全文获取类型
收费全文 | 8811篇 |
免费 | 242篇 |
国内免费 | 27篇 |
专业分类
化学 | 5333篇 |
晶体学 | 58篇 |
力学 | 221篇 |
综合类 | 3篇 |
数学 | 1708篇 |
物理学 | 1757篇 |
出版年
2023年 | 54篇 |
2022年 | 59篇 |
2021年 | 89篇 |
2020年 | 114篇 |
2019年 | 118篇 |
2018年 | 200篇 |
2017年 | 183篇 |
2016年 | 292篇 |
2015年 | 225篇 |
2014年 | 284篇 |
2013年 | 679篇 |
2012年 | 469篇 |
2011年 | 564篇 |
2010年 | 336篇 |
2009年 | 284篇 |
2008年 | 481篇 |
2007年 | 463篇 |
2006年 | 425篇 |
2005年 | 352篇 |
2004年 | 312篇 |
2003年 | 243篇 |
2002年 | 238篇 |
2001年 | 148篇 |
2000年 | 124篇 |
1999年 | 101篇 |
1998年 | 93篇 |
1997年 | 87篇 |
1996年 | 78篇 |
1995年 | 74篇 |
1994年 | 59篇 |
1993年 | 74篇 |
1992年 | 80篇 |
1991年 | 74篇 |
1990年 | 63篇 |
1989年 | 69篇 |
1988年 | 66篇 |
1987年 | 64篇 |
1986年 | 57篇 |
1985年 | 82篇 |
1984年 | 75篇 |
1983年 | 76篇 |
1982年 | 81篇 |
1981年 | 56篇 |
1980年 | 70篇 |
1979年 | 60篇 |
1978年 | 85篇 |
1977年 | 58篇 |
1976年 | 72篇 |
1975年 | 57篇 |
1974年 | 63篇 |
排序方式: 共有9080条查询结果,搜索用时 15 毫秒
31.
We report measured Stark shifts and widths of neutral flourine and chlorine lines. Wall stabilized arc is used as a plasma source. Electron densities 2–4×1022 m?3 are determined from the width of theH β line and electron temperatures 9500–10 000 K from plasma composition data. Experimental results for FI and ClI Stark widths and FI Stark shifts agree within 10% with semiclassical calculations. ClI Stark shifts are systematically smaller for about 20% than theoretical data with the only exception of the line from multiplet no. 15 where the discrepancy goes up to 49%. Results of investigation of similarities and regularities of Stark widths are in agreement with the study of Wiese and Konjevi?. Comparison of experimental Stark shifts shows certain types of regularities. 相似文献
32.
Beyer RL Hoang HN Appleton TG Fairlie DP 《Journal of the American Chemical Society》2004,126(46):15096-15105
Short peptides corresponding to two to four alpha-helical turns of proteins are not thermodynamically stable helices in water. Unstructured octapeptide Ac-His1-Ala2-Ala3-His4-His5-Glu6-Leu7-His8-NH(2) (1) reacts with two [Pd((15)NH(2)(CH(2))(2)(15)NH(2))(NO(3))(2)] in water to form a kinetically stable intermediate, [[Pden](2)[(1,4)(5,8)-peptide]](2), in which two 19-membered metallocyclic rings stabilize two peptide turns. Slow subsequent folding to a thermodynamically more stable two-turn alpha-helix drives the equilibrium to [[Pden](2)[(1,5)(4,8)-peptide]] (3), featuring two 22-membered rings. This transformation from unstructured peptide via turns to an alpha-helix suggests that metal clips might be useful probes for investigating peptide folding. 相似文献
33.
Summary From studies of aqueous solutions of dodecylammoniumnitrate an association mechanism has been proposed involving multiequilibrium. In the concentration range considered we can differentiate between two aspects: ranges of marked qualitative and quantitative changes and formation of differently structured surfactant species.
Zusammenfassung Aus der Untersuchung wäßriger Lösungen von Dodecylammoniumnitrat würde ein Assoziationsmechanismus abgeleitet, welcher ein Multiequilibrium beinhaltet. Im untersuchten Konzentrationsbereich können zwei Bereiche unterschieden werden: Bereiche mit ausgeprägten qualitativen und quantitativen Änderungen und Bereiche mit der Bildung von verschieden strukturierten oberflächenaktiven Spezies.相似文献
34.
