全文获取类型
收费全文 | 12992篇 |
免费 | 315篇 |
国内免费 | 4篇 |
专业分类
化学 | 6645篇 |
晶体学 | 159篇 |
力学 | 255篇 |
数学 | 2758篇 |
物理学 | 3494篇 |
出版年
2021年 | 156篇 |
2020年 | 175篇 |
2019年 | 164篇 |
2018年 | 211篇 |
2017年 | 234篇 |
2016年 | 473篇 |
2015年 | 424篇 |
2014年 | 457篇 |
2013年 | 857篇 |
2012年 | 625篇 |
2011年 | 743篇 |
2010年 | 497篇 |
2009年 | 431篇 |
2008年 | 411篇 |
2007年 | 380篇 |
2006年 | 289篇 |
2005年 | 174篇 |
2004年 | 210篇 |
2003年 | 203篇 |
2002年 | 199篇 |
2001年 | 170篇 |
2000年 | 188篇 |
1999年 | 174篇 |
1998年 | 165篇 |
1997年 | 158篇 |
1996年 | 150篇 |
1995年 | 142篇 |
1994年 | 141篇 |
1993年 | 143篇 |
1992年 | 144篇 |
1991年 | 126篇 |
1990年 | 144篇 |
1989年 | 130篇 |
1988年 | 118篇 |
1987年 | 132篇 |
1986年 | 113篇 |
1985年 | 156篇 |
1984年 | 169篇 |
1983年 | 122篇 |
1982年 | 148篇 |
1981年 | 136篇 |
1980年 | 125篇 |
1979年 | 141篇 |
1978年 | 139篇 |
1977年 | 122篇 |
1976年 | 146篇 |
1975年 | 139篇 |
1974年 | 131篇 |
1968年 | 127篇 |
1965年 | 131篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
91.
92.
G. P. Kamuntavičius 《Few-Body Systems》1986,1(2):91-109
We present a new method of a direct derivation of differential equations for the wave-function components of identical-pariticles systems. The method generates in a simple manner all the possible variants of these equations. In some cases they are the differential equations of Faddeev of Yakubovskii. It is shown that the case of the bound states allows to formulate very simple equations for the components which are equivalent to the Schrödinger equation for the complete wave function. The components with a minimal antisymmetry are defined and the corresponding equations are derived. 相似文献
93.
Unit cell parameters have been calculated from x-ray powder diffraction data of Mo2Br4
Py
4 (A), Mo2I4
Py
4 (B), Mo2I4
Pic
4 (C), Mo2(SCN)4
Py
4 (D) and Mo2(SCN)4
Pic
4 (E), A, B and C crystallize tetragonal. A witha=9,42,c=15,O2 Å; B witha=9,46,c=14,98 Å and C witha=9,66 andc=15,72 Å D and E crystallize orthorhombic. D witha=10,09,b=9,14,c=15,08 Å; E witha=10,22,b=9,41 andc=15,15 Å.Py=pyridine,Pic=4-methylpyridine. 相似文献
94.
Zusammenfassung An praktischen Beispielen wurde gezeigt, in welcher Weise die Trennung organischer Verbindungen mittels Papierchromatographie erzielt werden kann. Man ist nicht auf einige bewährte Lösungsmittel systeme allein angewiesen, sondern kann von Fall zu Fall systematisch neue und geeignete Systeme benützen. Es hat sich bewährt, sich nach den elementaren Löslichkeitsregeln für organische Stoffe zu richten, unter der Voraussetzung, daß die zu chromatographierende Verbindung in der stationären Phase gut, in der mobilen Phase dagegen weniger löslich ist. Durch Änderung der stationären Phase (Wasser, nicht wäßriges, polares Lösungsmittel, nicht polares Lösungsmittel) oder der Polarität und Zusammensetzung der mobilen Phase kann man das Wandern der Flecke am Chromatogramm beeinflussen, beliebige RfWerte erhalten und in vielen Fällen auch eine beliebige Reihenfolge der Verbindungen am Chromatogramm erzielen.Da die Löslichkeit organischer Verbindungen von intermolekularen Kräften abhängig ist, erscheint das Problem im Zusammenhang mit strukturellen Einflüssen sehr kompliziert und muß für jeden Fall auf eigene Weise gelöst werden. Die Löslichkeitseigenschaften können weiter durch Benutzung reaktiver Lösungsmittel beeinflußt werden, die z. B. die Verbindungen in wasserlösliche Salze überführen können. Dabei ist an die möglichen Komplikationen, die bei ionisierbaren Verbindungen durch Dissoziation und Hydrolyse entstehen können, zu achten.Von den Hauptfaktoren, die eine Trennung ermöglichen können, seien die folgenden erwähnt: funktionelle Gruppen, ihre Anzahl, Polarität, gegenseitige Stellung, bzw. ihre Basizität oder Azidität, C-Atomanzahl in homologen Verbindungen, inter- und intramolekulare Wasserstoffbindungen, sterische Faktoren u. a. Es ist dann von der Art des gewählten Lösungsmittelsystems abhängig, welche der genannten Faktoren im Vordergrund stehen und welche beseitigt werden.Wenn die Löslichkeitsunterschiede der zu trennenden Stoffe zu gering sind, um gute Trennungen zu ermöglichen, ist es zweckmäßig, die Verbindungen in solche Derivate zu überführen, deren Strukturunterschiede größer sind.
