全文获取类型
收费全文 | 664篇 |
免费 | 16篇 |
专业分类
化学 | 422篇 |
晶体学 | 1篇 |
力学 | 16篇 |
数学 | 123篇 |
物理学 | 118篇 |
出版年
2023年 | 7篇 |
2022年 | 30篇 |
2021年 | 24篇 |
2020年 | 25篇 |
2019年 | 19篇 |
2018年 | 19篇 |
2017年 | 12篇 |
2016年 | 29篇 |
2015年 | 26篇 |
2014年 | 30篇 |
2013年 | 34篇 |
2012年 | 53篇 |
2011年 | 44篇 |
2010年 | 31篇 |
2009年 | 28篇 |
2008年 | 38篇 |
2007年 | 35篇 |
2006年 | 31篇 |
2005年 | 19篇 |
2004年 | 12篇 |
2003年 | 14篇 |
2002年 | 16篇 |
2001年 | 6篇 |
2000年 | 5篇 |
1999年 | 6篇 |
1998年 | 3篇 |
1997年 | 2篇 |
1996年 | 5篇 |
1995年 | 6篇 |
1993年 | 4篇 |
1991年 | 5篇 |
1990年 | 1篇 |
1989年 | 5篇 |
1988年 | 2篇 |
1987年 | 3篇 |
1986年 | 4篇 |
1985年 | 8篇 |
1984年 | 3篇 |
1983年 | 2篇 |
1982年 | 4篇 |
1981年 | 2篇 |
1980年 | 4篇 |
1979年 | 6篇 |
1978年 | 2篇 |
1977年 | 1篇 |
1976年 | 6篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1973年 | 3篇 |
1967年 | 1篇 |
排序方式: 共有680条查询结果,搜索用时 15 毫秒
1.
Bubbles released from a porous plug into a gas-stirred ladle present different bubbly dispersion patterns that can be studied by CFD means. Recent modeling (Alexiadis et al.) has, in fact, led to numerical results in accord with experimental data. However, due to the high number of equations involved, it is not easy to understand the physical reasons of the transitions between these patterns. In the present paper, attention was focused on the role of fragmentation and coalescence and the pattern-transition modeled by means of intersection points between these functions. 相似文献
2.
Summary A statistical study of precipitation over the Po Valley and the Alps during four winters, based on the application of a principal
component (p.c.) method, exhibited a good correlation between the first three rotated eigenvectors of the cross-product matrix
(between time series of data recorded at 70 stations) and three typical atmospheric circulation schemes over Northern Italy.
The study is here continued, by relating these results to meteorological fields evaluated over a region wider than the area
previously considered. Our attention mainly concentrated on the fields of time trend of geopotential height at 850 hPa over
Europe, between latitude 34.5 and 51 degrees North and longitudes 0 and 21 degrees East. This was suggested by some peculiar
relationships shown by the statistical distributions of geopotential height and wind direction and speed with respect to the
first three p.c.’s. These relationships made us think of the possibility to use those trends as predictors of precipitation
fields. Our analysis puts into evidence that three spatial patterns of geopotential, height time trend can be safely associated
to the first three p.c.’s and, as a consequence, to the three precipitation modes corresponding to the spatial distributions
of the eigenvectors, previously identified by us. They can therefore be considered meaningful precursors of precipitation
field patterns over Northern Italy and Alpine regions.
Riassunto Uno studio statistico della precipitazione sulla pianura padana e sulle Alpi durante quattro inverni, basato sull’applicazione del metodo delle componenti principali (c.p.), ha mostrato una buona correlazione fra i primi tre autovettori rotati della matrice dei prodotti incrociati (fra le serie temporali dei dati registrati in 70 stazioni) e tre tipici schemi di circolazione atmosferica sull’Italia del Nord. Lo studio viene qui prosequito, mettendo in relazione tali risultati con campi meteorologici valutati su una zona piú ampia di quella precedentemente considerata. La nostra attenzione si è prevalentemente concentrata sui campi di tendenza temporale dell’altezza di geopotenziale a 850 hPa sull’Europa, a latitudini comprese tra 34.5 e 51 gradi Nord e longitudini fra 0 e 21 gradi Est. Ciò è stato suggerito da alcune relazioni peculiari mostrate dalle distribuzioni statistiche di altezza di geopotenziale e di direzione ed intensità del vento rispetto alle prime tre c.p., che ci hanno fatto pensare alla possibilità di usare tali tendenze come predittori del campo di precipitazione. La nostra analisi ha messo in evidenza il fatto che tre distribuzioni spaziali di tendenza temporale del campo di altezza di geopotenziale possono essere con sicurezza associate alle prime tre c.p. e., quindi, ai tre modi di precipitazione corrispondenti alle distribuzioni spaziali degli autovettori precedentemente da noi identificati. Essi possono pertanto essere considerati significativi precursori del campo di precipitazione sull’Italia del Nord e sulle regioni alpine.
