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排序方式: 共有622条查询结果,搜索用时 15 毫秒
101.
Santiago Gómez-Ruiz Goran N. Kalu?erovi? ?eljko ?i?ak Zorica D. Jurani? Mariano Fajardo 《Journal of organometallic chemistry》2009,694(13):1981-1987
The alkenyl-substituted titanocene complex [Ti(η5-C5H5)(η5-C5H4{CMe2(CH2CH2CHCH2)})Cl2] (1) has been synthesized and characterized using traditional methods. The reaction of 1 with 9-BBN gave the boryl substituted complex [Ti(η5-C5H5)(η5-C5H4{CMe2(CH2CH2CH2CH2BC8H14)})Cl2] (2). The cytotoxic activity of 1 and 2 was tested against tumour cell lines human adenocarcinoma HeLa, human myelogenous leukemia K562, human malignant melanoma Fem-x, human breast carcinoma MDA-MB-361 and normal immunocompetent cells peripheral blood mononuclear cells PBMC and compared with those of the reference complexes [Ti(η5-C5H5)2Cl2] (R1), [Ti(η5-C5H4Me)2Cl2] (R2) and [Ti(η5-C5H5)(η5-C5H4SiMe3)Cl2] (R3). Complex 1 showed higher cytotoxic activities on HeLa, Fem-x and K562 (IC50 values from 96.6 ± 3.4 to 149.2 ± 2.9 μM) than the reference complexes R1, R2 and R3 which presented IC50 values from 173.3 ± 6.0 to >200 μM. On the other hand, boryl substituted complex 2, present slightly lower cytotoxic activities than 1 on HeLa, Fem-x and K562 (IC50 values from 155.6 ± 5.5 to 167.9 ± 4.2 μM). However, 2 was the most active of the studied complexes against MDA-MB-361 (IC50 value of 161.1 ± 0.1 μM). Structural studies based on DFT calculations of 1 and 2 have also been carried out in order to gain a possible insight into the relationship between metal complex structure and cytotoxicity. 相似文献
102.
Jeffery S. Edmiston Jason W. Flora Mariano J. Scian Guoya Li Gaurav S. J. B. Rana Timothy B. Langston Tapas K. Sengupta Willie J. McKinney 《Analytical and bioanalytical chemistry》2009,394(6):1609-1620
Phosphorylation is the most widely studied posttranslational modification (PTM) and is an important regulatory mechanism used
during cellular responses to external stimuli. The kinases and phosphatases that regulate protein phosphorylation are known
to be affected in many human diseases. Cigarette smoking causes cardiovascular disease (CVD). Endothelial cells play a pivotal
role in CVD initiation and development; however, there have been limited investigations of the specific signaling cascades
and protein phosphorylations activated by cigarette smoke in endothelial cells. The purpose of this research was to better
understand the differential protein phosphorylation in endothelial cells stimulated with extracts of cigarette smoke total
particulate matter (CS-TPM) in vitro. Human microvascular endothelial cells were exposed in vitro to CS-TPM at concentrations
that were shown to cause endothelial cell dysfunction. The phosphorylated proteins were isolated using phosphoprotein-specific
chromatography, followed by enzymatic digestion and nano-flow capillary liquid chromatography (ncap-LC) coupled to high resolution
mass spectrometry. This study putatively identified 94 proteins in human microvascular endothelial cells that were differentially
bound to a phosphoprotein-specific chromatography column following exposure to CS-TPM suggesting differential phosphorylation.
Pathway analysis has also been conducted and confirmations of several observations have been made using immunoaffinity-based
techniques (e.g., Western blotting).
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
103.