Krishna Gopal Dongol M. Cristina Melo e Silva Kouki Matsubara Taisuke Matsumoto Shuntaro Mataka Thies Thiemann 《无机化学与普通化学杂志》2003,629(6):945-947
The preparation of two η6‐estra‐1, 3, 5(10), 6‐tetraene tricarbonylchromium complexes 4 and 6 are described. In both cases only one stereoisomer can be isolated, in contrast to other estrane‐tricarbonylchromium complexes, where complexations are non‐stereoselective. X‐ray crystal structural analysis of 4 discloses that only the more sterically hindered β‐facial isomer is formed. It is assumed that the 6, 7‐olefinic moiety exerts a directive influence on the complexation. 相似文献
35.
Zusammenfassung Die Temperaturabhängigkeit der Viskosität im System LiNO3–H2O und im Temperaturbereich 20–70°C wird in der Gleichung =A expB/T=T
0 zusammengefaßt; aus der so erhaltenen Beziehung werden Rückschlüsse auf die Struktur der Lösungen gezogen.
Temperature dependence of the viscosity in the system LiNO3–H2O is expressed by =A expB/T-T 0 in the temperature range 20–70°C. Possible relations to structural changes in the solutions are considered.相似文献
36.
When food containing fat is treated by ionizing radiation, a group of 2-alkylcyclobutanones is formed. These components contain the same number of carbon atoms as their precursor fatty acids and the alkyl group is located in ring position 2. Thus, from palmitic acid 2-dodecylcyclobutanone is derived. To date, there is no evidence that the cyclobutanones occur in unirradiated food. Therefore, these components cannot be considered inherent to food, and for questions pertaining to risk assessment of irradiated food it would be advisable to determine the genotoxic and toxic potentials of cyclobutanones. Measurements of DNA damage in cells exposed to 2-dodecylcyclobutanone, employing the single cell microgel electrophoresis technique, have been carried out. In vitro experiments using rat and human colon cells indicate that 2-docylcyclobutanone in the concentration range of about 0.30 – 1.25 mg/ml induces DNA strand breaks in the cells. Simultaneously, a concentration related cytotoxic effect is observed as was determined by trypan blue exclusion. To which extent these in vitro findings are of relevancy for the in vivo human exposure situation needs to be investigated in further studies. In vivo tests in rats are in progress. 相似文献
37.
Tomislav Došlić 《Journal of mathematical chemistry》2007,41(3):217-229
A global forcing set in a simple connected graph G with a perfect matching is any subset S of E(G) such that the restriction of the characteristic function of perfect matchings of G on S is an injection. The number of edges in a global forcing set of the smallest cardinality is called the global forcing number
of G. In this paper we prove several results concerning global forcing sets and numbers of benzenoid graphs. In particular, we
prove that all catacondensed benzenoids and catafused coronoids with n hexagons have the global forcing number equal to n, and that for pericondensed benzenoids the global forcing number is always strictly smaller than the number of hexagons. 相似文献
38.
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
39.
Inspired by the concept of multivalency and in pursuit of ever more intricate artificial molecular machines, we investigated the strict self-assembly of a triply threaded two-component superbundle, starting from a tritopic receptor in which three benzo[24]crown-8 macrorings are fused onto a triphenylene core and a trifurcated trication wherein three bipyridinium units are linked 1,3,5 to a central benzenoid core. The result of the investigation was quite unexpected and surprising. It transpired that the rapid formation of a doubly threaded two-component complex was followed by an extremely slow conversion (a week at 253 K in CD3COCD3 to reach equilibrium) of this kinetically controlled product into a thermodynamically controlled one, namely a triply threaded two-component superbundle. This intriguing observation begs the question: are there instances in nature where multivalency is expressed as a kinetically controlled process, prior to an equilibrium state being reached, and if so, what are the biological implications, if any? 相似文献
40.
Urška L. Štangar Urh Černigoj Polonca Trebše Ksenija Maver Silvia Gross 《Monatshefte für Chemie / Chemical Monthly》2006,137(5):647-655
Summary. Transparent TiO2 films with a high photodegradation activity towards an azo dye in aqueous solution were prepared by sol–gel processing. Films
on soda–lime glass supports protected with a thin silica barrier layer exhibited better crystallization and monodisperse nanoparticles,
higher absorption of light below 370 nm, and higher photocatalytic activity than those films deposited on bare glass supports
proving the detrimental effect of interdiffused sodium ions on the development of the anatase nanostructure. The effect of
substrate was more pronounced in thinner films (300 nm) than in thicker ones (1200 nm), which were achieved by adding a template
(i.e. Pluronic F127) to the sol. 相似文献