全文获取类型
收费全文 | 1912篇 |
免费 | 150篇 |
国内免费 | 169篇 |
专业分类
化学 | 1207篇 |
晶体学 | 32篇 |
力学 | 39篇 |
综合类 | 36篇 |
数学 | 171篇 |
物理学 | 746篇 |
出版年
2022年 | 27篇 |
2021年 | 25篇 |
2020年 | 23篇 |
2019年 | 17篇 |
2018年 | 19篇 |
2017年 | 41篇 |
2016年 | 32篇 |
2015年 | 30篇 |
2014年 | 37篇 |
2013年 | 90篇 |
2012年 | 74篇 |
2011年 | 80篇 |
2010年 | 61篇 |
2009年 | 77篇 |
2008年 | 80篇 |
2007年 | 124篇 |
2006年 | 122篇 |
2005年 | 112篇 |
2004年 | 118篇 |
2003年 | 92篇 |
2002年 | 84篇 |
2001年 | 64篇 |
2000年 | 48篇 |
1999年 | 38篇 |
1998年 | 28篇 |
1997年 | 25篇 |
1996年 | 41篇 |
1995年 | 21篇 |
1994年 | 33篇 |
1993年 | 35篇 |
1992年 | 33篇 |
1991年 | 21篇 |
1990年 | 16篇 |
1989年 | 32篇 |
1988年 | 24篇 |
1987年 | 23篇 |
1986年 | 22篇 |
1985年 | 31篇 |
1984年 | 26篇 |
1983年 | 13篇 |
1982年 | 16篇 |
1981年 | 29篇 |
1980年 | 13篇 |
1978年 | 25篇 |
1977年 | 18篇 |
1976年 | 13篇 |
1975年 | 11篇 |
1974年 | 21篇 |
1973年 | 24篇 |
1972年 | 12篇 |
排序方式: 共有2231条查询结果,搜索用时 15 毫秒
101.
Alex. G. Harrison R. Krishna Mohan Rao Kallury 《Journal of mass spectrometry : JMS》1980,15(5):249-256
A study of the electron impact and chemical ionization (H2, CH4, and iso-C4H10) mass spectra of stereoisomeric benzoin oximes and phenylhydrazones indicates that while the former can be distinguished only by their chemical ionization mass spectra the latter are readily distinguishable by both their electron impact and chemical ionization mass spectra. The electron impact mass spectra of the isomeric oximes are practically identical; however, the chemical ionization spectra show that the E isomer forms more stable [MH]+ and [MH? H2O]+ ions than the Z isomer for which both the [MH]+ and [MH? H2O]+ ions are relatively unstable. In electron impact the Z-phenylhydrazone shows a lower [M]+˙ ion abundance and more facile loss of H2O than does the E isomer. This more facile H2O loss also is observed for the [MH]+ ion of the Z isomer under chemical ionization conditions. 相似文献
102.
The preparation and properties of cyanobiphenyl liquid crystal droplets encapsulated by the polymerizable lecithin 1,2-bis(10,12-tricosadiynoyl)-sn-glyero-3-phosphocholine (DC8,9PC) are described. Under a wide variety of preparation conditions the droplets obtain a diameter of approximately 10 mum. These droplets are stable for periods of over one year at room temperature. Furthermore, they are stable upon temperature cycling between the nematic and isotropic phases and between the smectic A to nematic to isotropic phase transitions. 相似文献
103.
In this work we show through an analytic solution of the set of two coupled dynamic equations for the slowly varying amplitudes of the Stokes optical field and material density in stimulated Brillouin scattering (SBS), its analysis and a set of experiments, that the SBS-induced delay of an output Stokes pulse which is amplified by the SBS interaction is due exclusively to the inertia of the acoustic wave excitation. 相似文献
104.
árpád Somogyi Alex G. Harrison Béla Paizs 《Journal of the American Society for Mass Spectrometry》2012,23(12):2055-2058
Middle-sized b n (n????5) fragments of protonated peptides undergo selective complex formation with ammonia under experimental conditions typically used to probe hydrogen?Cdeuterium exchange in Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Other usual peptide fragments like y, a, a*, etc., and small b n (n????4) fragments do not form stable ammonia adducts. We propose that complex formation of b n ions with ammonia is characteristic to macrocyclic isomers of these fragments. Experiments on a protonated cyclic peptide and N-terminal acetylated peptides fully support this hypothesis; the protonated cyclic peptide does form ammonia adducts while linear b n ions of acetylated peptides do not undergo complexation. Density functional theory (DFT) calculations on the proton-bound dimers of all-Ala b 4 , b 5 , and b 7 ions and ammonia indicate that the ionizing proton initially located on the peptide fragment transfers to ammonia upon adduct formation. The ammonium ion is then solvated by N+-H??O H-bonds; this stabilization is much stronger for macrocyclic b n isomers due to the stable cage-like structure formed and entropy effects. The present study demonstrates that gas-phase guest?Chost chemistry can be used to selectively probe structural features (i.e., macrocyclic or linear) of fragments of protonated peptides. Stable ammonia adducts of b 9 , b 9 -A, and b 9 -2A of A8YA, and b 13 of A20YVFL are observed indicating that even these large b-type ions form macrocyclic structures. 相似文献
105.
106.
