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排序方式: 共有155条查询结果,搜索用时 43 毫秒
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Flash vacuum pyrolysis (fvp) of some substituted [1,2,4]triazolo[3,4-c][1,2,4]benzotriazine derivatives (1a-d) has been studied between 450 and 600 °C. The only transformation observed up to 525 °C was the unexpected valence bond isomerization of the angularly fused starting compounds to the isomeric linearly fused [1,2,4]triazolo[4,3-b][1,2,4]benzotriazine derivatives (9a-d), whereas at higher temperatures fragmentation products such as aromatic nitriles were also formed. Kinetic measurements revealed negative entropies of activation in the isomerization process, which suggest a concerted ring closure reaction to an intermediate antiaromatic diazirine. Reversibiblity of the title isomerization reaction was also proved by FVP experiments. 相似文献
4.
Davor Margeti? 《Tetrahedron》2007,63(20):4338-4346
Four new substituted methano-bridged or heteroatom-bridged norbornadienomaleic anhydrides have been prepared and converted to sesquinorbornadiene anhydrides by reaction with cyclic 1,3-dienes. The versatility of parity reversal, in conjunction with N-substituent steric effects, has been used to produce all three possible stereoisomers of the N,O-sesquinorbornadiene anhydrides in separate, stereoselective cycloadditions. The anhydrides have been synthesized by cyclization of their diacids (in situ production) or by flash vacuum pyrolysis of their furan adducts (yielding crystalline products); further fragmentation occurs at these or higher temperatures to produce five-membered carbocyclic or heterocyclic anhydrides. Activation energies have been evaluated for the fragmentation and cycloaddition processes using DFT calculations (B3LYP/6-31G∗) and these calculations correctly predict, which reaction can be intercepted at the norbornadienomaleic anhydride stage and preferred stereochemistry of cycloadducts. 相似文献
5.
S. Padmaja V. Ramakrishnan J. Rajaram J. C. Kuriacose 《Journal of Chemical Sciences》1988,100(4):297-303
The borate radical is produced by the flash photolysis of an aqueous alkaline solution of NaBO2 and K2S2O8. The absorption spectrum of the transient borate radical shows two maxima. The self decay of this radical is second order.
Rate constants for the reactions of this radical with some organic substrates have been determined. 相似文献
6.
Summary The suitability of flash chromatography for the fractionation of coal liquids in compound classes has been studied. TLC data
obtained from standards were used for establishing the sequence, composition and volume of eluents in order to collect the
main components of coal liquids in six fractions of increasing polarity. The method was tested by the fractionation of a SCG
coal extract and separations were evaluated by TLC, SEC, and IR and NMR spectroscopy. 相似文献
7.
T. P. Elango V. Ramakrishnan S. Vancheesan J. C. Kuriacose 《Journal of Chemical Sciences》1984,93(1):47-52
Rate constants for the reaction of carbonate radical with aniline and some parasubstituted anilines have been determined by
the flash photolysis technique. Using σ+ para values the rate constants at pH 8.5 correlate very well with the Hammett equation yielding ρ= − 1. The carbonate radical oxidises aniline giving the anilino radical. The products so formed have been identified through
studies under conditions of continuous irradiation. 相似文献
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以高校基础化学实验"从海带中提取碘""三草酸合铁(Ⅲ)酸钾的制备"为例,分别探讨了微视频技术在化学基本操作实验和综合设计型实验中的具体应用;此外,举例说明利用Flash软件制作的虚拟微视频可以在仪器分析实验中清晰地再现仪器真实操作中的每一个步骤,弥补了学生在实验前无法实际操作仪器的不足。实践证明,微视频技术的应用,丰富了基础化学实验教学模式,增强了学生自主学习的能力和动手能力,提高了实验成功率和实验教学效果。 相似文献
9.
研究了客体模型FTO的闪光照相系统X光输运过程,给出了直穿照射量、散射照射量、直散比、直穿照射量能谱、散射照射量能谱、直穿X光通量能谱和散射X光通量能谱在记录平面的空间分布。结果表明:后锥是照射量散射成分的主要来源,后锥照射量占总散射量97%;后锥也是造成散射的空间分布不均匀的主要器件,这一不均匀性高达58%。照相系统的最小直散比非常小,表明锥造成的散射已经严重地淹没了直穿(轫致辐射)信号。计算中使用高空间分辨率记录法进行分点,合成图像对吸收系数的复原结果与国外报道的结果相符。 相似文献
10.
Yannick Weesepoel Jean‐Paul Vincken Raluca Maria Pop Kun Liu Harry Gruppen 《Journal of mass spectrometry : JMS》2013,48(7):862-874
The microalga Haematococcus pluvialis produces the pigment astaxanthin mainly in esterified form with a multitude of fatty acids, which results in a complex mixture of carotenol mono‐ and diesters. For rapid fingerprinting of these esters, matrix‐assisted laser desorption ionization time of flight mass spectrometry (MALDI‐TOF/TOF‐MS) might be an alternative to traditional chromatographic separation combined with MS. Investigation of ionization and fragmentation of astaxanthin mono‐ and diester palmitate standards in MALDI‐TOF/TOF‐MS showed that sodium adduct parent masses [M + Na]+ gave much simpler MS2 spectra than radical / protonated [M]+● / [M + H]+ parents. [M + Na]+ fragments yielded diagnostic polyene‐specific eliminations and fatty acid neutral losses, whereas [M]+● / [M + H]+ fragmentation resulted in a multitude of non‐diagnostic daughters. For diesters, a benzonium fragment, formed by polyene elimination, was required for identification of the second fatty acid attached to the astaxanthin backbone. Parents were forced into [M + Na]+ ionization by addition of sodium acetate, and best signal‐to‐noise ratios were obtained in the 0.1 to 1.0 mM range. This method was applied to fingerprinting astaxanthin esters in a crude H. pluvialis extract. Prior to MALDI‐TOF/TOF‐MS, the extract was fractionated by normal phase Flash chromatography to obtain fractions enriched in mono‐ and diesters and to remove pheophytin a, which compromised monoester signals. All 12 types of all‐trans esterified esters found in LC were identified with MALDI‐TOF/TOF‐MS, with the exception of two minor monoesters. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献