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71.
Keiichi Kimura Ryoko Mizutani Tatsuya Suzuki Masaaki Yokohama 《Journal of inclusion phenomena and macrocyclic chemistry》1998,32(2-3):295-310
Design of two types of ion-conducting systems using photochromic crown ethers as the photocontrol agents is described; one type is based on the phase transition of azobenzene derivatives induced by their photoisomerization and the other based on the molecular control of metal ion complexation by crowned spirobenzopyrans. The photoresponsive ion-conducting systems are applicable to electrostatic imaging and photorefractive materials. 相似文献
72.
A membrane having an amine moiety was prepared by plasma-grafting 2-(N,N-dimethyl)aminoethyl methacrylate (DAMA) onto a microporous polyethylene substrate. Permselectivity of the membrane for CO2 over N2 was achieved in both dry and water swollen conditions. When the CO2 partial pressure in the feed gas was 0.047 atm, the selectivity of CO2 over N2 reached 130 for the highly swollen water containing membrane. This value was found to agree with that obtained with a mobile carrier membrane (supported liquid membrane) using DAMA as the carrier. The effects of several experimental conditions such as degree of grafting, feed partial pressure and temperature on the membrane performance were studied. It was suggested that the membrane acted as a fixed carrier membrane for CO2 facilitated transport in under the dry condition and acted as a fixed reaction site membrane in the water swollen condition. The carrier transport mechanism is discussed for dry and aqueous membranes. 相似文献
73.
本文利用光在多层膜介质中的传播模型,计算了可录型光盘(CD R)中染料媒体的光学特性.表明在适合于CD R光盘记录的780nm波长处,由于多层膜中光的干涉作用,样品反射率随薄膜的厚度变化发生振荡.振荡的幅度和周期依赖于染料薄膜的复数折射率(n+ik).当记录介质层的复数折射率在2.1+i0.02至2.8+i0.12之间时,能够满足CD R光盘对染料介质的要求.通过对三种菁染料薄膜的光谱性质分析及光学参数的模拟计算,证实了该方法用于染料薄膜光学特性研究的合理性.并为选择适合于光记录的染料薄膜的厚度范围提供了简便的方法 相似文献
74.
Dr. Kenichi Kato Dr. Hidetaka Kasai Dr. Akihiro Hori Prof. Dr. Masaki Takata Prof. Dr. Hiroshi Tanaka Prof. Dr. Susumu Kitagawa Akira Kobayashi Dr. Nobuki Ozawa Prof. Dr. Momoji Kubo Dr. Hidekazu Arikawa Prof. Dr. Tatsuya Takeguchi Dr. Masaaki Sadakiyo Prof. Dr. Miho Yamauchi 《化学:亚洲杂志》2016,11(10):1537-1541
The layered P2‐NaxMO2 (M: transition metal) system has been widely recognized as electronic or mixed conductor. Here, we demonstrate that Co vacancies in P2‐NaxCoO2 created by hydrogen reductive elimination lead to an ionic conductivity of 0.045 S cm?1 at 25 °C. Using in situ synchrotron X‐ray powder diffraction and Raman spectroscopy, the composition of the superionic conduction phase is evaluated to be Na0.61(H3O)0.18Co0.93O2. Electromotive force measurements as well as molecular dynamics simulations indicate that the ion conducting species is proton rather than hydroxide ion. The fact that the Co‐stoichiometric compound Nax(H3O)yCoO2 does not exhibit any significant ionic conductivity proves that Co vacancies are essential for the occurrence of superionic conductivity. 相似文献
75.
Nakayama T Kurosawa Y Furui S Kerman K Kobayashi M Rao SR Yonezawa Y Nakano K Hino A Yamamura S Takamura Y Tamiya E 《Analytical and bioanalytical chemistry》2006,386(5):1327-1333
Polymerase chain reaction (PCR) is an essential part of research based on genomics or cell analysis. The development of a
microfluidic device that would be suitable for high-temperature-based reactions therefore becomes an important contribution
towards the integration of micro-total analysis systems (μTAS). However, problems associated with the generation of air bubbles
in the microchannels before the introduction of the assay liquid, which we call the “initial start-up” in this study, made
the flow irregular and unstable. In this report, we have tried to address these problems by adapting a novel liquid-flow method
for high-temperature-based reactions. A PDMS-based microfluidic device was fabricated by soft-lithography techniques and placed
on a cartridge heater. The generation of the air bubbles was prevented by introducing the fluorinated oil, an inert and highly
viscous liquid, as the cap just before the introduction of the sample solutions into the microchannels. The technique was
applied for continuous-flow PCR, which could perform PCR on-chip in a microfluidic system. For the evaluation of practical
accuracy, plasmid DNA that serves as a reference molecule for the quantification of genetically modified (GM) maize was used
as the template DNA for continuous-flow PCR. After PCR, the products were collected in a vial and analyzed by gel electrophoresis
to confirm the accuracy of the results. Additionally, quantitative continuous-flow PCR was performed using TaqMan technology
on our PCR device. A laser detection system was also used for the quantitative PCR method. We observed a linear relationship
between the threshold cycle (Ct) and the initial DNA concentration. These results showed that it would be possible to quantify
the initial copies of the template DNA on our microfluidic device. Accurate quantitative DNA analysis in microfluidic systems
is required for the integration of PCR with μTAS, thus we anticipate that our device would have promising potential for applications
in a wide range of research. 相似文献
76.
