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91.
Repická Zuzana Moncol Jan Puchoňová Miroslava Jorík Vladimír Mikloš Dušan Lis Tadeusz Padělková Zdenka Mazúr Milan Valigura Dušan 《Structural chemistry》2010,21(5):1093-1102
Novel copper(II) X-salicylate complexes with N,N-diethylnicotinamide (dena) of the formula [Cu(RCOO)2(dena)2(H2O)2] (RCOO = 3-methylsalicylate anion (3-Mesal, 1), 4-methylsalicylate anion (4-Mesal, 2), 5-methylsalicylate anion (5-Mesal, 3), 5-methoxysalicylate anion (5-MeOsal, 4) or 4-methoxysalicylate anion (4-MeOsal, 5)), and complex [Cu(3-MeOsal)2(dena)2(H2O)2]∙2H2O (3-MeOsal = 3-methoxysalicylate anion (6)) have been prepared in the crystalline forms and characterized by spectroscopic methods (IR, Vis–UV, EPR). All the compounds
according to their composition (1–5) seem to possess octahedral copper(II) stereochemistry. The complex 1 has been prepared in two different forms. X-ray analyses of the complexes 1, 4, and 5 were carried out and they featured a tetragonal-bipyramidal geometry around the copper atoms. The tetragonal planes are created
by X-salicylate anions bonded to the copper(II) atoms via unidentate carboxylate oxygen atoms and the pyridine ring nitrogen
atoms of the neutral ligand N,N-diethylnicotinamide, while in axial positions are water molecules. The two forms of complex 1 present conformation polymorphs and supramolecular isomers. 相似文献
92.
Zechao Yang Lukas Fromm Tim Sander Julian Gebhardt Tobias A. Schaub Andreas Grling Milan Kivala Sabine Maier 《Angewandte Chemie (International ed. in English)》2020,59(24):9549-9555
Demonstrated here is a supramolecular approach to fabricate highly ordered monolayered hydrogen‐ and halogen‐bonded graphyne‐like two‐dimensional (2D) materials from triethynyltriazine derivatives on Au(111) and Ag(111). The 2D networks are stabilized by N???H?C(sp) bonds and N???Br?C(sp) bonds to the triazine core. The structural properties and the binding energies of the supramolecular graphynes have been investigated by scanning tunneling microscopy in combination with density‐functional theory calculations. It is revealed that the N???Br?C(sp) bonds lead to significantly stronger bonded networks compared to the hydrogen‐bonded networks. A systematic analysis of the binding energies of triethynyltriazine and triethynylbenzene derivatives further demonstrates that the X3‐synthon, which is commonly observed for bromobenzene derivatives, is weaker than the X6‐synthon for our bromotriethynyl derivatives. 相似文献
93.
Andreas Herburger Dr. Milan Ončák Dr. Chi-Kit Siu Ephrem G. Demissie Jakob Heller Dr. Wai Kit Tang Prof. Dr. Martin K. Beyer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(43):10165-10171
Understanding the intrinsic properties of the hydrated carbon dioxide radical anions CO2.−(H2O)n is relevant for electrochemical carbon dioxide functionalization. CO2.−(H2O)n (n=2–61) is investigated by using infrared action spectroscopy in the 1150–2220 cm−1 region in an ICR (ion cyclotron resonance) cell cooled to T=80 K. The spectra show an absorption band around 1280 cm−1, which is assigned to the symmetric C−O stretching vibration νs. It blueshifts with increasing cluster size, reaching the bulk value, within the experimental linewidth, for n=20. The antisymmetric C−O vibration νas is strongly coupled with the water bending mode ν2, causing a broad feature at approximately 1650 cm−1. For larger clusters, an additional broad and weak band appears above 1900 cm−1 similar to bulk water, which is assigned to a combination band of water bending and libration modes. Quantum chemical calculations provide insight into the interaction of CO2.− with the hydrogen-bonding network. 相似文献
94.