Falcone RD Correa NM Biasutti MA Silber JJ 《Journal of colloid and interface science》2006,296(1):356-364
The behavior of acridine orange base (AOB) in nonaqueous reverse micelles composed of n-heptane/AOT/polar solvent has been performed. Ethylene glycol (EG), propylene glycol (PG), glycerol (GY), formamide (FA), dimethylformamide (DMF), and dimethylacetamide (DMA) were employed as water substitutes. The studies were performed by static and time-resolved emission spectroscopy. Thus, the distribution of AOB between the two pseudophases of the aggregates was quantified by measuring the partition constants from emission spectra at different surfactant concentration. Similar values to those obtained by means of absorption spectroscopy were obtained. This match is indicating that AOB is not experiencing partition during the lifetime of the excited state. Partitioning to the micelles is strongly favored in micelles containing hydrogen-bond donor (HBD) solvents rather than non-HBD solvents. Variations of fluorescence lifetimes with AOT concentration confirm these results. By the solvatochromic behavior of AOB in the different systems it is shown that the microenvironment at the interface is distinct from that of the bulk polar solvent, indicating that the probe senses no "free" solvent. The steady state anisotropy (r) was measured for EG/AOT/n-heptane and DMF/AOT/n-heptane systems as representatives for HBD and non-HBD polar solvents, respectively. The value of r is higher in the micelles containing EG than that obtained with DMF, and increases with AOT concentration. This is explained as due to highly structured polar solvents in the inner core. EG is interacting with the polar heads of AOT through hydrogen-bond interaction, while DMF can only interact with the Na+ counterions. This is confirmed by the time-resolved emission spectra (TRES) of the probe in the micellar systems, in comparison with the bulk solvents. 相似文献
104.
We investigate Einstein theories of gravity, coupled to a scalar field j{\varphi} and point-like matter, which are characterized by a scalar field-dependent matter coupling function eH(j){e^{H(\varphi)}} . We show that under mild constraints on the form of the potential for the scalar field, there are a broad class of Einstein-like
gravity models—characterized by the asymptotic behavior of H—which allow for a non-Newtonian weak-field limit with the gravitational potential behaving for large distances as ln r. The Newtonian term GM/r appears only as sub-leading. We point out that this behavior is also shared by gravity models described by f (R) Lagrangians. The relevance of our results for the building of infrared modified theories of gravity and for modified Newtonian
dynamics is also discussed. 相似文献
105.
Mattia Spano Alessandro Maccelli Giacomo Di Matteo Cinzia Ingallina Mariangela Biava Maria Elisa Crestoni Jean-Xavier Bardaud Anna Maria Giusti Alessia Mariano Anna Scotto DAbusco Anatoly P. Sobolev Alba Lasalvia Simonetta Fornarini Luisa Mannina 《Molecules (Basel, Switzerland)》2021,26(17)
The metabolite profile of fresh Goji berries from two cultivars, namely Big Lifeberry (BL) and Sweet Lifeberry (SL), grown in the Lazio region (Central Italy) and harvested at two different periods, August and October, corresponding at the beginning and the end of the maturation, was characterized by means of nuclear magnetic resonance (NMR) and electrospray ionization Fourier transform ion cyclotron resonance (ESI FT-ICR MS) methodologies. Several classes of compounds such as sugars, amino acids, organic acids, fatty acids, polyphenols, and terpenes were identified and quantified in hydroalcoholic and organic Bligh-Dyer extracts. Sweet Lifeberry extracts were characterized by a higher content of sucrose with respect to the Big Lifeberry ones and high levels of amino acids (glycine, betaine, proline) were observed in SL berries harvested in October. Spectrophotometric analysis of chlorophylls and total carotenoids was also carried out, showing a decrease of carotenoids during the time. These results can be useful not only to valorize local products but also to suggest the best harvesting period to obtain a product with a chemical composition suitable for specific industrial use. Finally, preliminary studies regarding both the chemical characterization of Goji leaves generally considered a waste product, and the biological activity of Big Lifeberry berries extracts was also investigated. Goji leaves showed a chemical profile rich in healthy compounds (polyphenols, flavonoids, etc.) confirming their promising use in the supplements/nutraceutical/cosmetic field. MG63 cells treated with Big Lifeberry berries extracts showed a decrease of iNOS, COX-2, IL-6, and IL-8 expression indicating their significant biological activity. 相似文献
106.
D Intrieri M Mariani A Caselli F Ragaini E Gallo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(34):10487-10490
Shedding light on azides: [Ru(TPP)CO] (TPP=tetraphenyl porphyrin dianion), white light and O(2) were found to be a suitable catalyst combination to perform the annulation of several biaryl azides. The high chemoselectivity of the process allows the synthesis of phenanthridines and dihydrophenanthridines in good yield and purity. 相似文献
107.