Abstract The molecular and crystal structure of a 1:1 co-crystal of 4,4′-dimethyl-7,7′-bi([1,2,5]thiadiazolo[3,4-b]pyridylidene)–chloranilic acid, (1), has been determined by X-ray diffraction at the monoclinic space group P21/c with cell parameters of a = 8.422(6), b = 7.343(4), c = 16.112(7) ?, β = 104.988(8)°, V = 962.5(10) ?3 and Z = 2. In the crystal structure, two components connect via the intermolecular O–H···N hydrogen bonds [2.804(4) ?] and S···O
heteroatom interaction [2.945(3) ?] with R
2
2(7) couplings to form a unique and infinite one-dimensional supramolecular tape structure. The calculations of (1) at the HF/6-31G(d), MP2/6-31G(d), and B3LYP/6-31G(d) levels can almost reproduce X-ray geometry. In addition, the distances
of the intermolecular O–H···N and S···O interactions by MP2/6-31G(d) and B3LYP/6-31G(d) levels agree well with those in the
crystal. The calculated binding energies corrected BSSE and ZPE are −4.487 (HF), −7.473 (MP2), and −5.640 (B3LYP) kcal/mol.
The results suggest that the complex (1) is very stable and the dispersion interaction is significantly important for the attractive intermolecular interaction in
(1). The NBO analysis has revealed that the n(N) → σ*(O–H) interaction gives the strongest stabilization to the system and the major interaction for the intermolecular
S···O contact is n(O) → σ*(S–N).
Index Abstract In the crystal structure of the title compound, the molecules are linked by intermolecular O–H···N hydrogen bonds and short
S···O heteroatom interactions with R
2
2(7) couplings to construct a unique and infinite one-dimensional supramolecular tape structure.
相似文献
77.
Yamaguchi T Sunatsuki Y Ishida H Kojima M Akashi H Re N Matsumoto N Pochaba A Mroziński J 《Inorganic chemistry》2008,47(13):5736-5745
Heterodinuclear [(Ni (II)L)Ln (III)(hfac) 2(EtOH)] (H 3L = 1,1,1-tris[(salicylideneamino)methyl]ethane; Ln = Eu, Gd, Tb, and Dy; hfac = hexafluoroacetylacetonate) complexes ( 1.Ln) were prepared by treating [Ni(H 1.5L)]Cl 0.5 ( 1) with [Ln(hfac) 3(H 2O) 2] and triethylamine in ethanol (1:1:1). All 1.Ln complexes ( 1.Eu, 1.Gd, 1.Tb, and 1.Dy) crystallized in the triclinic space group P1 (No. 2) with Z = 2 with very similar structures. Each complex is a face-sharing dinuclear molecule. The Ni (II) ion is coordinated by the L (3-) ligand in a N 3O 3 coordination sphere, and the three phenolate oxygen atoms coordinate to an Ln (III) ion as bridging atoms. The Ln (III) ion is eight-coordinate, with four oxygen atoms of two hfac (-)'s, three phenolate oxygen atoms of L (3-), and one ethanol oxygen atom coordinated. Temperature-dependent magnetic susceptibility and field-dependent magnetization measurements showed a ferromagnetic interaction between Ni (II) and Gd (III) in 1.Gd. The Ni (II)-Ln (III) magnetic interactions in 1.Eu, 1.Tb, and 1.Dy were evaluated by comparing their magnetic susceptibilities with those of the isostructural Zn (II)-Ln (III) complexes, [(ZnL)Ln(hfac) 2(EtOH)] ( 2.Ln) containing a diamagnetic Zn (II) ion. A ferromagnetic interaction was indicated in 1.Tb and 1.Dy, while the interaction between Ni (II) and Eu (III) was negligible in 1.Eu. The magnetic behaviors of 1.Dy and 2.Dy were analyzed theoretically to give insight into the sublevel structures of the Dy (III) ion and its coupling with Ni (II). Frequency dependence in the ac susceptibility signals was observed in 1.Dy. 相似文献
78.
