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61.
62.
Synthesis of Aminoboronic Acid Derivatives from Amines and Amphoteric Boryl Carbonyl Compounds
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Diego B. Diaz Dr. Conor C. G. Scully Sean K. Liew Dr. Shinya Adachi Dr. Piera Trinchera Dr. Jeffrey D. St. Denis Prof. Dr. Andrei K. Yudin 《Angewandte Chemie (International ed. in English)》2016,55(41):12659-12663
Herein, we demonstrate the use of α‐boryl aldehydes and acyl boronates in the synthesis of aminoboronic acid derivatives. This work highlights the untapped potential of boron‐substituted iminium ions and offers insights into the behavior of N‐methyliminodiacetyl (MIDA) boronates during condensation and tautomerization processes. The preparative value of this contribution lies in the demonstration that various amines, including linear and cyclic peptides, can be readily conjugated with boron‐containing fragments. A mild deprotection of amino MIDA‐boronates enables access to α‐ and β‐aminoboronic acids in high chemical yields. This simple process should be applicable to the synthesis of a wide range of bioactive molecules as well as precursors for cross‐coupling reactions. 相似文献
63.
The reaction of [60]fullerene with organolithium and Grignard reagents carrying orthoester, acetal or other end groups yielded adducts 3-5 at the 6-6 bond of C60 after quenching with trifluoroacetic acid. The adducts could be easily methylated or benzylated with methyl iodide or benzyl bromide in the presence of potassium tert-butoxide to yield exclusively the 1,4-disubstituted C60 6 and 7a,b. Cleavage of the orthoester, acetal and silylether groups gave the corresponding carboxylic acid 9, aldehydes 10a,b and 11 and alcohols 12 and 13a,b. The carboxylic acid 9 readily reacted with alanine ethyl ester under standard peptide coupling conditions to give 14 in 55% yield. Attempts to generate a silyl enol ether from the reaction of aldehyde 10b with TIPSOTf and triethylamine failed. Instead the reaction led to a cyclized ether 16a (or alcohol 16b in the absence of silylating agent) resulting from the addition of an initially formed fulleride anion to the aldehyde group. The corresponding acetal 4b reacted similarly. The reaction of aldehyde 10b with aniline also gave a cyclized product 19. Surprisingly, aldehyde 11, which no longer carried an acidic fullerene proton reacted with aniline to give a product 20 resulting from an intramolecular Diels-Alder reaction followed by aromatization of a primarily formed N-phenylimine. Alcohol 13b could be readily converted to the corresponding bromide using tetramethyl-α-bromoenamine. The bromide was reacted with the carbanion derived from the protected glycine derivative to yield the diastereomeric fullerene amino acid derivatives 1-benzyl-4-[α-propyl-tert-butylglycinate benzophenone imine] 1,4-dihydro[60]fullerenes 24a and 24b. 相似文献
64.
A method has been developed to analyse for malachite green (MG), leucomalachite green (LMG), crystal violet (CV) and leucocrystal violet (LCV) residues in salmon. Salmon samples were extracted with acetonitrile:McIIIvain pH 3 buffer (90:10 v/v), sample extracts were purified on a Bakerbond strong cation exchange solid phase extraction cartridge. Aliquots of the extracts were analysed by LC-MS/MS. The method was validated in salmon, according to the criteria defined in Commission Decision 2002/657/EC. The decision limit (CCalpha) was 0.17, 0.15, 0.35 and 0.17 microg kg(-1), respectively, for MG, LMG, CV and LCV and for the detection capability (CCbeta) values of 0.30, 0.35, 0.80 and 0.32 microg kg(-1), respectively, were obtained. Fortifying salmon samples (n=6) in three separate assays, show the accuracy to be between 77 and 113% for MG, LMG, LCV and CV. The precision of the method, expressed as RSD values for the within-laboratory reproducibility, for MG, LMG and LCV at the three levels of fortification (1, 1.5 and 2.0 microg kg(-1)), was less than 13%. For CV a more variable precision was obtained, with RSD values ranging between 20 and 25%. 相似文献
65.
Dr. Emmanuel Roussakis Dr. Zongxi Li Dr. Alexander J. Nichols Prof. Dr. Conor L. Evans 《Angewandte Chemie (International ed. in English)》2015,54(29):8340-8362
Oxygen monitoring has been a topic of exhaustive study given its central role in the biochemistry of life. The ability to quantify the physiological distribution and real‐time dynamics of oxygen from sub‐cellular to macroscopic levels is required to fully understand the mechanisms associated with both normal physiology and disease states. This Review will present the most significant recent advances in the development of oxygen‐sensing materials and techniques, including polarographic, nuclear medicine, magnetic resonance, and optical approaches, that can be applied specifically for the real‐time monitoring of oxygen dynamics in cellular and tissue environments. As some of the most exciting recent advances in synthetic methods and biomedical applications have been in the field of optical oxygen sensors, a major focus will be on the development of these toolkits. 相似文献
66.