The water/sodium bis(2-ethylhexyl) phosphate (NaDEHP) reverse micelle (RM) system is revisited by using, for the first time, molecular probes to investigate interface properties. The solvatochromic behavior of 1-methyl-8-oxyquinolinium betaine (QB) and 6-propionyl-2-(N,N-dimethyl)aminonaphthalene (PRODAN) in the water/NaDEHP/toluene system is studied, and the results are compared with those obtained in water/sodium 1,4-bis(2-ethylhexyl) sulfosuccinate (AOT)/toluene RM media. The results demonstrate that the micropolarity, microviscosity, interfacial water structure, molecular probe partition, and intramolecular electron-transfer processes are dramatically altered for NaDEHP RM interfaces in comparison to the AOT systems. Because of organic nonpolar solvent penetration into the interface, NaDEHP RM media offer an interface with lower micropolarity and microviscosity than AOT media. Also, the interfacial water in the NaDEHP system shows enhanced water-water hydrogen-bond interaction in comparison with bulk water. The AOT RM interface represents a unique environment for PRODAN to undergo dual emission. 相似文献
108.
Formaggio F Crisma M Ballano G Peggion C Venanzi M Toniolo C 《Organic & biomolecular chemistry》2012,10(12):2413-2421
The fully-extended, multiple C(5), conformation or 2.0(5) helix is a very appealing peptide secondary structure, in particular for its potential use as a molecular spacer, as it is characterized by the longest elevation (as high as 3.62 ?) between the α-carbon atoms of two consecutive α-amino acids. Despite this intriguing property, however, it is only poorly investigated and understood. Here, using a complete series of C(α,α)-diethylglycine (Deg) homo-oligopeptide esters to the pentamer level, we exploited the properties of a fluorophore and a quencher, synthetically positioned at the N- and C-termini of the main chain, respectively, to check the applicability of the fully-extended conformation as a rigid molecular spacer. The fluorescence study was complemented by FT-IR absorption and NMR conformational investigations. The X-ray diffraction structures of selected compounds are also reported. Unfortunately, we find that, even in a solvent of low polarity, such as chloroform, in this peptide series an equilibrium does take place between the fragile fully-extended conformation and the 3(10)-helical structure, the latter becoming more and more stable as the main chain is elongated. Since the Deg homo-peptide esters lacking any terminal aromatic group, previously investigated, are known to adopt a stable fully-extended conformation in chloroform solution, we tend to attribute the 3D-structure instability observed in this work to the presence of multiple aromatic rings in their blocking groups. 相似文献
109.
Jian Dong Zhihao Zhuang Feng Song Debra Dunaway‐Mariano Paul R. Carey 《Journal of Raman spectroscopy : JRS》2012,43(1):65-71
4‐Hydroxybenzoyl‐CoA (4‐HB‐CoA) thioesterase from Arthrobacter is the final enzyme catalyzing the hydrolysis of 4‐HB‐CoA to produce coenzyme A and 4‐hydroxybenzoic acid in the bacterial 4‐chlorobenzoate dehalogenation pathway. Using a mutation E73A that blocks catalysis, stable complexes of the enzyme and its substrate can be analyzed by Raman difference spectroscopy. Here we have used Raman difference spectroscopy, in the non‐resonance regime, to characterize 4‐HB‐CoA bound in the active site of the E73A thioesterase. In addition, we have characterized complexes of the wild‐type enzyme complexed with the unreactive substrate analog 4‐hydroxyphenacyl‐CoA (4‐HP‐CoA). Both sets of complexes show evidence for two forms of the ligand in the active site: one population has the 4‐hydroxy group protonated, 4‐OH; while the second has the group as the hydroxide, 4‐O−. For bound 4‐HP‐CoA, X‐ray data show that glutamate 78 is close to the 4‐OH in the complex and it is likely that this is the proton acceptor for the 4‐OH proton. Although the pKa of the 4‐OH group on the free substrate in aqueous solution is 8.6, the relative populations of ionized and neutral 4‐HB‐CoA bound to E73A remain invariant between pH 7.3 and 9.8. The invariance with pH suggests that the 4‐OH and the ‐COO− of E78 constitute a tightly coupled pair where their separate pKa ‘s lose their individual qualities. Narrow band profiles are seen in the CO double bond and C‐S regions, suggesting that the hydrolyzable thioester group is rigidly bound in the active site in a syn gauche conformation. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
110.
Mariano Serrao Alberto Ranavolo Ole K?seler Andersen Carmela Conte Romildo Don Francesca Cortese Silvia Mari Francesco Draicchio Luca Padua Giorgio Sandrini Francesco Pierelli 《BMC neuroscience》2012,13(1):1-15