Summary Practical examples are given to show how organic compounds can be separated by means of paper chromatography. The operator is not limited to tested solvent systems, but can use new suitable systems as the occasion demands. It has been found best to abide by the elementary rules of solubility of organic compounds, provided the compound to be chromatographed is quite soluble in the stationary phase but less soluble in the mobile phase. By altering the stationary phase (water, nonaqueous, polar solvent, non-polar solvent) or the polarity and composition of the mobile phase, the migration of the stains in the chromatogram can be influenced, selectedR f -values can be obtained, and in many cases it is also possible to secure a desired succession of the compounds on the chromatogram.Since the solubility of organic compounds depends on intermolecular forces, the problem in connection with structural influences appears very complicated and must be solved individually for each case. Moreover, the solubility characteristics can be affected by using reactive solvents; for instance, the compounds can be converted into water soluble salts. Under such circumstances, sight must not be lost of the complications which may arise because of the dissociation and hydrolysis of ionizable compounds. The following are among the chief factors, which may make a separation possible: functional groups, their number, polarity, relative position, their basicity or acidity, C-atom number in homologous compounds, inter- and intramolecular hydrogen bonds, steric factors, etc. It then depends on the type of solvent system selected, which of these factors are predominant and which can be neglected or eliminated.If the solubility differences are too slight to permit good separations, the compounds to be separated should, if possible, be converted into derivatives whose structural differences are more pronounced.
Résumé Des exemples pratiques montrent comment il est possible d'effectuer la séparation de combinaisons organiques par Chromatographie sur papier. Il n'est pas uniquement fait appel à des systèmes de solvants éprouvés mais, dans certains cas, de nouveaux systèmes appropriés sont systématiquement utilisés.Il s'est avéré satisfaisant de faire appel aux règles élémentaires de solubilité des substances organiques sous réserve que la combinaison à chromatographier soit suffisamment soluble dans la phase stationnaire et moins soluble dans la phase mobile. En faisant varier la phase stationnaire (eau, solvant non aqueux, solvant polaire, solvant non polaire) ou la polarité et la composition de la phase mobile, il est possible d'influencer la migration des taches du chromatogramme, d'obtenir des valeurs deR f désirées et, dans de nombreux cas, d'obtenir les combinaisons dans un ordre déterminé sur le chromatogramme.La solubilité des combinaisons organiques étant fonction des forces intermoléculaires il en résulte que le problème se complique considérablement dans la mesure où l'on considère les influences structurelles et que chaque cas particulier doit recevoir une solution qui lui est propre. Les propriétés de solubilité peuvent en outre être influencées par l'emploi de solvants réactifs qui peuvent transformer, par exemple les combinaisons en sels solubles dans l'eau. Il faut alors tenir compte des possibilités de complications qui peuvent apparaître par dissociation et hydrolyse des combinaisons ionisables.Parmi les principaux facteurs qui permettent une séparation, il convient de mentionner les suivants: les groupes fonctionnels, leur nombre, leur polarité, leur position relative, ou encore leur acidité ou leur basicité, le nombre d'atomes de carbone de combinaisons homologues, les liaisons hydrogène inter- et intramoléculaires, les facteurs stériques, etc. Suivant la nature du système solvant choisi pourront alors varier les facteurs dont l'effet est prépondérant et ceux dont l'effet est nul. Lorsque les différences de solubilité des substances à séparer sont trop faibles pour permettre des séparations satisfaisantes, il est commode de transformer les combinaisons en dérivés dont les différences de structure soient plus importantes.相似文献
95.
