全文获取类型
收费全文 | 719篇 |
免费 | 21篇 |
国内免费 | 3篇 |
专业分类
化学 | 538篇 |
晶体学 | 17篇 |
力学 | 10篇 |
数学 | 106篇 |
物理学 | 72篇 |
出版年
2022年 | 4篇 |
2021年 | 12篇 |
2020年 | 5篇 |
2019年 | 8篇 |
2018年 | 5篇 |
2017年 | 10篇 |
2016年 | 13篇 |
2015年 | 14篇 |
2014年 | 15篇 |
2013年 | 33篇 |
2012年 | 27篇 |
2011年 | 48篇 |
2010年 | 14篇 |
2009年 | 21篇 |
2008年 | 29篇 |
2007年 | 44篇 |
2006年 | 35篇 |
2005年 | 35篇 |
2004年 | 28篇 |
2003年 | 35篇 |
2002年 | 40篇 |
2001年 | 20篇 |
2000年 | 6篇 |
1999年 | 11篇 |
1998年 | 8篇 |
1997年 | 9篇 |
1996年 | 14篇 |
1995年 | 11篇 |
1994年 | 15篇 |
1993年 | 7篇 |
1992年 | 9篇 |
1991年 | 6篇 |
1990年 | 9篇 |
1989年 | 11篇 |
1988年 | 7篇 |
1987年 | 7篇 |
1986年 | 8篇 |
1985年 | 11篇 |
1984年 | 9篇 |
1983年 | 11篇 |
1982年 | 9篇 |
1981年 | 14篇 |
1980年 | 8篇 |
1979年 | 11篇 |
1978年 | 6篇 |
1977年 | 6篇 |
1976年 | 5篇 |
1974年 | 5篇 |
1973年 | 4篇 |
1926年 | 2篇 |
排序方式: 共有743条查询结果,搜索用时 15 毫秒
731.
Deniz E Battal M Cusido J Sortino S Raymo FM 《Physical chemistry chemical physics : PCCP》2012,14(29):10300-10307
We synthesized five BODIPY-oxazine dyads in one to four synthetic steps from known precursors. They differ in the nature of the unsaturated spacer linking the oxazine photochrome to either the conjugated framework or the boron center of the BODIPY fluorophore. Despite the π-character of the linkers, the two functional components are electronically isolated in the ground state and the BODIPY fluorophore maintains its absorption and, with one exception, emission properties unaltered. Instead, the photochemical response of the photochromic component is completely suppressed within all dyads. Rather than the expected opening of the oxazine ring, the laser excitation of these molecular assemblies results in the effective population of the BODIPY triplet in four of the five dyads. Control experiments with appropriate model compounds indicate that the local excitation of the oxazine component results first in intersystem crossing and then energy transfer to the BODIPY component. In fact, the transfer of energy from the triplet state of the former to the triplet state of the latter competes successfully with the opening of the oxazine ring and prevents the isomerization of the photochromic component. These observations demonstrate, for the very first time, that the photoinduced opening of these photochromic oxazines occurs along the potential energy surface of their triplet state. Such valuable mechanistic insights into their excitation dynamics can guide the design of novel members of this family of photochromic compounds with improved photochemical properties. 相似文献
732.
Covering: up to the end of 2011The world's oceans are a rich source of natural products with extremely interesting chemistry. Biosynthetic pathways have been worked out for a few, and the story is being enriched with crystal structures of interesting pathway enzymes. By far, the greatest number of structural insights from marine biosynthetic pathways has originated with studies of curacin A, a poster child for interesting marine chemistry with its cyclopropane and thiazoline rings, internal cis double bond, and terminal alkene. Using the curacin A pathway as a model, structural details are now available for a novel loading enzyme with remarkable dual decarboxylase and acetyltransferase activities, an Fe(2+)/α-ketoglutarate-dependent halogenase that dictates substrate binding order through conformational changes, a decarboxylase that establishes regiochemistry for cyclopropane formation, and a thioesterase with specificity for β-sulfated substrates that lead to terminal alkene offloading. The four curacin A pathway dehydratases reveal an intrinsic flexibility that may accommodate bulky or stiff polyketide intermediates. In the salinosporamide A pathway, active site volume determines the halide specificity of a halogenase that catalyzes for the synthesis of a halogenated building block. Structures of a number of putative polyketide cyclases may help in understanding reaction mechanisms and substrate specificities although their substrates are presently unknown. 相似文献
733.