Резюме Статистическое исследование выпадения осадков над долиной реки По и Альпами в течение четырех зим, основанное на применении метода главных компонент, обнаруживает хорошую корреляцию между первыми тремя вращающимися собственными векторами матрицы векторного произведения (между временными последовательностями данных, зарегистрированных на 70 станциях) и тремя схемами типичной атмосферной циркуляции над Северной Италией. В этой работе продолжены исследования. Полученные результаты связывайотся с метеорологическими полями, вычисленными над областью, которая шире ранее рассмотренной области. Главное внимание мы обращаем на поля временного хода для геопотенциальной высоты при 850гПа над Европой, между 34.5щ и 51щ северной широты и между 0щ и 21щ восточной долготы. Это следует из специальных соотношений, полученных с помощью статистических распределений геопотенциальной высоты и направления и скорости ветра относительно первых трех главных компонент. Эти соотношения позволяют нам использовать исследованные тенденции, как предсказатели полей вьшадения осадков. Нам анализ подтверждает, что три пространственным распределения временного хода для геопотенциальной высоты могут быть связаны с первыми тремя главными компонентами и, как следствие, с тремя моделями выцадения осадков, которые соответствуют пространственным распределениям собственных векторов, ранее идентифицированных в работе [Ш]. Следовательно, они могут рассматриватяся как предвестники для распределений полей осадков над Северной Италией и над Альпами.相似文献
3.
4.
Specific programming of automated HPLC systems allows total on-line qualification, validation and stability monitoring using the concept of deferred standards. Setting up such a process for routine analyses in an automated HPLC system requires specific autosampler programming as well as specific monitoring software. With an autosampler, a double injection procedure is programmed, the first introducing the sample, and the second, a few minutes deferred, the deferred control standard. Two additional compounds are therefore added to the sample before and during the chromatographic process: the intemal standard for sample quantification and the deferred standard for system control. Specific methodologies are described of how to obtain classical quantitative analysis information as well as system qualification validation stability information. Experiments were performed to develop specified methodologies to monitor the quality of quantitative analysis during the life of the column by using the deferred standard concept to probe the effects of column ageing on separation characteristics. 相似文献
5.
Zanoni G Porta A Meriggi A Franzini M Vidari G 《The Journal of organic chemistry》2002,67(17):6064-6069
Regioconvergent synthesis of the key lactone 1 from an equimolar mixture of the two olefins 4 and 5 was achieved by unique Pd(II) chemistry. The synthetic versatility of lactone 1 has been demonstrated in the synthesis of iridoids and of the endo-Corey lactone 2, which is a key intermediate for the F(2)-isoprostane synthesis. Upon exposure of the sodium salts of 4 and 5 to a catalytic amount of Pd(OAc)(2) under oxygen, in the presence of AcOH, an isomeric lactone 12 was obtained in addition to the title compound 1. The Pd(II) lactonization was optimized by fine-tuning all the factors participating in the catalytic cycle: solvent, oxidant, co-oxidant, and Pd(II) source. The Hosokawa's heterobimetallic couple emerged as the catalyst of choice. With a Cu(II)-Pd(II) couple, the redox process was transferred to copper, and the formal oxidation state of palladium remained constant during the reaction. By virtue of this new methodology, lactone 1 was obtained in a rewarding 60% yield, along with isomeric lactone 12 in 30% yield. A detailed mechanistic study was carried out in order to elucidate the formation of lactones 1 and 12. Lactone 1 was formed from either olefin 8 or olefin 10; on the other hand, lactone 12 was formed exclusively from olefin 10. An intramolecular 1,2-acyloxypalladiation was invoked for the transformation of 8 into 1, whereas the pi-allyl complexes 13 and 11 were involved in the transformation of olefin 10 into 12 and 1, respectively. 相似文献
6.
