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71.
A cationic fluorescent nanogel thermometer based on thermo‐responsive N‐isopropylacrylamide and environment‐sensitive benzothiadiazole was developed with a new azo compound bearing imidazolium rings as the first cationic radical initiator. This cationic fluorescent nanogel thermometer showed an excellent ability to enter live mammalian cells in a short incubation period (10 min), a high sensitivity to temperature variations in live cells (temperature resolution of 0.02–0.84 °C in the range 20–40 °C), and remarkable non‐cytotoxicity, which permitted ordinary cell proliferation and even differentiation of primary cultured cells.  相似文献   
72.
SUMMARY: This study identified that physiologically the superior pharyngeal constrictor muscle at the level of the base of the tongue contributes to retrusive movement of the tongue with constriction of the mid-pharyngeal cavity and possesses unique properties in terms of motor speech control along with the genioglossus muscle. From a kinematic study involving trans-nasal fiberscopy and lateral X-ray fluorography, retrusive movement of the tongue was highly correlated with constrictive movement of the mid-pharyngeal cavity. An electromyographic study revealed that the superior pharyngeal constrictor muscle at the level of the base of the tongue contributes to retrusive movement of the tongue and that the genioglossus muscle contributes to protrusive movement. We also noted that this relationship between the activities of these two muscles were in response to postural changes during vowel productions without changes in the acoustic features. These findings suggest that these two muscles act not only antagonistically to produce retrusive and protrusive movement of the tongue, but also they complement each other to conserve the shape of the vocal tract for speech production. The functional relationship between these two muscles could contribute the consecutive movement of human speech production under various conditions and might be useful when applying rehabilitation approaches for the patients with neurological speech and swallowing disorders.  相似文献   
73.
74.
A new glass capillary microelectrode for L-glutamate is described using pulled glass capillaries (tip size, approximately 12.5 microm) with a very small volume (approximately 2 microl) of inner solution containing glutamate oxidase (GluOx) and ascorbate oxidase. The operation of the electrode is based on capillary action that samples L-glutamate into the inner solution. The enzyme reaction by GluOx generates hydrogen peroxide that is detected at an Os-gel-HRP polymer modified Pt electrode in a three-electrode configuration. The amperometric response behavior of the electrode was characterized in terms of the capillarity, response time, sensitivity and selectivity for measurements of L-glutamate. The currents at 0 V vs. Ag/AgCl increased linearly with the L-glutamate concentration from 10 to 150 microM for in vitro and in situ calibrations. The response was highly selective to L-glutamate over ascorbate, dopamine, serotonin and other amino acids. The detection of L-glutamate in the extracellular fluids of different regions of mouse hippocampal slices under stimulation of KCl was demonstrated.  相似文献   
75.
Recently, we have proposed a new concept for cross-linking agents with inducible reactivity, in which the highly reactive cross-linking agent, the 2-amino-6-vinylpurine nucleoside analogue (1), can be regenerated in situ from its stable precursors, the phenylsulfide (4) and the phenylsulfoxide (3) derivatives, by a hybridization-promoted activation process with selectivity to cytidine. The phenylsulfide precursor (4) exhibited cross-linking ability despite its high stability toward strong nucleophiles such as amines and thiols. In this study, we investigated the substituent effects of the phenylsulfide group on the cross-linking reaction, and determined the 2-carboxy substituent of the phenylsulfide derivative (11k) as an efficient cross-linking agent with inducible reactivity. Detailed investigations have shown that the phenylsulfoxide (3) and phenylsulfide (4) precursors produce the 2-amino-6-vinylpurine nucleoside (1) as the common reactive species. It has been concluded that the nature of the inducible reactivity of the precursors (3 and 4) is acceleration of their elimination to the 2-amino-6-vinylpurine nucleoside (1) through the selective process in the duplex with the ODN having cytidine at the target site.  相似文献   
76.