We report crystalline mixed-ligand copper complexes with phenanthroline and isocyanides with almost millesecond emission lifetimes that are efficient dioxygen sensors. The oxygen sensitivity of the prototype ([Cu(CN-xylyl)(2)(dmp)]tfpb, dmp = 2,9-dimethyl-1,10-phenanthroline; CN-xylyl = 2,6-dimethylphenylisocyanide; tfpb = tetrakis(bis-3,5-trifluoromethylphenylborate) is 38 times better than that of [Ru(phen)(3)]tfpb(2) (phen = 1,10-phenanthroline). 相似文献
67.
A fast, sensitive, and selective method for the determination of histamine in human urine samples by ultrahigh pressure liquid chromatography (LC) with fluorescence and mass spectrometry (MS) detection is investigated. A fluorescent reagent, 4-(1-pyrene) butyric acid N-hydroxysuccinimide ester was conjugated to the primary and secondary amino moieties of histamine. The structure of dipyrene-labeled histamine in human urine was determined by quadrupole time-of-flight MS with electospray ionization interface. The determination of the dipyrene derivative of histamine in urine samples was achieved within 3.9 min on an ultrahigh pressure LC Eclipse Zorbax XDB-C(18) column with 1.8 μm particle diameter. In this work, histamine separation was achieved significantly faster (3.9 min) with improved detection limit (signal-to-noise = 3) of 0.04 nM than 19.5 min with a detection limit of 0.183 nM as reported in a previous method. 相似文献
68.
Conor McLoughlin Pádraig Hough John Costello Jean-Paul Mosnier 《Applied Surface Science》2009,255(10):5338-5341
We report results on the pulsed laser deposition of ZnO obtained with the help of a new apparatus that includes in situ reflectron time-of-flight mass spectrometry, with a view to progress the understanding of the role of clusters in the laser deposition of nanostructured materials. Experiments were carried out using a Nd-YAG laser at its fundamental frequency and frequency tripled, with a fluence on target of ∼7.7 J/cm2, in vacuum (10−4 Pa) or oxygen (1 Pa) atmospheres. The results show that under certain conditions there is preferential clusterisation of the material into certain mass numbers and finally that there exists a correlation between cluster presence in the plume and the deposition of nanostructures. 相似文献
69.
Conor Crean Dr. Jie Shao Byeong Hwa Yun Nicholas E. Geacintov Prof. Dr. Vladimir Shafirovich Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(40):10634-10640
The in vivo metabolism of plasma lipids generates lipid hydroperoxides that, upon one‐electron reduction, give rise to a wide spectrum of genotoxic unsaturated aldehydes and epoxides. These metabolites react with cellular DNA to form a variety of pre‐mutagenic DNA lesions. The mechanisms of action of the radical precursors of these genotoxic electrophiles are poorly understood. In this work we investigated the nature of DNA products formed by a one‐electron reduction of (13S)‐hydroperoxy‐(9Z,11E)‐octadecadienoic acid (13S‐HPODE), a typical lipid molecule, and the reactions of the free radicals thus generated with neutral guanine radicals, G(?H).. A novel approach was devised to generate these intermediates in solution. The two‐photon‐induced ionization of 2‐aminopurine (2AP) within the 2′‐deoxyoligonucleotide 5′‐d(CC[2AP]TCGCTACC) by intense nanosecond 308 nm excimer laser pulses was employed to simultaneously generate hydrated electrons and radical cations 2AP.+. The latter radicals either in cationic or neutral forms, rapidly oxidize the nearby G base to form G(?H).. In deoxygenated buffer solutions (pH 7.5), the hydrated electrons rapidly reduce 13S‐HPODE and the highly unstable alkoxyl radicals formed undergo a prompt β‐scission to pentyl radicals that readily combine with G(?H).. Two novel guanine products in these oligonucleotides, 8‐pentyl‐ and N2‐pentylguanine, were identified. It is shown that the DNA secondary structure significantly affects the ratio of 8‐pentyl‐ and N2‐pentylguanine lesions that changes from 0.9:1 in single‐stranded, to 1:0.2 in double‐stranded oligonucleotides. The alkylation of guanine by alkyl radicals derived from lipid hydroperoxides might contribute to the genotoxic modification of cellular DNA under hypoxic conditions. Thus, further research is warranted on the detection of pentylguanine lesions and other alkylguanines in vivo. 相似文献
70.
We report Monte Carlo calculations of the charge carrier energy level disorder in polar amorphous organic solids arising from electrostatic interactions between polarizable molecular charge distributions. In contrast with previous reports in which the discrete molecular polarizibilities are modeled as a dielectric continuum having dielectric constant epsilon, our calculations take account of the molecular-scale polarization inhomogeneity. We find that the previously reported 1/epsilon scaling rule underestimates the charge carrier energy level disorder by more than a factor of 2 for typical values of epsilon. Such an underestimation strongly impacts the analysis of charge carrier transport in polar amorphous organic thin films, due to the strong dependence of the charge carrier mobility on the energy disorder. 相似文献