Milan Melník Peter Mikuš 《Phosphorus, sulfur, and silicon and the related elements》2020,195(5):367-370
AbstractIn this review, the structural data of monomeric platinum(II) complexes with inner coordination spheres of Pt(η2-P2L)(SiL)2, Pt(η2-P2L)(η2-Si2L) and Pt(η2-P,SiL)2 are classified and analyzed. These complexes crystallize in three crystal systems: monoclinic (8 examples), triclinic (4 examples) and orthorhombic (4 examples). Distorted square-planar environments about the Pt(II) atoms are built up by combination of homobi-P,P with two monodentate Si donor ligands; homobi-PP with homo-Si,Si donor ligands, or heterobi-P,Si donor ligands. The chelating ligands create metallacycles with the following angles: 65.0° (SiOSi) < 83.1° (SiC2Si) < 85.2° (PC2P) < 88.8° (SiSi2Si)). The mean Pt-P and Pt-Si bond distances in Pt(η2-P2L)·(SiL)2 complexes are 2.319 and 2.365?Å; in Pt(η2-P2L)(η2-Si2L) the values are 2.316 and 2.360?Å. The complex [Pt{η2-Me2P(C2B10H10)SiMe2}2] exists in two isomeric forms, a monoclinic cis- and a triclinic trans-isomer. The structural data are compared and discussed with the complexes of inner coordination spheres: Pt(η2-P2L)(XL)2 (X?=?O, N, CN, BL, Cl, SL, SeL, Br, or I) and Pt(η2-P2L)(η2-X2L) (X?=?OL, NL, SL or SeL). 相似文献
95.
Milan Skalicky Jan Kubes Hajihashemi Shokoofeh Md. Tahjib-Ul-Arif Pavla Vachova Vaclav Hejnak 《Molecules (Basel, Switzerland)》2020,25(22)
There are 11 different varieties of Beta vulgaris L. that are used in the food industry, including sugar beets, beetroots, Swiss chard, and fodder beets. The typical red coloration of their tissues is caused by the indole-derived glycosides known as betalains that were analyzed in hypocotyl extracts by UV/Vis spectrophotometry to determine the content of betacyanins (betanin) and of betaxanthins (vulgaxanthin I) as constituents of the total betalain content. Fields of beet crops use to be also infested by wild beets, hybrids related to B. vulgaris subsp. maritima or B. macrocarpa Guss., which significantly decrease the quality and quantity of sugar beet yield; additionally, these plants produce betalains at an early stage. All tested B. vulgaris varieties could be distinguished from weed beets according to betacyanins, betaxanthins or total betalain content. The highest values of betacyanins were found in beetroots ‘Monorubra’ (9.69 mg/100 mL) and ‘Libero’ (8.42 mg/100 mL). Other beet varieties contained less betacyanins: Sugar beet ‘Labonita’ 0.11 mg/100 mL; Swiss chard ‘Lucullus,’ 0.09 mg/100 mL; fodder beet ‘Monro’ 0.15 mg/100 mL. In contrast with weed beets and beetroots, these varieties have a ratio of betacyanins to betaxanthins under 1.0, but the betaxanthin content was higher in beetcrops than in wild beet and can be used as an alternative to non-red varieties. Stability tests of selected varieties showed that storage at 22 °C for 6 h, or at 7 °C for 24 h, did not significantly reduce the betalain content in the samples. 相似文献
96.
Jakob Heller Tobias F. Pascher Dr. Christian van der Linde Dr. Milan Ončák Prof. Dr. Martin K. Beyer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(66):16367-16376
Hydrated aluminium cations have been investigated as a photochemical model system with up to ten water molecules by UV action spectroscopy in a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. Intense photodissociation was observed starting at 4.5 eV for two to eight water molecules with loss of atomic hydrogen, molecular hydrogen and water molecules. Quantum chemical calculations for n=2 reveal that solvation shifts the intense 3s–3p excitations of Al+ into the investigated photon energy range below 5.5 eV. During the photochemical relaxation, internal conversion from S1 to T2 takes place, and photochemical hydrogen formation starts on the T2 surface, which passes through a conical intersection, changing to T1. On this triplet surface, the electron that was excited to the Al 3p orbital is transferred to a coordinated water molecule, which dissociates into a hydroxide ion and a hydrogen atom. If the system remains in the triplet state, this hydrogen radical is lost directly. If the system returns to singlet multiplicity, the reaction may be reversed, with recombination with the hydroxide moiety and electron transfer back to aluminium, resulting in water evaporation. Alternatively, the hydrogen radical can attack the intact water molecule, forming molecular hydrogen and aluminium dihydroxide. Photodissociation is observed for up to n=8. Clusters with n=9 or 10 occur exclusively as HAlOH+(H2O)n-1 and are transparent in the investigated energy range. For n=4–8, a mixture of Al+(H2O)n and HAlOH+(H2O)n-1 is present in the experiment. 相似文献
97.
