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41.
Shaakov S Galili T Stavitski E Levanon H Lukas A Wasielewski MR 《Journal of the American Chemical Society》2003,125(21):6563-6572
We have synthesized a series of structurally related, covalently linked electron donor-acceptor triads having highly restricted conformations to study the effects of radical ion pair (RP) structure, energetics, and solvation on charge recombination. The chromophoric electron acceptor in these triads is a 4-aminonaphthalene-1,8-dicarboximide (6ANI), in which the 4-amine nitrogen atom is part of a piperazine ring. The second nitrogen atom of the piperazine ring is part of a para-substituted aniline donor, where the para substituents are X = H, OMe, and NMe(2). The imide group of 6ANI is linked to a naphthalene-1,8:4,5-bis(dicarboximide) (NI) electron acceptor across a phenyl spacer in a meta relationship. The triads undergo two-step photoinduced electron transfer to yield their respective XAn(*)(+)-6ANI-Ph-NI(*)(-) RP states, which undergo radical pair intersystem crossing followed by charge recombination to yield (3)NI. Time-resolved electron paramagnetic resonance experiments on the spin-polarized RPs and triplet states carried out in toluene and in E-7, a mixture of nematic liquid crystals (LCs), show that for all three triads, the XAn(*)(+)-6ANI-Ph-NI(*)(-) RPs are correlated radical pairs and directly yield values of the spin-spin exchange interaction, J, and the dipolar interaction, D. The values of J are all about -1 mT and show that the LC environment most likely enforces the chair conformation at the piperazine ring, for which the RP distance is larger than that for the corresponding boat conformation. The values of D yield effective RP distances that agree well with those calculated earlier from the spin distributions of the radical ions. Within the LC, changing the temperature shows that the CR mechanism can be changed significantly as the energy levels of the RPs change relative to that of the recombination triplet. 相似文献
42.
Rutile Ni
x
Ti1-3x
Sb2x
O2 solid solution nanoparticles were synthesized by a sol-gel route using propylene oxide as a gelation agent. Titanium oxide
nanopowder and 12% TiCl3 solution were used as the source for titanium to investigate the influence of the titanium precursors on the formation of
the target materials. It was found that the nanoparticles prepared using 12% TiCl3 solution showed a much lower phase formation temperature (700°C) as compared to those prepared from TiO2 nanoparticles (1000°C). This lower phase formation temperature allowed a substantial reduction of the aggregation of the
particles during calcination leading to the formation of nearly mono-dispersed nanoparticles of about 20 nm. The results of
this work show that the epoxide assisted sol-gel method is capable to produce titanium-based ternary oxide solid solution
nanoparticles, owing to the formation of a highly homogeneous precursor gel intermediate. 相似文献
43.
Abstract— The photooxidation of reduced lumiflavin in its acidic form, LfH 3 + , takes place in two consecutive steps. Upon illumination of LfH 3 + in its absorption band at 313 nm the semiquinone, LfH 3 + , is formed. Two LfH 2 + ions are consumed for every LfH 2 + formed. Illumination of the semiquinone in its absorption band at 495 nm causes further oxidation so that the oxidized LfH+ ion is formed. In this reaction one LfH 3 + ion is photolyzed for every LfH+ formed. In addition, a hydrogen atom is released in the photooxidation of LfH 2 + . Mechanisms for the two photoreactions are proposed. 相似文献
44.
The photoexcited triplet state of phenazine in toluene glasses at 35 K is investigated by light modulation-EPR spectroscopy. From the transient EPR spectra and the kinetics in the three canonical orientations (p = x, y, z) the rate parameters are determined. Thus, the depopulation rate constants kp, the anisotropic spin lattice relaxation rate constants Wp, and the ratios between the population constants Ap are calculated: kx = (2.2 ± 0.3) × 102 s?1, ky = (0.21 ± 0.04) × 102 s?1, kz = (0.06 ± 0.03) × 102 s?1, Wx = (8.6 ± 0.9) × 103 s?1, Wy = (11.0 ± 1.0) × 103 s?1, Wz = (14.0 ± 1.4) × 103 s?1, and Ax: Ay:Az ≈ 1:0.04:0.02. It is concluded therefore that the in-plane spin state |τx > is the active one. 相似文献
45.
