全文获取类型
收费全文 | 10030篇 |
免费 | 246篇 |
国内免费 | 20篇 |
专业分类
化学 | 5907篇 |
晶体学 | 67篇 |
力学 | 202篇 |
数学 | 2168篇 |
物理学 | 1952篇 |
出版年
2023年 | 63篇 |
2022年 | 77篇 |
2021年 | 156篇 |
2020年 | 141篇 |
2019年 | 171篇 |
2018年 | 266篇 |
2017年 | 234篇 |
2016年 | 344篇 |
2015年 | 261篇 |
2014年 | 310篇 |
2013年 | 728篇 |
2012年 | 520篇 |
2011年 | 675篇 |
2010年 | 402篇 |
2009年 | 367篇 |
2008年 | 565篇 |
2007年 | 550篇 |
2006年 | 525篇 |
2005年 | 431篇 |
2004年 | 369篇 |
2003年 | 277篇 |
2002年 | 247篇 |
2001年 | 164篇 |
2000年 | 130篇 |
1999年 | 94篇 |
1998年 | 87篇 |
1997年 | 82篇 |
1996年 | 76篇 |
1995年 | 69篇 |
1994年 | 54篇 |
1993年 | 74篇 |
1992年 | 71篇 |
1991年 | 73篇 |
1990年 | 63篇 |
1989年 | 65篇 |
1988年 | 56篇 |
1987年 | 59篇 |
1986年 | 60篇 |
1985年 | 82篇 |
1984年 | 96篇 |
1983年 | 83篇 |
1982年 | 82篇 |
1981年 | 68篇 |
1980年 | 74篇 |
1979年 | 72篇 |
1978年 | 94篇 |
1977年 | 68篇 |
1976年 | 64篇 |
1975年 | 60篇 |
1974年 | 61篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
91.
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
92.
A monitoring of the quality of waters was attempted determining metal accumulation in target organs as otoliths of freshwater fish. Tenchs of age ranging between 2 and 10 years were sampled in three different canals receiving wastewater from industrial, agricultural and urban activities. Metal contents were determined in both lapilli and asterisci otoliths, using inductively coupled plasma-atomic emission spectroscopy (ICP-AES). Analytical data are reported for minor metals and for some trace metals. Al, Fe and Zn have contents depending on the environment where the fish has lived, while Na, K, Ca and Sr contents are insensitive to the different aquatic habitat. Considering the two types of otolith separately, lapilli display a different affinity for trace metals (Al, Fe and Zn), while in asterisci this affinity is matched only for zinc. The high affinity of zinc for both types of otoliths suggests using this metal for discriminating the fresh waters by checking its accumulation in otoliths, as well as correlating this accumulation with age of the fish: a negative power curve equation is proposed. Since highest concentrations are found in individuals of 2-3 yr., it is advisable to use this fish for such environmental studies. 相似文献
93.
Ivan Gutman Sabina Gojak Niko Radulović Boris Furtula 《Monatshefte für Chemie / Chemical Monthly》2006,137(3):277-284
Summary. In a recent work it was demonstrated that in linear hexagonal chains the distribution of π-electrons into rings (as computed
by means of the Randić–Balaban method) is uniform, irrespective of the nature of the terminal fragments. We now establish that an analogous, yet somewhat
more complex, uniformity in the π-electron distribution exists also in double linear hexagonal chains, as well as in some
other benzenoid systems. 相似文献
94.
Synthesis and fluorescent properties of some new unsymmetricbis-benzothiazolyl furans and thiophenes
L. Racane V. Tralić-Kulenović G. Karminski-Zamola L. Fišer-Jakić 《Monatshefte für Chemie / Chemical Monthly》1995,126(12):1375-1381
Summary Some newmono- andbis-benzothiazolyl compounds with furan or thiophene nuclei were synthesized by multistep reactions from the corresponding furan and thiophene aldehydes. The data obtained from emission spectra show a large influence of the benzothiazole rings on the relative quantum efficiency of the compounds under investigation.