Boca R Gembický M Herchel R Haase W Jäger L Wagner C Ehrenberg H Fuess H 《Inorganic chemistry》2003,42(22):6965-6967
Triethylenetetramine (L(4)) was used as a tetradentate blocking ligand that, after complexation with Ni(II), leaves two sites ready for ligation with tricyanomethanide. The formed binuclear complex [L(4)Ni(NCC(CN)CN)(2)NiL(4)](ClO(4))(2) exhibits a ferromagnetic coupling with J/hc = +0.15 cm(-1) and g(Ni) = 2.126; below 16 K, a ferromagnetic ordering is evidenced by ac magnetic susceptibility (both in-phase and out-of-phase), magnetization, field-cooled magnetization, and zero-field-cooled magnetization measurements. 相似文献
98.
Erich Widmer Milan Soukup Reinhard Zell Emil Broger Hans Peter Wagner Marquard Imfeld 《Helvetica chimica acta》1990,73(4):861-867
Starting from the readily available, optically active (4R)-4-hydroxy-2,2,6-trimethylcyclohexanone ( 1 ), a new technical synthesis of (3R,3′R)-zeaxanthin is described. According to a 2(C9 + C6) + C10 = C40 construction scheme, the ketone 1 was first transformed with (E)-3-methylpent-2-en-4-yn-1-ol ( 5 ) into a C15-intermediate which, by a three-step sequence, could be converted into the known olefinic C15-Wittig salt 4 . Optimized conditions for the final Wittig reaction of 4 with the C10-dialdehyde 3 are discussed. Based on 1 , the overall yield of the entire technical process is ca. 40%. 相似文献
99.
Zusammenfassung Die dünnschichtchromatographische Trennung des Urans von Metallen der Ammoniumsulfidgruppe wurde beschrieben. Als Laufmittel dient ein Gemisch Aceton-Isobutanol-Salzsäure-Wasser. Nach Ablösung der Sorptionsschicht wird das Uran ausgewaschen und mit MDCM spektralphotometrisch bestimmt. pH- und Zeitabhängigkeit des Uran-MDCM-Komplexes werden untersucht und die Genauigkeit der Methode angegeben.
Summary The thin layer Chromatographic separation of uranium from metals of the ammonium sulfide group is described. The mobile phase is an acetoneisobutanol-hydrochloric acid-water mixture. After dissolving off the sorption layer, the uranium is washed out and determined spectrophotometrically with MDCM. The pH- and time relationship of the uranium-MDCM complex were studied and the precision of the method is given.
Résumé On décrit la séparation de l'uranium des métaux du groupe sulfure d'ammonium, par Chromatographie en couche mince. On utilise comme phase mobile un mélange acétone-isobutanol-acide chlorhydrique. Après lessivage de la couche de sorption, on élimine l'uranium par lavage et on le dose spectrophotométriquement par le MDCM. On étudie l'influence du pHet du temps sur le complexe uranium-MDCM et l'on indique la précision de la méthode.相似文献
100.
The mixed dissociation constants of four anticancer drugs - camptothecine, 7-ethyl-10-hydroxycamptothecine, 10-hydroxycamptothecine and 7-ethylcamptothecine, including diprotic and triprotic molecules at various ionic strengths I of range 0.01 and 0.4, and at temperatures of 25 and 37 °C - were determined with the use of two different multiwavelength and multivariate treatments of spectral data, SPECFIT32 and SQUAD(84) nonlinear regression analyses and INDICES factor analysis. A proposed strategy for dissociation constants determination is presented on the acid-base equilibria of camptothecine. Indices of precise modifications of the factor analysis in the program INDICES predict the correct number of components, and even the presence of minor ones, when the data quality is high and the instrumental error is known. The thermodynamic dissociation constant was estimated by nonlinear regression of {pKa, I} data at 25 and 37 °C: for camptothecine and 3.02(8), and 10.23(8); for 7-ethyl-10-hydroxycamptothecine, and 2.46(6), and 8.74(3), and 9.47(8); for 10-hydroxycamptothecine and 2.84(5), and 8.92(2), and 9.98(4); and for 7-ethylcamptothecine and 3.30(16), and 10.98(18). Goodness-of-fit tests for various regression diagnostics enabled the reliability of the parameter estimates found to be proven. Pallas and Marvin predict pKa being based on the structural formulae of drug compounds in agreement with the experimental value. 相似文献