全文获取类型
收费全文 | 724篇 |
免费 | 28篇 |
国内免费 | 3篇 |
专业分类
化学 | 591篇 |
晶体学 | 6篇 |
力学 | 10篇 |
数学 | 86篇 |
物理学 | 62篇 |
出版年
2024年 | 1篇 |
2023年 | 10篇 |
2022年 | 32篇 |
2021年 | 45篇 |
2020年 | 23篇 |
2019年 | 24篇 |
2018年 | 19篇 |
2017年 | 23篇 |
2016年 | 29篇 |
2015年 | 33篇 |
2014年 | 27篇 |
2013年 | 51篇 |
2012年 | 48篇 |
2011年 | 65篇 |
2010年 | 29篇 |
2009年 | 33篇 |
2008年 | 33篇 |
2007年 | 38篇 |
2006年 | 32篇 |
2005年 | 30篇 |
2004年 | 27篇 |
2003年 | 20篇 |
2002年 | 19篇 |
2001年 | 10篇 |
2000年 | 6篇 |
1999年 | 5篇 |
1998年 | 6篇 |
1997年 | 3篇 |
1996年 | 6篇 |
1995年 | 2篇 |
1994年 | 1篇 |
1993年 | 2篇 |
1992年 | 1篇 |
1991年 | 2篇 |
1989年 | 1篇 |
1988年 | 3篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 3篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1978年 | 2篇 |
1977年 | 1篇 |
1975年 | 1篇 |
1973年 | 2篇 |
1969年 | 1篇 |
1964年 | 1篇 |
排序方式: 共有755条查询结果,搜索用时 31 毫秒
1.
Marilena Vasilescu Titus Constantinescu Mariana Voicescu Helge Lemmetyinen Elina Vuorimaa 《Journal of fluorescence》2003,13(4):315-322
The spectrophotometric study of luminol (LH2) in dimethyl sulfoxide (DMSO), DMSO-water solutions, and alkaline DMSO and DMSO-water solutions has been done, focusing on the effect of the KOH additon on LH2 absorption and fluorescence properties. The absorption spectra indicate an acid-base equilibrium, and the luminol dianion (L2–) formation at 3 × 10–4 – 2.4 × 10–3
M KOH. The decrease of the fluorescence intensity and the variation of the excitation spectra of LH2-DMSO-KOH solutions with KOH concentration have been similarly explained. The acid-base process is reversible. The addition of HCl to the solution with 3.0 × 10–3 M KOH leads to an increase of the fluorescence intensity to its highest value, observed in pure DMSO. The addition of HCl to the LH2-DMSO solution leads to the decrease of the fluorescence intensity as a result of the LH+
3 cation formation. In LH2-DMSO-water, the fluorescence band is shifted from 405 nm to 424 nm and increased in the intensity. In the presence of KOH (in LH2-DMSO-water-KOH solution) a new band appears, with the maximum at 485 nm and the band at 405 nm decreased. The changes in fluorescence lifetimes also evidence the different chemical species formed. 相似文献
2.
V. Badescu M. Radu M. Zaharescu A. Vasilescu 《Journal of Sol-Gel Science and Technology》1994,2(1-3):43-49
Gas-chromatography coupled with mass spectrometry was used to investigate the hydrolysis and condensation of tetra-ethoxysilane (TEOS) in nonparental solvents (MeOH and nPrOH). In the presence of nonparental solvents, the reaction that advanced at highest rate is alkoxy group scrambling, that changes the precursor at the molecular level. Subsequent stages of hydrolysis-polycondensation process are essentially determined by the reactivity of the new molecular species formed. 相似文献
3.
JPC – Journal of Planar Chromatography – Modern TLC - Separations of eight methyl esters of higher fatty acids on RP-18 stationary phase with methanol—water and... 相似文献
4.
Alina Constantinescu 《Applications of Mathematics》2007,52(4):321-326
In one if his paper Luo transformed the problem of sum-fuzzy rationality into artificial learning procedure and gave an algorithm
which used the learning rule of perception. This paper extends the Luo method for finding a sum-fuzzy implementation of a
choice function and offers an algorithm based on the artificial learning procedure with fixed fraction. We also present a
concrete example which uses this algorithm. 相似文献
5.
6.