Kütt A Movchun V Rodima T Dansauer T Rusanov EB Leito I Kaljurand I Koppel J Pihl V Koppel I Ovsjannikov G Toom L Mishima M Medebielle M Lork E Röschenthaler GV Koppel IA Kolomeitsev AA 《The Journal of organic chemistry》2008,73(7):2607-2620
A general route to functionalized pentakis(trifluoromethyl)phenyl (C6(CF3)5) derivatives, promising building blocks for designing novel stable carbenes, radical species, superacids, weakly coordinating anions and other practically and theoretically useful species, is presented. This pertrifluoromethylation route proceeds via conveniently pregenerated (trifluoromethyl)copper (CF3Cu) species in DMF, stabilized by addition of 1,3-dimethyl-2-imidazolidinone (DMI). These species react with hexaiodobenzene at ambient temperature to give the potassium pentakis(trifluoromethyl)phenoxide along with hexakis(trifluoromethyl)benzene and pentakis(trifluoromethyl)benzene in a combined yield of 80%. A possible reaction pathway explaining the formation of pentakis(trifluoromethyl)phenoxide is proposed. Pentakis(trifluoromethyl)phenol gives rise to easily functionalized pentakis(trifluoromethyl)chlorobenzene and pentakis(trifluoromethyl)aniline. Pertrifluoromethylation of pentaiodochlorobenzene and pentaiodotoluene allows straightforward access to pentakis(trifluoromethyl)chlorobenzene and pentakis(trifluoromethyl)toluene, respectively. XRD structures of several C6(CF3)5 derivatives were determined and compared with the calculated structures. Due to the steric crowding the aromatic rings in all C6(CF3)5 derivatives are significantly distorted. The gas-phase acidities (Delta Gacid) and pKa values in different solvents (acetonitrile (AN), DMSO, water) for the title compounds and a number of related compounds have been measured. The origin of the acidifying effect of the C6(CF3)5 group has been explored using the isodesmic reactions approach. 相似文献
79.
Sakurai J Oguchi T Watanabe K Abe H Kanno S Ishikawa M Katoh T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(3):829-837
Biologically important and structurally unique marine natural products avarone (1), avarol (2), neoavarone (3), neoavarol (4) and aureol (5), were efficiently synthesized in a unified manner starting from (+)-5-methyl-Wieland-Miescher ketone 10. The synthesis involved the following crucial steps: i) Sequential BF(3)Et(2)O-induced rearrangement/cyclization reaction of 2 and 4 to produce 5 with complete stereoselectivity in high yield (2 --> 5 and 4 --> 5); ii) strategic salcomine oxidation of the phenolic compounds 6 and 8 to derive the corresponding quinones 1 and 3 (6 --> 1 and 8 --> 3); and iii) Birch reductive alkylation of 10 with bromide 11 to construct the requisite carbon framework 12 (10 + 11 --> 12). An in vitro cytotoxicity assay of compounds 1-5 against human histiocytic lymphoma cells U937 determined the order of cytotoxic potency (3 > 1 > 5 > 2 > 4) and some novel aspects of structure-activity relationships. 相似文献
80.
Yamada M Hagiwara H Torigoe H Matsumoto N Kojima M Dahan F Tuchagues JP Re N Iijima S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(17):4536-4549
A family of spin-crossover (SC) complexes, [Fe(II)H(3)L(Me)]Cl.X (X(-) = PF(6) (-), AsF(6) (-), SbF(6) (-), CF(3)SO(3) (-)), 1-4, has been synthesized, in which H(3)L(Me) denotes the hexadentate N(6) tripod-like ligand tris[2-{[(2-methylimidazol-4-yl)methylidene]amino}ethyl]amine, containing three imidazole groups, with a view to establishing the effect of the counter anion on the SC behavior. These complexes have been found to crystallize in the same monoclinic crystal system with similar cell dimensions. The general crystal structure consists of a two-dimensional (2D) extended network constructed by NH...Cl- hydrogen bonds between Cl- and the imidazole NH groups of three neighboring [Fe(II)H(3)L(Me)]2+ ions, while the anion X exists as an isolated counter anion and occupies the space between the 2D sheets. Magnetic susceptibilities and M?ssbauer spectra have revealed a variety of SC behaviors depending on the counter anion, including a one-step HS<==>(HS + LS)/2 (1, X = PF(6) (-)), a two-step HS<==>(HS + LS)/2<==>LS with a slow thermal relaxation (2, X = AsF(6) (-)), a gradual one-step HS<==>LS (3, X = SbF(6) (-)), and a steep one-step HS<==>LS with hysteresis (4, X = CF(3)SO(3) (-)). The complexes assume the space group P2(1)/n in the HS state, P2(1) in the HS + LS state, and P2(1)/n in the LS state. The Fe-N bond lengths and the N-Fe-N bond angles are indicative of the HS, HS + LS, and LS states. The molecular volumes, V, of the counter anions have been evaluated by quantum-chemical calculations as follows: 53.4 A(3) (BF(4) (-)), 54.4 A(3) (ClO(4) (-)), 73.0 A(3) (PF(6) (-)), 78.5 A(3) (AsF(6) (-)), 88.7 A(3) (SbF(6) (-)), and 86.9 A(3) (CF(3)SO(3) (-)). The size and shape of the counter anion affects the flexible 2D network structure constructed by the hydrogen bonds, leading to modifications of the SC behavior. These estimated relative sizes of the counter anions correlate well with the observed SC behaviors. 相似文献