Synthese und Fluoreszenzeigenschaften von neuen unsymmetrischenbis-Benzothiazolylfuranen und thiophenen
Zusammenfassung Einige neuebis-Benzothiazolylverbindungen mit einem Furan- bzw. Thiophenenring wurden in einer mehrstufigen Reaktion dargestellt. Die Fluoreszenzdaten der untersuchten Verbindungen zeigen einen großen Einfluß der Benzothiazolringe auf die relative Fluoreszenzquantenausbeute.相似文献
95.
Zusammenfassung Durch elektrolytische Oxydation einer Bi-Anode in gesättigter NaCl-Lösung können Bi3+-Ionen in Lösung gebracht werden. Dieser Prozeß ermöglicht die coulometrische Bestimmung anwesender Anionen, die schwerlösliche Bi-Verbindungen bilden.Es wurden Semimikro- und Mikrobestimmungen von Phosphationen durch elektrolytisch erzeugte Bi3+-Ionen bei konstanter Stromstärke ausgeführt. Die Endpunktbestimmung erfolgte amperometrisch bei konstantem Potential mit einer Indikatorelektrode — tropfende Quecksilberelektrode — und mit einer gesättigten Kalomelelektrode als Bezugselektrode. Die coulometrische Wismutometrie bietet eine weitere Möglichkeit der coulometrischen Eichung volumetrischer Lösungen im Sinne des seinerzeitigen Vorschlags vonTutundi.
Vorgetragen beim Symposium für analytische Chemie in Graz, 29. September bis 1. Oktober 1965.
Wir danken Herrn Dipl.-Ing.Vladimir Pantovi für seine Hilfe bei unserer experimentellen Arbeit. 相似文献
Summary Bi3+ ions can be brought into solution through electrolytic oxidation of a Bi-anode in saturated NaCl solution. This process makes possible the coulometric determination of the anions present that yield difficulty soluble bismuth compounds.Semimicro- and micro-determinations of phosphate ions were made via Bi3+-ions produced electrolytically at constant current strength. The endpoint was determined amperometrically at constant potential with an indicator electrode-dropping mercury electrode-and with a saturated calomel electrode as reference electrode. The coulometric bismuthometry affords a further possibility of the coulometric standardization of volumetric solutions in the sense of the proposal previously advanced byTutundi.
Résumé On peut utiliser les ions Bi3+ en solution par oxydation électrolytique d'une anode en bismuth, en solution de chlorure de sodium saturée. Ce procédé permet le dosage coulométrique des anions présents qui forment des composés peu solubles avec le bismuth.On a mis au point le dosage semimicro et micro des ions phosphates par les ions Bi3+ formés électrolytiquement sous intensité constante. On détermine par ampérométrie le point équivalent à potentiel constant à l'aide d'une électrode indicatrice — électrode de mercure à goutte pendante —et avec une électrode au calomel saturée comme électrode de référence. La «bismuthométrie» coulométrique offre de grandes possibilités pour l'étalonnage coulométrique de solutions volumétriques, suivant l'idée queTutundi a émise en son temps.
Vorgetragen beim Symposium für analytische Chemie in Graz, 29. September bis 1. Oktober 1965.
Wir danken Herrn Dipl.-Ing.Vladimir Pantovi für seine Hilfe bei unserer experimentellen Arbeit. 相似文献
96.