A. Gosman P. Podhájecký J. Sedláček 《Journal of Radioanalytical and Nuclear Chemistry》1976,30(1):293-298
This paper presents the method of double labelling in the study of the kinetics of homogeneous isotope exchange reactions.
This method was tested by the determination of the Sn(II)−Sn(IV) exchange rate in hydrochloric acid medium. The system was
labelled by the tracer119mSn [initially in the Sn(IV) state]; when the isotope equilibrium was established, Sn(IV) was again labelled by tracer113Sn. The separation of Sn(II) and Sn(IV) in the given time of exchange was performed by the extraction of Sn(IV)-hydroxyquinolate
into chloroform. The specific activities of the separated components were determined from the ratio of113Sn and119mSn activities. The exchange rate was calculated from the time dependence of specific activities. The advantage and possibilities
of the method of double labelling in the study of isotope exchange are discussed. 相似文献
96.
θ-Conditions, the temperature coefficient of unperturbed dimensions of the macromolecules and the thermodynamic interaction parameters ψ and κ were determined for solutions of poly(methyl methacrylate) in 2-alkoxyethanols (methoxy, ethoxy and butoxy). The results for this series of solvents fit the data reported for other solvents and dln . The dependence of parameters ψ and κ exhibited deviations from the theoretical dependence, mainly near the limiting value ψ = 0.5. 相似文献
97.
Measurement has been made of the dependence of the molecular weight distribution on the ratio of the catalytic system components and on the polymerization time for polycaprolactam obtained by anionic polymerization. A bimodal character of the curves was observed for products made using molar ratios of activator (N-benzoylcaprolactam) to initiator (sodium dihydro-bis(methoxyethoxy)aluminate) of 1:1 and 1:3, when the polymerization times were less than 1 hr. This course is explained by the influence of fast side-reactions, mainly condensations. For a ratio of 3:1 of the components of the catalytic system, smooth integral distribution curves are obtained, accounting for a very fast decrease in the strong base concentration in the initial stages of the polymerization. 相似文献
98.
The rapid determination of chloride and inorganic phosphate in blood serum based on continuous flow spectrophotometry was adapted to Flow Injection Analysis by applying dialysis as well as differential dilution of the injected samples. In addition to the manual injection procedure, an automated microsampling unit was developed and used. By continuous dialysis, chloride could be determined reproducibly at a sampling rate of 125 samples per hour at sample volumes of 60 μl or less. A similar sampling rate and high precision were obtained for the determination of inorganic phosphate by using differential dilution. 相似文献
99.
The basic principles of Flow Injection Analysis are outlined. The parameters governing the dispersion of the injected sample zone in the system are discussed, and it is demonstrated how these parameters can be manipulated in order to suit the requirements of an individual analytical procedure. A number of examples illustrating the practical application of f.i.a. are described, comprising the use of automated, stopped-flow, merging-zones, extraction techniques as well as f.i.a. scanning and methods based on intermittent pumping. Updated lists on f.i.a. procedures published and species that can be determined by f.i.a. are included. 相似文献
100.
The tetranuclear Cu4OBrnCl(6-n)L4 complexes, where L = 3-methylpyridine (3-Mepy), 4-methylpyridine (4-Mepy) and n=0–6 with trigonal bipyramidal coordination of copper(II) were prepared and their infrared and electronic absorption spectra
as well as cyclic voltammograms in nitromethane solutions were measured. The polyhedra in Cu4OBrnCl(6−n) (3-Mepy)4 molecules are less distorted comparing with those of 4-Mepy analogues as indicated by infrared Cu4O absorptions, far infrared Cu—Br, Cu—Cl, and Cu—N absorptions, d—d bands in electronic spectra and potentials, measured by cyclic voltammetry. The 3-Mepy complexes exhibit strong single infrared
Cu4O absorptions, while for related 4-Mepy complexes doubly split Cu4O bands were observed. Two strongly overlapped d—d bands in electronic absorption spectra of the 3-and 4-Mepy complexes in nitromethane were resolved by Gaussian fitting. The
4-Mepy ligand produces slightly stronger ligand field than its 3-Mepy analogue. The maxima of high-energy d—d bands are in a linear correlation with the number of bromide ligands. The correlations for corresponding low-energy bands
are considerably deviated from linearity. The halfwave potentials of the complexes in nitromethane correlate with both the
number of bromides and the data of electronic absorption spectra suggesting that the reducing electron at the electrode process
enters the half-filled d
z
2 orbital of the copper(II) atom. The origin of a difference between the 3-and 4-Mepy complexes in their spectral and electrochemical
properties is also discussed. 相似文献