The pyrimidine nucleobases contained in DNA undergo a variety of photoinduced reactions in which two moieties become joined to form a product (e.g. formation of cyclobutane dimers and [6-4] adducts). Herein, we describe a new type of photoconjugation reaction that has been shown to occur for 5-methylcytosine (5-MeC), 1,5-dimethylcytosine (1,5-diMeC), 1-methylthymine and thymidine; in this reaction the 5-methyl group of one nucleobase (or nucleoside) becomes attached to the 4-position of the second moiety. For example, 5-MeC forms α-4'-(5'-methylpyrimidin-2'-one)-5-methylcytosine. The various (α-4) conjugates are produced upon irradiation of the parent compound in frozen aqueous solution at -78.5°C. The UV spectra of these compounds display a characteristic "double humped" profile, similar to that expected from overlaying the spectrum of parent nucleobase with that of a 2'-pyrimidone moiety. Preliminary results suggest that thymine and 5-methyl-2'-deoxycytidine (5-MedCyd) form analogous photoproducts. A variety of other previously unreported photoproducts are described as well for the 5-MeC, 1,5-diMeC and 5-MedCyd systems. 相似文献
734.
We investigate the effect of magic angle spinning on heteronuclear spin decoupling in solids. We use an analytical Floquet-van Vleck formalism to derive expressions for the powder-averaged signal as a function of time. These expressions show that the spectrum consists of a centerband at the isotropic frequency of the observed spin, omega(0), and rotational decoupling sidebands at omega(0)+/-omega(1)+/-momega(r), where omega(1) is the decoupling field strength and omega(r) is the rotation frequency. Rotary resonance occurs when the rotational decoupling sidebands overlap with the centerband. Away from the rotary resonance conditions, the intensity of the centerband as a function of omega(r)/omega(1) is simply related to the total intensity of the rotational decoupling sidebands. Notably, in the absence of offset terms it is shown that as omega(1) decreases, the centerband intensity can decrease without any associated broadening. Furthermore, the centerband width is shown to be independent of spinning speed, to second order for the effects we consider. The effects of I spin chemical shift anisotropy and homonuclear dipolar couplings are also investigated. The analytical results are compared to simulations and experiments. 相似文献
735.
Kajikawa S Fais L Mugitani R Werker JF Amano S 《The Journal of the Acoustical Society of America》2006,120(4):2278-2284
This study explored sensitivity to word-level phonotactic patterns in English and Japanese monolingual infants. Infants at the ages of 6, 12, and 18 months were tested on their ability to discriminate between test words using a habituation-switch experimental paradigm. All of the test words, neek, neeks, and neekusu, are phonotactically legitimate for English, whereas the first two words are critically noncanonical in Japanese. The language-specific phonotactical congruence influenced infants' performance in discrimination. English-learning infants could discriminate between neek and neeks at the age of 18 months, but Japanese infants could not. There was a similar developmental pattern for infants of both language groups for discrimination of neek and neeks, but Japanese infants showed a different trajectory from English infants for neekusu/neeks. These differences reflect the different status of these word patterns with respect to the phonotactics of both languages, and reveal early sensitivity to subtle phonotactic and language input patterns in each language. 相似文献
736.
