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11.
Vigalok A Rybtchinski B Gozin Y Koblenz TS Ben-David Y Rozenberg H Milstein D 《Journal of the American Chemical Society》2003,125(51):15692-15693
An unprecedented metal-stabilized phenoxonium cation was prepared by a process involving dearomatization of a phenoxy complex. The unique eta2 C=O-metal (iridium) coordination mode leaves the positive charge delocalized within the former aromatic ring. The X-ray structure and conversion into eta2 C=O-coordinated metal-quinone complex are described. 相似文献
12.
Diskin-Posner Y Patra GK Goldberg I 《Chemical communications (Cambridge, England)》2002,(13):1420-1421
Targeted synthesis of new supramolecular motifs of metalloporphyrins in crystals by a concerted mechanism of molecular recognition in three dimensions, aided by organic ligands, is presented; it involves induced assembly of [tetrakis(4-hydroxyphenyl)porphyrinato]zinc species by a combination of axial coordination through bridging bipyridyls and of lateral hydrogen bonding. 相似文献
13.
Dr. Koushik Chandra Dr. Tapta Kanchan Roy Dr. Deborah E. Shalev Prof. Abraham Loyter Prof. Chaim Gilon Prof. R. Benny Gerber Prof. Assaf Friedler 《Angewandte Chemie (International ed. in English)》2014,53(36):9450-9455
We present a new approach for peptide cyclization during solid phase synthesis under highly acidic conditions. Our approach involves simultaneous in situ deprotection, cyclization and trifluoroacetic acid (TFA) cleavage of the peptide, which is achieved by forming an amide bond between a lysine side chain and a succinic acid linker at the peptide N‐terminus. The reaction proceeds via a highly active succinimide intermediate, which was isolated and characterized. The structure of a model cyclic peptide was solved by NMR spectroscopy. Theoretical calculations support the proposed mechanism of cyclization. Our new methodology is applicable for the formation of macrocycles in solid‐phase synthesis of peptides and organic molecules. 相似文献
14.
A series of substituted thiophene dioxides was tested as diene substrates for the antibody 1E9, which was elicited with a hexachloronorbornene derivative and normally catalyzes the inverse electron‐demand Diels–Alder reaction between 2,3,4,5‐tetrachlorothiophene dioxide (TCTD) and N‐ethylmaleimide (NEM). Previous structural and computational studies had suggested that the catalytic efficiency of this system derives in part from a very snug fit between the apolar active site and the transition state of this reaction. Nevertheless, replacing all the Cl‐atoms in the hapten with Br‐atoms leads to no loss in affinity (Kd=0.1 nM ), indicating substantial conformational flexibility in the residues that line the binding pocket. Consistent with this observation, the 2,3,4,5‐tetrabromothiophene dioxide is a good substrate for the antibody (kcat=1.8 min?1, KNEM=14 μM ), despite being considerably larger than TCTD. In contrast, normal electron‐demand Diels–Alder reactions between NEM and unsubstituted thiophene dioxide or 2,3,4,5‐tetramethylthiophene dioxide, which are much smaller or nearly isosteric with TCTD, respectively, are not detectably accelerated. These results show that the electronic properties of the 1E9 active site are optimized to a remarkable degree for the inverse electron‐demand Diels–Alder reaction for which it was designed. Indeed, they appear to play a more important role in catalysis than simple proximity effects. 相似文献
15.
16.
We show that a weakly integral braided fusion category ${{\mathcal C}}$ such that every simple object of ${{\mathcal C}}$ has Frobenius-Perron dimension ≤?2 is solvable. In addition, we prove that such a fusion category is group-theoretical in the extreme case where the universal grading group of ${{\mathcal C}}$ is trivial. 相似文献
17.
This paper is concerned with a new version of on-line storage allocation in which the durations of all processes are known at their arrival time. This version of the problem is motivated by applications in communication networks and has not been studied previously. We provide an on-line algorithm for the problem with a competitive ratio of O(min{log Δ,log τ}), where Δ is the ratio between the longest and shortest duration of a process, and τ is the maximum number of concurrent active processes that have different durations. For the special case where all durations are powers of two, the competitive ratio achieved is O(loglog Δ). 相似文献
18.
