silica nanofilms deposited on silver nanolayers is reported. The preparation of the material is described in detail. The intensity of SPCE exceeds 10 times that of free space fluorescence and total linear light polarization in the SPCE ring is observed. A new experimental setup and an original data collection method is presented. Our material completely preserves its fluorescence properties for at least eight months. 相似文献
998.
Deperasińska I Karpiuk E Banasiewicz M Makarewicz A Kozankiewicz B 《Physical chemistry chemical physics : PCCP》2011,13(5):1872-1878
Fluorescence excitation spectra of single dibenzoterrylene (DBT) molecules embedded in naphthalene (N) and 2,3-dimethylnaphthalene (2,3-DMN) crystals were studied at 5 K. The frequencies characterizing the vibronic structure of single DBT molecules in an N crystal agree with the theoretical prediction for the isolated DBT molecule. The 'dipolar' disorder encountered in 2,3-DMN crystals leads to a broad distribution of frequencies of the (0,0) lines of single DBT molecules. Moreover, the observed vibronic frequencies and intensities in the spectrum of DBT in 2,3-DMN crystals are slightly different to those in an N crystal. We conclude that the structure of DBT molecules in a 2,3-DMN crystal is disturbed in comparison with isolated DBT and the main change concerns its central tetracene moiety. 相似文献
999.
Sawyer BC Stuhl BK Yeo M Tscherbul TV Hummon MT Xia Y Kłos J Patterson D Doyle JM Ye J 《Physical chemistry chemical physics : PCCP》2011,13(42):19059-19066
Cold molecules promise to reveal a rich set of novel collision dynamics in the low-energy regime. By combining for the first time the techniques of Stark deceleration, magnetic trapping, and cryogenic buffer gas cooling, we present the first experimental observation of cold collisions between two different species of state-selected neutral polar molecules. This has enabled an absolute measurement of the total trap loss cross sections between OH and ND(3) at a mean collision energy of 3.6 cm(-1) (5 K). Due to the dipolar interaction, the total cross section increases upon application of an external polarizing electric field. Cross sections computed from ab initio potential energy surfaces are in agreement with the measured value at zero external electric field. The theory presented here represents the first such analysis of collisions between a (2)Π radical and a closed-shell polyatomic molecule. 相似文献
1000.
The high-temperature (HT) phase of Y(BH(4))(3) has been prepared by heating of the as mechanochemically synthesised low-temperature (LT) phase of Y(BH(4))(3) to 194-216 °C and subsequent rapid cooling to ambient temperature. Although the differences in the crystal structure and vibrational spectra for these closely-related polymorphs are rather small, yet the NMR MAS (1)H and CP MAS (89)Y spectra reveal clear differences in the chemical shifts for both nuclei. The thermal decomposition process of both forms differs noticeably below 260 °C, decomposition being faster and more facile for the HT phase. The activation energy for thermal decomposition, calculated according to the Kissinger equation, is nearly three times lower for the HT than for the LT polymorph for the first step of the thermal decomposition signalling giant improvement of kinetics of H(2) desorption. 相似文献