Application of the HPLC hyphenated techniques of LC-two-dimensional (2D) NMR using pre-concentration column trapping and LC-MS was demonstrated by the identification of two major degradation products, DP-1 and DP-2, in stressed commercial tablets of amlodipine maleate. The molecular formulas were estimated by LC-MS. Sample pre-concentration by column trapping was conducted to obtain adequate 2D-NMR signals by reducing the peak widths of the degradation products and making sure that the maximum amount of each component was inside the flow cell for NMR detection. Double-quantum filtered correlation spectroscopy (DQF-COSY) was applied to identify DP-1 as beta-N-lactosylamlodipine by suppressing the residual water signal without affecting the sample signal and by measuring the coupling constant of the lactose anomeric proton. Heteronuclear multiple bond coherence spectroscopy (HMBC) was applied to characterize DP-2 as an aspartic acid derivative of amlodipine by detecting long-range CH correlations. The chemical structures of the degradation products could be successfully elucidated unambiguously without an isolation process.  相似文献   
77.
Summary: In non‐polar solvents such as toluene, Cp‐Ni and ‐Pd complexes (Cp = η5‐C5H5) with appropriate activators have been found to induce the addition polymerization of norbornene in excellent yields, for example (Cp)Pd(allyl)/[Ph3C][B(C6F5)4] gave 105 120 kg‐polymer/cat‐mol · h at room temperature. While the Cp‐Pd system was not suitable in the presence of ester‐substituted norbornenes, the Cp‐Ni system, for example (Cp)Ni(Cl)(PPh3)/AlMe3/B(C6F5)3 can copolymerize norbornene with 5‐norbornene‐2‐carboxylic acid methyl ester in toluene to give high yields (up to 68% in 2 h at room temperature) of copolymer with variable contents of the methyl ester monomer unit (17.4–60.7 mol‐%). These copolymers have high molecular weights ( = 234 100–109 500) and narrow molecular weight distributions ( = 1.78–1.89). In addition, they are soluble in common organic solvents giving flexible and transparent films on casting, that show very high Tg in the range of 352.8 to 316.0 °C. The same Ni‐catalyst system can also copolymerize norbornene derivatives with bulky substituents, i.e., 2‐butyl‐5‐norbornene and 5‐norbornene‐2‐carboxylic acid butyl ester. The Tg of these copolymers are lower (294.9–267.3 °C) than the methyl ester‐based copolymers, demonstrating that the Tg of the polynorbornene copolymer film can be tailored simply by changing the alkyl group of the monomer to within the range of 352 to 267 °C.

Figure showing the addition polymerization of norbornene using Cp‐Ni complex with appropriate activators.  相似文献   

78.
Colloidal crystals formed by polymer-grafted silica particles were immobilized by a stepwise procedure consisting of gelation by radical copolymerization followed by solidification by ring-opening radical polymerization. In the first step, the poly(methyl methacrylate) (PMMA)-grafted silica colloidal crystal suspension was incorporated into the gel without altering the crystal structure by copolymerization of cross-linker, 1,2-dimethylacryloyloxyethane (DME) and methyl methacrylate (MMA). In the second step, ring-opening radical polymerization was performed after substituting the solvent with vinylidene-1,3-dioxolane. By this two-step procedure, the silica particle array of colloidal crystals was immobilized and made into durable material.  相似文献   
79.
Catalytic alkynylation of diverse ketones and aldehydes using nonmetallic benzyltrimethylammonium hydroxide or a basic resin of the hydroxide type in DMSO is described. Aliphatic or alicyclic carbonyl partners gave satisfactory results, whereas aromatic ones afforded products with low yields. When aromatic aldehydes were reacted with phenylacetylene, enones such as chalcone derivatives were obtained in place of ynols. These organobase-catalyzed systems provide a practical nonmetallic protocol for C[bond]C formation.  相似文献   
80.
The convergent total synthesis of gambierol (1) is described. The octacyclic ether framework of 1 was constructed via the intramolecular allylation of alpha-chloroacetoxy ether followed by ring-closing metathesis. A modified Stille coupling was successfully applied to the synthesis of the triene side chain.  相似文献   
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