Luca Serventi Joseph Sachleben Yael Vodovotz 《Journal of Thermal Analysis and Calorimetry》2011,106(1):117-121
Microwavable baked goods are used frequently by the food industry to enrobe meat, vegetable, and sweet items for convenient
meal delivery but suffer from poor texture upon microwave re-heating. Par-baking the dough prior to the reheating stage provides
an opportunity to supply fresh baked goods with a simple baking stage at retail locations. Nonetheless, reheating conditions
significantly affect texture of reheated par-baked products, resulting in shrinkage, porosity reduction, and crust softening.
Appropriate formula modifications have been shown to reduce microwave-induced toughness of reheated bread by virtue of water-binding
agents and lipids. The objective of this study was, therefore, to assess the effect of soy addition on the water state of
microwavable par-baked doughs. Four dough formulations were developed by substituting wheat flour with increasing amounts
of a soy blend. Addition of soy at 20 and 26% levels improved textural properties of microwaved products, resulting in a softer
and less chewy texture. Thermogravimetric analysis (TG) showed increased water binding in soy formulations 20 and 26% with
a broadening of the main peak (attributed to water loss) that shifted from 40 to 80 °C. Differential scanning calorimetry
(DSC) depicted a transition in the −25/−10 °C range, attributed to soy lipids melting, which broadened at high soy addition.
This change in water dynamics was confirmed by proton nuclear magnetic resonance (1H NMR) relaxation tests, T
1 and T
2, having lower values in soy products, and therefore, depicting a more solid-like matrix. Soy addition above 20% significantly
improved the texture of microwave reheated par-baked flat doughs. 相似文献
19.
Rotem Shemesh Maksym Krepker Diana Goldman Yael Danin‐Poleg Yechezkel Kashi Nadav Nitzan Anita Vaxman Ester Segal 《先进技术聚合物》2015,26(1):110-116
Active antimicrobial packaging is a promising form of active packaging that can kill or inhibit microorganism growth in order to maintain product quality and safety. One of the most common approaches is based on the release of volatile antimicrobial agents from the packaging material such as essential oils. Due to their highly volatile nature, the challenge is to preserve the essential oils during the high‐temperature melt processing of the polymer, while maintaining high antimicrobial activity for a desired shelf life. This study suggests a new approach in order to achieve this goal. Antimicrobial active films are developed based on low‐density polyethylene (LDPE), organo‐modified montmorillonite clays (MMT) and carvacrol (used as an essential oil model). In order to minimize carvacrol loss throughout the polymer compounding, a pre‐compounding step is developed in which clay/carvacrol hybrids are produced. The hybrids exhibit a significant increase in the d‐spacing of clay and enhanced thermal stability. The resulting LDPE/(clay/carvacrol) films exhibit superior and prolonged antibacterial activity against Escherichia coli and Listeria innocua, while polymer compounded with pure carvacrol loses the antibacterial properties within days. The films also present an excellent antifungal activity against Alternaria alternata, used as a model plant pathogenic fungus. Furthermore, infrared spectroscopy analysis of the LDPE/(clay/carvacrol) system displayed significantly higher carvacrol content in the film as well as a slower out‐diffusion of the carvacrol molecules in comparison to LDPE/carvacrol films. Thus, these new films have a high potential for antimicrobial food packaging applications due to their long‐lasting and broad‐spectrum antimicrobial efficacy. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
20.
Livanov K Madhu V Balaraman E Shimon LJ Diskin-Posner Y Neumann R 《Inorganic chemistry》2011,50(22):11273-11275
The catalytic photocleavage of CS(2) to S(8) and a (C(x)S(y))(n) polymer with visible light using a dinuclear ruthenium(II) compound with a bipyridine units for photoactivity and a vicinal tertiary amine binding site for CS(2) activation was studied. The catalyst was characterized by X-ray diffraction, (1)H NMR, and (13)C NMR, ESI-MS and elemental analysis. CS(2) photocleavage was significant (240 turnovers, 20 h) to yield isolable S(8) and a (C(x)S(y))(n) polymer. A mononuclear catalyst or one without an amine binding site showed significantly less activity. XPS of the (C(x)S(y))(n) polymer showed a carbon/sulfur ratio ~1.5-1.6 indicating that in part both C-S bonds of CS(2) had been cleaved. Catalyst was also included within the polymer. The absence of peaks in the (1)H NMR verified the (C(x)S(y))(n) nature of the polymer, while (13)C NMR and IR indicated that the polymer had multiple types of C-S and C-C bonds. 相似文献