Alex G. Harrison 《Journal of the American Society for Mass Spectrometry》2013,24(10):1555-1564
The fragmentation reactions of the MH+ ions as well as the b7, a7, and a7* ions derived therefrom have been studied in detail for the octapeptides MAAAAAAA, AAMAAAAA, AAAAMAAA, and AAAAAAMA. Ionization was by electrospray using a QqToF mass spectrometer, which allowed a study of the evolution of the fragmentation channels as a function of the collision energy. Not surprisingly, the product ion mass spectra for the b7 ions are independent of the original precursor sequence, indicating macrocyclization and reopening to the same mixture of protonated oxazolones prior to fragmentation. The results show that this sequence scrambling results in a distinct preference to place the Met residue in the C-terminal position of the protonated oxazolones. The a7 and a7* ions also produce product ion mass spectra independent of the original peptide sequence. The results for the a7 ions indicate that fragmentation occurs primarily from an amide structure analogous to that observed for a4 ions (Bythell et al. in J Am Chem Soc 132:14766–14779, 2010). Clearly, the rearrangement reaction they have proposed applies equally well to an ions as large as a7. The major fragmentation modes of the MH+ ions at low collision energies produce b7, b6, and b5 ions. As the collision energy is increased further fragmentation of these primary products produces, in part, non-direct sequence ions, which become prominent at lower m/z values, particularly for the peptides with the Met residue near the N-terminus. Figure
? 相似文献
107.
Alex G. Harrison Cagdas Tasoglu Talat Yalcin 《Journal of the American Society for Mass Spectrometry》2013,24(10):1565-1572
The fragmentation reactions of the MH+ ions of Leu-enkephalin amide and a variety of heptapeptide amides have been studied in detail as a function of collision energy using a QqToF beam type mass spectrometer. The initial fragmentation of the protonated amides involves primarily formation of bn ions, including significant loss of NH3 from the MH+ ions. Further fragmentation of these bn ions occurs following macrocyclization/ring opening leading in many cases to bn ions with permuted sequences and, thus, to formation of non-direct sequence ions. The importance of these non-direct sequence ions increases markedly with increasing collision energy, making peptide sequence determination difficult, if not impossible, at higher collision energies. Figure
? 相似文献
108.
Gregory B. Kharas Sonia E. Chavez Harrison S. Browning Jennifer A. Sepe Mario E. Romanelli Melissa K. Susnis 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(10):751-755
Electrophilic trisubstituted ethylenes, ring-disubstituted methyl 2-cyano-3-phenyl-2-propenoates, RPhCH?C(CN)CO2CH3, where R is 2,5-dichloro, 3,5-dichloro, 2,3-difluoro, 3-chloro-2-fluoro, 3-chloro-4-fluoro, 4-chloro-3-fluoro, 2-chloro-5-nitro, and 2-chloro-6-nitro were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-disubstituted benzaldehydes and methyl cyanoacetate, and characterized by CHN analysis, IR, 1H and 13C-NMR. All the ethylenes were copolymerized with styrene (M1) in solution with radical initiation (ABCN) at 70°C. The compositions of the copolymers were calculated from nitrogen analysis and the structures were analyzed by IR, 1H and 13C-NMR. The order of relative reactivity (1/r1) for the monomers is 4-Cl-3-F (4.87) > 2,3-F2 (4.49) > 3-Cl-4-F (3.50) > 3-Cl-2-F (2.96) > 2-Cl-5-NO2 (2.02) > 2,5-Cl2 (1.54) > 2-Cl-6-NO2 (1.00) > 3,5-Cl2 (0.41). Relatively high Tg of the copolymers in comparison with that of polystyrene indicates a decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500ºC range with residue (1.5–34.5% wt), which then decomposed in the 500-800ºC range. 相似文献
109.
Abstract High molecular weight polyphenyl-as-triazines were prepared at ambient temperature by the cyclopolycondensation of perfluoroglutaramidrazone and perfluoroadipamidrazone with various bis(1,2-dicarbonyl) monomers. The effect which the perfluoroalkylene group had upon certain chemical and physical properties of the polymers was determined. Thermal evaluation involved TGA, DSC, TMA, and isothermal weight loss studies of films at 232 °C in air. The polymers exhibited excellent hydrolytic stability as evidenced by retention of n inh after boiling in water (24 hr) and 10% sodium hydroxide solution (8 hr). A stable uncyclized intermediate was isolated from the reaction of perfluoroadipamidrazone and benzil which was cyclized to the phenyl-as-triazine model compound [3,3′ -perfluorotetramethylenedi (5,6-diphenyl-as-triazine)]. 相似文献
110.
选择具有强给电子能力的1,2,4-三唑为配体,成功合成了银基金属有机骨架材料(Ag-MOF)并用于电催化还原CO2反应(CO2RR)。借助粉末X射线衍射、透射电子显微镜、扫描电子显微镜、计时电流法等表征手段对材料的晶体结构、形貌和电催化CO2RR性能进行了系统的研究。与商品化的纳米Ag颗粒对比,Ag-MOF展现出更优异的电催化CO2RR产物选择性、催化活性和稳定性,在-0.9 V (vs RHE)时,CO的法拉第效率高达96.1%。当电压为-1.1 V (vs RHE)时,电流密度可达17 mA·cm-2,且电极可以稳定运行300 min。这说明通过选择合适的配体结构,可以改变催化位点周围的化学环境,从而高效将CO2转化为目标产物。 相似文献