Cole ML Junk PC Proctor KM Scott JL Strauss CR 《Dalton transactions (Cambridge, England : 2003)》2006,(27):3338-3349
The stoichiometric treatment of 2,6-dibenzylphenol (HOdbp) or 2,2"-dimethoxy-2,6-dibenzylphenol (HOdbpOMe) with n-butyllithium or sodium bis(trimethylsilyl)amide (the latter as a solution in THF) in Et2O or DME affords the dimeric alkali metal phenolates [{M(Odbp)(L)}2] (M = Li; L = Et2O (1), L = DME (2), M = Na; L = Et2O (5), L = DME (6)), [{Li(OdbpOMe)}2] (3) and [{M(OdbpOMe)(L)}2] (M = Li; L = DME (4), M = Na; L = THF (7), L = DME (8)). Complexes 3 and 7 exhibit -OdbpOMe methoxy coordination and all four sodium complexes (5-8) display pi-aryl contacts from one phenolate radial arm to each sodium centre. The attempted synthesis of {Na(odbp)}n by direct sodiation of HOdbp yields a small quantity of the 2-benzylphenolate [{Na(Ombp)(DME)}4] (9) (-Ombp = -OC6H4-2-CH2Ph), providing a rare example of benzyl C-C bond scission. 相似文献
737.
Rakic B Clarke J Tremblay TL Taylor J Schreiber K Nelson KM Abrams SR Pezacki JP 《Chemistry & biology》2006,13(10):1051-1060
The hepatitis C virus (HCV) is a growing global health problem. Small molecules that interfere with host-viral interactions can serve as powerful tools for elucidating the molecular mechanisms of pathogenesis and defining new strategies for therapeutic development. Using a cell-based screen involving subgenomic HCV replicons, we identified the ability of 18 different abscisic acid (ABA) analogs, originally developed as plant growth regulators, to inhibit HCV replication. Three of these were further studied. One compound, here named origamicin, showed antiviral activity through the inhibition of host proteins involved in protein folding. Origamicin could therefore be an important tool for studying the maturation of both host and viral proteins. Herein we demonstrate an application for molecular scaffolds based on ABA for mammalian cell targets involved in protein folding. 相似文献
738.
The title technique, high-resolution magic angle spinning NMR of suspensions, constitutes a powerful new tool for investigating the structures and mobilities of immobilized species and, thus, for optimizing heterobimetallic catalyst systems, such as the Sonogashira coupling of terminal alkynes and aryl halides. 相似文献
739.
Sums of Hilbert space frames 总被引:1,自引:0,他引:1
Sofian Obeidat Peter G. Casazza Janet C. Tremain 《Journal of Mathematical Analysis and Applications》2009,351(2):579-585
We give simple necessary and sufficient conditions on Bessel sequences {fi} and {gi} and operators L1, L2 on a Hilbert space H so that {L1fi+L2gi} is a frame for H. This allows us to construct a large number of new Hilbert space frames from existing frames. 相似文献
740.
Suneetha Devpura Jagdish S. Thakur Janet M. Poulik Rajah Rabah Vaman M. Naik Ratna Naik 《Journal of Raman spectroscopy : JRS》2013,44(3):370-376
Raman spectroscopy is a nondestructive technique that can provide information at the molecular level about the biochemicals in tissues. We have investigated the cellular regions in neuroblastoma and ganglioneuroma using Raman spectroscopy and compared their spectral characteristics with those of the corresponding normal adrenal gland. Thin sections from both the frozen and the corresponding formalin‐fixed paraffin‐processed (FFPP) tissues were studied in conjunction with the pathological examination of the tissues. Investigation of the spectral data shows that the normal adrenal gland tissues have higher levels of carotenoids, lipids, and cholesterol compared with the neuroblastoma and ganglioneuroma frozen tissues. However, in comparison with the frozen tissues, the FFPP tissues show a significant alteration of several biochemicals, including the complete removal of carotenoids, lipids, and cholesterol in the adrenal tissues. A quantitative analysis using chemometric methods of principal component analysis and discriminant function analysis of the Raman spectral data obtained from the frozen tissues show a clear‐cut classification among pathological groups with high sensitivity and specificity. We have validated the classification results of the FFPP tissues against a training set data obtained from the archived FFPP tissues of nine other patients. The validation process correctly identified and grouped the data with the training set of normal adrenal gland (>97% of the time) and neuroblastoma (100% of the time) tissues, whereas the validation was not so strong for ganglioneuroma. This study shows that Raman spectroscopy combined with chemometric methods can be successfully used to distinguish neuroblastoma and ganglioneuroma at cellular level in frozen tissue sections. This study also shows that formalin fixation and paraffinization/deparaffinization of tissues can alter their biochemical composition. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献