Szklarzewicz Janusz Samotus Alina Nowicka Beata Burgess John Fawcett John Russell David R. 《Transition Metal Chemistry》1999,24(2):177-182
The X-ray crystal structure of (bpyH2)2[W(CN)8]·4H2 O (bpyH2=2,2-bipyridinium) is described. The [W(CN)8]4– anion has an approximately square antiprismatic (D4d) conformation, seemingly imposed by strong anion–water–cation hydrogen-bonding interactions. Bond distances in the anion are: WC 2.150(5), 2.163(5); CN 1.128(6), 1.145(6)Å and the angles WCN are 177.6(5), 178.3(5)°. The dihydrate and the anhydrous salt are both intensely black solids, exhibiting ion-pair charge-transfer interaction between cation and anion. E.s.r. spectra indicate that 30% of the tungsten is present as WV in the solid state, but that in solution only the WIV complex is present. The electron withdrawing effect of the cation is discussed and compared with that in a series of salts with different bipyridinium cations. 相似文献
7.
A systematic study for the optimization and implementation of high-performance capillary electrophoresis (HPCE) in conjunction with negative ion electrospray ionization-quadrupole time of flight-tandem mass spectrometry (ESI-QTOF-MS/MS) for the analysis of complex glycolipids is described. The performance of the capillary electrophoresis (CE) and off-line CE/ESI-QTOF-MS approach has been explored for screening a complex ganglioside mixture from bovine brain. All instrumental and solution parameters demonstrated to require special adjustment and to have the most substantial effect on the CE separation, abundance of product ions produced in a low-energy collision-induced dissociation (CID) process and their detection by MS/MS, when attempting to identify and sequence single ganglioside molecular species from CE eluted fractions. Upon optimization of the experimental parameters, an efficient methodology emerged providing the general basic requirements for combined CE/ESI-MS analysis of this type of complex glycoconjugate. 相似文献
8.
A recently introduced technique, simultaneous multiple sample light scattering (SMSLS), was used to monitor parallel polymerization reactions in situ. SMSLS is designed for real-time, high-throughput screening and provides a time-dependent light scattering signature for each reaction, which contains both qualitative and semiquantitative information. Qualitatively, the signature immediately indicates whether the reaction occurs or not, whether there is an initial lag period, and how long the reaction takes until it stops. The signature also provides estimates of the reaction rate and weight average molecular mass M(w), and its shape can help identify mechanistic aspects, for example, controlled versus free radical polymerization, presence of impurities, etc. The method is inherently adapted to small sample volumes and requires no special sample preparation or postpolymerization characterization. The demonstration here involved the free radical polymerization of acrylamide under varying conditions and should be readily applicable to a wide variety of other reactions. Results were cross-checked with multi-detector gel permeation chromatography. 相似文献
9.
Misbahul Ain Khan Alina Guerra Cosenza Gwynn Pennant Ellis 《Journal of heterocyclic chemistry》1982,19(5):1077-1085
Various 1H,6H-pyrano[2,3-c]pyrazol-6-ones (III-XXIII) were obtained from β-keto esters and 1H-pyrazol-5-ones or hydrazines. Nitrations, chlorinations and brominations of these pyranopyrazoles were also carried out giving the corresponding derivatives (XXIV-LXIV). The pyrone ring is the more reactive one in these reactions and the preferred position of attack is the 5-position. The substitution products are formed by the addition-elimination route. 相似文献
10.
Henrik Land Alina Sekretareva Ping Huang Holly J. Redman Brigitta Nmeth Nakia Polidori Lívia S. Mszros Moritz Senger Sven T. Stripp Gustav Berggren 《Chemical science》2020,11(47):12789
[FeFe]-hydrogenases are known for their high rates of hydrogen turnover, and are intensively studied in the context of biotechnological applications. Evolution has generated a plethora of different subclasses with widely different characteristics. The M2e subclass is phylogenetically distinct from previously characterized members of this enzyme family and its biological role is unknown. It features significant differences in domain- and active site architecture, and is most closely related to the putative sensory [FeFe]-hydrogenases. Here we report the first comprehensive biochemical and spectroscopical characterization of an M2e enzyme, derived from Thermoanaerobacter mathranii. As compared to other [FeFe]-hydrogenases characterized to-date, this enzyme displays an increased H2 affinity, higher activation enthalpies for H+/H2 interconversion, and unusual reactivity towards known hydrogenase inhibitors. These properties are related to differences in active site architecture between the M2e [FeFe]-hydrogenase and “prototypical” [FeFe]-hydrogenases. Thus, this study provides new insight into the role of this subclass in hydrogen metabolism and the influence of the active site pocket on the chemistry of the H-cluster.Characterization of a group D putative sensory [FeFe]-hydrogenase reveals how the active site can be tuned to decrease CO inhibition and increase stability of a reduced H-cluster while retaining the ability to catalyze H+/H2 interconversion. 相似文献