A series of 4,4'-disilyl-substituted-2,2'-bipyridine ligands were prepared using a metathesis reaction of the dianion of 4,4'-dimethyl-2,2'-bipyridine with several trialkylsilyl chlorides: 4,4'bis(tert-butyldimethylsilylmethyl)-2,2'-bipyridine (dTBDMSbipy), 4,4'-bis(dimethylthexylsilylmethyl)-2,2'-bipyridine (dTHEXbipy), and 4,4'-bis(neophyldimethylsilylmethyl)-2-2'-bipyridine (dNEObipy). It was observed that the side chain length correlated with the ability of the ligand to form hydrocarbon soluble complexes of copper(I) bromide, with dNEObipy forming the most soluble and easily crystallized complexes. The atom transfer radical polymerization (ATRP) of styrene using dNEObipy as the ligand displayed molecular weight control equivalent to other ATRP systems in which solubilizing ligands, such as 4,4'-di-5-nonyl-2,2'-bipyridine or 4,4'-di-n-heptyl-2,2'-bipyridine, were used. The one-to-one complex of dNEObipy with CuBr was prepared and its crystal structure was determined. The resulting complex had the ionic formulation [(dNEObipy)2Cu]+[CuBr2]- and displayed similar activities in styrene ATRP as the standard 2 dNEObipy/CuBr catalyst system. These and other polymerization results in addition to NMR experiments suggest that the predominant copper(I) species formed in ATRP solutions is the 2-to-1 ligand-to-copper(I) cation, [(dNEObipy)2Cu]+, with either a dihalocuprate or halide counteranion, depending upon the conditions. 相似文献
46.
Amos Korin Moshe Levy David Vofsi 《Journal of polymer science. Part A, Polymer chemistry》1980,18(1):109-121
Vinyl fluoride was polymerized by photochemical initiation in a continuous-flow cylindrical reactor at room temperature and at pressures of up to 30 atm. Copolymers with vinyl acetate were prepared in order to improve the solubility and processability of poly(vinyl fluoride) (PVF). The copolymers were hydrolyzed to the corresponding vinyl alcohol copolymers and yielded hydrophilic films that are strong and flexible only when swollen by water. It was found that on hydrolysis the Tg, Tm, and heat of fusion as well as degree of crystallinity increased. It was suggested that PVF and the copolymers with vinyl alcohol are isomorphous. 相似文献
47.
Rosario Pardo Marcos Zayat David Levy 《Journal of Sol-Gel Science and Technology》2006,40(2-3):365-370
A photochromic naphthopyran derivative was embedded in sol-gel prepared thin ormosil films. The resulting samples show high
transparency and exhibit a strong red colouration upon irradiation with UV light. The photostability of the photochromic molecules
is strongly related to the nature of the embedding ormosil matrix. The introduction of organic functional groups into the
inner pore surface of the matrix allows tailoring the chemical environment where the dye molecules will be allocated, in terms
of the effectiveness of the interaction between the photochromic molecules and the Si-OH groups on the surface of the pores,
affecting the stability of the molecules upon prolonged exposition to UV light.
The photostability of the molecules was increased in matrices functionalized with larger organic groups, or with larger amount
of modifying groups. In this way the photodegradation of the photochromic molecules could be reduced by a factor of 5, as
compared with the photodegradation of the molecules in unfunctionalized silica matrix. 相似文献
48.
49.
50.
Yoel Tsur Harold H. Levine Moshe Levy 《Journal of polymer science. Part A, Polymer chemistry》1974,12(7):1515-1529
Polybenzimidazoles were prepared in poly(phosphoric acid) from isophthalic, m- and p-phenylene diacetic, succinic, adipic, suberic, and sebacic acids and 3,3′-diaminobenzidine, 3,3′,4,4′-tetraaminodiphenyl ether and 3,3′,4,4′-tetraaminodiphenylmethane. The thermal, mechanical, and bonding properties were studied. A 3:1 copolymer of isophthalic and m-phenylenediacetic acid with 3,3′-diaminobenzidine showed the best results as far as isothermal oxidation resistance and thermal and processing characteristics. 相似文献