James D. Korp Ivan Bernal Steven F. Watkins F. R. Fronczek 《Journal of heterocyclic chemistry》1982,19(3):459-462
The molecular structure of 10-(1,3-Dithiolan-2-ylidene)-10H-indeno[1,2-f] -1,2,3,4,5-pentathiepin S7C12H89 has been determined by single crystal X-ray diffraction. The crystals are triclinic, space group PI, with two molecules in a unit cell of dimensions α = 8.931(2), b = 9.387(2), c = 10.175(2) Å, α = 75.73(2), β = 73.35(1), γ = 64.37(2)°. The structure was solved by direct methods, and refined to a final R value of 3.3% for 1925 independent reflections. The molecule consists of an indene core with a nearly co-planar dithiolane and a fused pentasulfide chain. The S5C2 ring is in the chair configuration, with an average S? S distance of 2.052 Å. There is no variation of bond lengths as is frequently seen in multi-sulfur chains. The indenone ring shows no evidence of any delocalization, while the dithiolane ring is disordered at the two methylene positions. No attempt was made to resolve the disorder, since it is frequently seen and has been thoroughly investigated previously. 相似文献
97.
Djaković-Sekulić Tatjana Perišić-Janjić Nada Sârbu Costel Lozanov-Crvenković Zagorka 《平面色谱法杂志一现代薄层色谱法》2007,20(4):251-257
JPC – Journal of Planar Chromatography – Modern TLC - Reversed-phase (RP) HPTLC with aqueous ammonia-organic modifier (acetonitrile, dioxane, acetone) mobile phases has been used to... 相似文献
98.
The mechanism and stereochemistry of δ-C atom functionalisation in the reactions of secondary straight-chain aliphatic alcohols with lead tetraacetate, ceric ammonium nitrate, and heavy metal (Pb4+, Hg2+, Ag+) salts (AcO)?1, O2?, CO32?-halogen (I2, Br2, Cl2) combinations are discussed. By demonstrating the intermediacy of 5-bromo-2-hexanol, it was confirmed that the dark silver oxidebromine induced cyclisation of 2-hexanol (and alcohols in general) involves (as the other hypohalite reactions) intramolecular 1,5-hydrogen abstraction by alkoxy radicals and formation of δ-bromohydrins. A novel and simple procedure for obtaining tetrahydrofurans from alcohols by way of the hypochlorite reaction, using silver or mercuric salts and chlorine, is described. 相似文献
99.
The adsorption of ovalbumin, -globulin, and lysozyme on uniform spherical hematite and chromium hydroxide particles in aqueous media has been studied as a function of the pH at a constant ionic strength. The uptake of ovalbumin and -globulin was greatest at their isoelectric points and differed little at 10–2 and 10–3 mol dm–3 NaNO3. The adsorption of lysozyme was strongly influenced by the ionic strength.The deposition of ovalbumin on hematite in the presence of Mg (NO3)2 was significantly greater than that with NaNO3 under otherwise comparable conditions. Dialysis experiments with ovalbumin against magnesium nitrate solutions showed Mg2+ to be specifically bound to the protein.The shapes of isotherms indicated monolayer coverage for ovalbumin and multilayer coating for lysozyme for both adsorbents. The shapes of isotherms of -globulin on hematite point to a rearrangement of the protein on the particle surface, while a monolayer was found on chromium hydroxide particles.Supported by the NSF Grant CHE-9108420Part of a Ph.D. thesis 相似文献
100.
An inductively coupled plasma atomic emission spectrometry (ICP-AES) procedure has been developed and examined for the determination of boron content (0.01 up to about 2% B) in boron-alloyed steels such as POLDI ATA BOR (65% Fe, 19%Cr, 12% Ni, 1.5% Mn, 1% B), POLDI ATA BOR EXTRA (62% Fe, 18% Cr, 13% Ni, 2.5% Mo, 1.5% Mn, 1% B) and POLDI ATA BOR-R (75% Fe, 18% Cr, 3.5% Ti, 1.8% B). The steel sample is dissolved with a mixture of hydrochloric, nitric, sulfuric and phosphoric acids in a quartz vessel. Borides of alloyed metals, especially of iron and chromium, are quantitatively decomposed. The presence of phosphoric acid in a sample solution reduces the volatility of boric acid with water vapour.Presented in part at the 1989 European Winter Conference on Plasma Spectrochemistry, Reutte, Austria 相似文献