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131.
Masami Kamigaito Mitsuo Sawamoto Toshinobu Higashimura 《Journal of polymer science. Part A, Polymer chemistry》1993,31(12):2987-2994
Phosphoric and phosphinic acid derivatives (R1R2PO2H; R1, R2 = OPh, OPh; OnBu, OnBu; Ph, Ph; Ph, H) in conjunction with zinc chloride (ZnCl2) led to living cationic polymerization of isobutyl vinyl ether (IBVE) in toluene below 0°C. The number-average molecular weights (M?n) of the polymers (M?n > 2 × 104) were directly proportional to monomer conversion and in excellent agreement with the calculated values assuming that one polymer chain forms per R1R2PO2H molecule. Throughout the reaction, the molecular weight distributions (MWDs) stayed narrow (M?w/M?n ? 1.1). A dibasic acid, PhOP (O) (OH)2, coupled with ZnCl2, also induced living cationic polymerization of IBVE where one molecule of the acid generated two living polymer chains. The polymerization by (PhO)2PO2H/ZnCl2 and its model reactions were directly analyzed by 31P and 1H-NMR spectroscopy. The analysis showed that the acid initially forms the adduct [CH3CH(OiBu)OP(O)(OPh)2], the phosphate linkage of which is in turn activated by ZnCl2 so as to initiate living propagation. The finding thus indicates that (PhO)2PO2H indeed acts as an initiator in the living polymerization. The NMR analysis also suggested that an exchange reaction occurs between the phosphate group at the polymer terminal and the chlorine in ZnCl2. The occurrence of living IBVE polymerization with these various R1R2PO2H/ZnCl2 systems shows that phosphoric and phosphinic acids are another general class of protonic acids which are effective initiators for the living cationic polymerization assisted by Lewis acids. © 1993 John Wiley & Sons, Inc. 相似文献
132.
Horie M Oishi M Ishikawa F Shindo T Yasui A Ogino S Ito K 《Journal of AOAC International》2006,89(4):1042-1047
A method for the determination of Cinchona extract (whose main components are the alkaloids cinchonine, cinchonidine, quinidine, and quinine) in beverages by liquid chromatography was developed. A beverage with an alcohol content of more than 10% was loaded onto an OASIS HLB solid-phase extraction cartridge, after it was adjusted to pH 10 with 28% ammonium hydroxide. Other beverages were centrifuged at 4000 rpm for 5 min, and the supernatant was loaded onto the cartridge. The cartridge was washed with water followed by 15% methanol, and the Cinchona alkaloids were eluted with methanol. The Cinchona alkaloids in the eluate were chromatographed on an L-column ODS (4.6 mm id x 150 mm) with methanol and 20 mmol/L potassium dihydrogen phosphate (3 + 7) as the mobile phase. Cinchona alkaloids were monitored with an ultraviolet (UV) detector at 230 nm, and with a fluorescence detector at 405 nm for cinchonine and cinchonidine and 450 nm for quinidine and quinine (excitation at 235 nm). The calibration curves for Cinchona alkaloids with the UV detector showed good linearity in the range of 2-400 microg/mL. The detection limit of each Cinchona alkaloid, taken to be the concentration at which the absorption spectrum could be identified, was 2 microg/mL. The recovery of Cinchona alkaloids added at a level of 100 microg/g to various kinds of beverages was 87.6-96.5%, and the coefficients of variation were less than 3.3%. A number of beverage samples, some labeled to contain bitter substances, were analyzed by the proposed method. Quinine was detected in 2 samples of carbonated beverage. 相似文献
133.
The influence of the acidic and basic characters of constituent amino acid residues on the peptide fragment ions produced by in-source decay under matrix assisted laser desorption/ionization (MALDI) conditions has been studied using positive- and negative-ion experiments. Whereas the in-source decay spectra of peptides containing basic Arg and/or Lys residues near the N-terminus showed so-called cn- and an-series ions in positive-ion mode, a peptide that has an acidic amino acid cluster near the N-terminus and a basic residue near the C-terminus characteristically formed yn- and zn-series ions in the positive-ion in-source decay spectrum. These results indicated that fragment ion series produced by in-source decay depend strongly upon the acidic and basic characters of the constituent amino acid residues and the near N- and C-termini. It was suggested that in-source decay processes occur intrinsically at NH–Cα and CO–NH bonds independent of the formation of molecular-related ions, and that the cleavages at the NH–Cα and CO–NH bonds occurred independently and were dependent on the matrix used. 相似文献
134.
Isamu Onishi Kyung‐Youl Baek Yuzo Kotani Masami Kamigaito Mitsuo Sawamoto 《Journal of polymer science. Part A, Polymer chemistry》2002,40(12):2033-2043
A half‐metallocene iron iodide complex [Fe(Cp)I(CO)2] induced living radical polymerization of methyl acrylate (MA) in conjunction with an iodide initiator [(CH3)2C(CO2Et)I, 1 ] and Al(Oi‐Pr)3 to give polymers of controlled molecular weights and narrow molecular weight distributions (MWDs) (Mw/Mn < 1.2). With the use of chloride and bromide initiators, the MWDs were broader, whereas the molecular weights were similarly controlled. Other acrylates such as n‐butyl acrylate (nBA) and tert‐butyl acrylate (tBA) can be polymerized with 1 /Fe(Cp)I(CO)2 in the presence of Ti(Oi‐Pr)4 and Al(Oi‐Pr)3, respectively, to give living polymers. The 1 /Fe(Cp)I(CO)2 initiating system is applicable for the synthesis of block and random copolymers of acrylates (MA, nBA, and tBA) and styrene of controlled molecular weights and narrow MWDs (Mw/Mn = 1.2–1.3). © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2033–2043, 2002 相似文献
135.