Alessandro de Robertis Concetta de Stefano Silvio Sammartano Carmelo Rigano 《Analytica chimica acta》1986
An algorithm for computing equilibrium concentrations by the “equilibrium constant” method is described. The main features of this algorithm are: (a) a damping procedure in conjunction with the Newton-Raphson technique that avoids divergence in dealing with very complicated (simultaneous presence of simple, mixed, protonated, polynuclear and hydroxypolynuclear species) and/or very large systems; (2) the use of devices to decrease core requirements, calculation time, and ill-conditioned problems; and (3) the calculation of errors in free and species concentrations from the uncertainties in analytical concentrations and in formation constants. Four systems are used for testing computer programs on calculation of equilibrium concentrations. 相似文献
7.
The formation and stability of protonated diamines-carboxylic ligand complexes was studied potentiometrically (H(+)-glass electrode). Species formed are ALH(r) (A=cadaverine, putrescine, L=acetate, malate, tartrate, malonate, citrate, 1,2,3-propanetricarboxylate, 1,2,3,4-butanetetracarboxylate and glutamate; r=1...m+1, where m is the maximum degree of protonation of the carboxylic ligand), and their stability is a function of charges involved in the formation reaction. For the equilibrium H(i)A(i+)+H(j)L((j-z))=ALH((i+j-z))(i+j) the following linear relationships can be written: logK(1j)=-0.25+0.75 |j-z|, logK(2j)=0.50+0.90 |j-z| (by also considering some ethylenediamine and 1,2-diaminopropane complexes). Medium effects were considered. Comparison was made with analogous inorganic polyanion complexes. The simplest relationships -DeltaG(0)=6.5+/-0.3 and -DeltaG(0)=7.9+/-0.6 kJ mol(-1)n(-1) (n=number of possible salt bridges) were found for carboxylic and inorganic anions, respectively. 相似文献
8.
Formation and stability of proton-mixed ligand complexes have been studied for the systems H(+)-lysine-aspartic acid, H(+)-lysine-succinic acid and H(+)-glycine malonic acid, in aqueous solution at 25 degrees , by potentiometric technique using the (H(+))-glass electrode. For all these systems it has been found that the species ABH(j) (A and B, first and second ligand, respectively; j = 1, 2, ... m + n - 1; m and n are the maximum protonation degrees of the two ligands, respectively) are formed. The stability of these species is discussed with respect to various factors and, in particular, as a function of speciation problems. 相似文献
9.
Yang Shen Ioanna Kalograiaki Alessio Prunotto Matthew Dunne Samy Boulos Nicholas M. I. Taylor Eric T. Sumrall Marcel R. Eugster Rebecca Martin Alicia Julian-Rodero Benjamin Gerber Petr G. Leiman Margarita Menndez Matteo Dal Peraro Francisco Javier Caada Martin J. Loessner 《Chemical science》2021,12(2):576
Endolysins are bacteriophage-encoded peptidoglycan hydrolases targeting the cell wall of host bacteria via their cell wall-binding domains (CBDs). The molecular basis for selective recognition of surface carbohydrate ligands by CBDs remains elusive. Here, we describe, in atomic detail, the interaction between the Listeria phage endolysin domain CBD500 and its cell wall teichoic acid (WTA) ligands. We show that 3′O-acetylated GlcNAc residues integrated into the WTA polymer chain are the key epitope recognized by a CBD binding cavity located at the interface of tandem copies of beta-barrel, pseudo-symmetric SH3b-like repeats. This cavity consists of multiple aromatic residues making extensive interactions with two GlcNAc acetyl groups via hydrogen bonds and van der Waals contacts, while permitting the docking of the diastereomorphic ligands. Our multidisciplinary approach tackled an extremely challenging protein–glycopolymer complex and delineated a previously unknown recognition mechanism by which a phage endolysin specifically recognizes and targets WTA, suggesting an adaptable model for regulation of endolysin specificity.Combining genetic, biochemical and computational approaches, we elucidated the molecular mechanisms underlying the recognition of Listeria wall teichoic acid by bacteriophage-encoded SH3b repeats. 相似文献
10.
Copper(II) complexes with the herbicide N-(phosphonomethyl)glycine (glyphosate) have been investigated in aqueous solution by means of pH-metric measurements at different temperatures, 5 = T = 45 degrees C, calorimetry and visible spectrophotometry. Potentiometric data, at all the considered temperatures in the range 2.5 = pH = 10.5, can be explained assuming the formation of the species CuLH(0), CuL(-), CuLH(2 -)(- 1), CuL(4 -)(2) and Cu(2)L(+). By using thermodynamic data and calculated electronic spectra for each complex a structural definition is proposed for the different species. Copper(II)-glyphosate complexes are quite stable and must be taken into account in the speciation of natural fluids. 相似文献