The relaxation time of a polymer chain in an elongational flow field was investigated for hydroxypropylcellulose (HPC) semidilute solution systems by two methods: phenomenological analysis of elongational flow-induced birefringence, and dynamic light scattering (DLS) and rheological measurements. To understand the relaxation time of an entangled semiflexible polymer solution in an elongational flow field, scaling analysis of the elongational flow-induced birefringence curve was performed. The results of both temperature and concentration scaling analyses showed that birefringence curves at different temperatures and at several HPC concentrations were described well by a universal birefringence–strain rate curve. This scaling behavior was compared with the "fuzzy cylinder" model. The critical strain rate corresponded to the correlation time of the slow relaxation mode determined by DLS measurement and the relaxation spectrum obtained by dynamic viscoelasticity measurement. The elongational flow-induced birefringence observed in an HPC semidilute solution was concluded to be attributed to the orientation of the HPC segment in the entangled molecular system, because the dominant relaxation mode is found to be the concentration fluctuation of an entangled molecular cluster in a quiescent state. 相似文献
136.
Akio Tanizaki Mitsuo Sawamoto Toshinobu Higashimura 《Journal of polymer science. Part A, Polymer chemistry》1986,24(1):87-96
The cationic polymerization of p-methylstyrene initiated by acetyl perchlorate at ?78°C led to long-lived (living-like) polymers with a narrow molecular weight distribution (M?w/M?n = 1.1–1.4) in methylene chloride containing a common ion salt (n-Bu4NClO4) or in a less polar solvent (CH2Cl2/toluene, 1/4v/v). Under these conditions, the number-average molecular weight (M?n) of the polymers increased in proportion to monomer conversion and was regulated by the monomer-to-initiator ratio. When fresh feeds of the monomer were repeatedly added to a completely polymerized solution, the polymerization ensued at the same rate as before and the linear increase in M?n with monomer conversion continued. The effects of solvent polarity and the common ion salt on the polymerization showed the suppression of the ionic dissociation of the propagating species, resulting in a “nondissociated species,” to be the key factor for the formation of the long-lived polymers. 相似文献
137.
Ryuhei Wakita Masanori Miyakoshi Yohji Nakatsuji Mitsuo Okahara 《Journal of inclusion phenomena and macrocyclic chemistry》1991,10(1):127-139
A series of noncyclic neutral ionophores has been synthesized by the reaction of oligoethylene glycol dihalides with 8-quinolinol. Complexation properties for alkali metal picrates were evaluated from solvent extraction and bulk liquid membrane transport experiments. Complexation profiles of the newly synthesized ionophores with a hexyl chain were similar to those of their homologues without the hexyl chain in the extraction experiments. Among them, the pentaethylene glycol derivatives showed the highest extraction efficiency and selectivity towards potassium ion. From the1H NMR spectra (400 MHz), the change in chemical shifts of the aromatic protons upon the addition of alkali metal thiocyanates suggested the existence of a stabilization effect which is caused by intramolecular stacking conformations between the quinoline rings during complexation. Aryl stacking interactions depend on the size of the cations and on the chain length of the oligoethylene glycol. The relationship between transport ability towards alkali metal cations and lipophilicity of these ionophores is also discussed. 相似文献
138.
A stereoselectivity in an intramolecular cycloaddition of the olefinic -quinodimethanes 13 and 23 generated from the thermolysis of optically active 4β-[2-(4-methoxybenzocyclobutenyl)ethyl] -5α-methoxymethyl-3-phenyl-thio-methylenefuran-2-ones 12 and 22, respectively, is studied and a stereoselective synthesis of (+)--4,5-( 4-methoxybenzo) -1β,7aβ-(2α-methoxymethyl-5-oxofuro)hydrindane 1 is also described. 相似文献
139.
Novel synthesis of heterocyclic spirans by tandem cycloaddition to sulfur-containing heterocumulenes
Yoshiki Ohshiro Hitoshi Nanimoto Hiroyuki Tanaka Mitsuo Komatsu Toshio Agawa Noritake Yasuoka Yasushi Kai Nobutami Kasai 《Tetrahedron letters》1985,26(25):3015-3018
Novel Ni(C0)4-promoted tandem cycloadditions of diphenylcyclo- propenone to isothiocyanates and to CS2 were found to provide new heterocyclic spirans, pyrroline-2-one-5-spiro-5′-thiolene-4′-ones and a thiolene-2-one-5-spiro-5′-thiolene-4′-one, respectively, in moderate yields. 相似文献
140.
This paper discusses recent progress in transition‐metal‐catalyzed living radical polymerizations, partly focusing on the search of metal complex catalysts that play a critical role in controlling polymer molecular weights, then‐distributions, and architectures. Following a brief overview of the design of initiating systems (initiators and metal catalysts), half‐metallocene‐type complex catalysts are presented that induce living radical polymerizations of methacrylates, acrylates, and styrene to give markedly narrow molecular weight distributions and controlled molecular weights. Some of these halfmetallocenes also work in water where suspension living radical polymerization is feasible. 相似文献