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31.
Malgorzata Frik Dr. Josefina Jiménez Ismael Gracia Prof. Larry R. Falvello Sarya Abi‐Habib Karina Suriel Prof. Theodore R. Muth Prof. María Contel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(12):3659-3674
The reaction of new dinuclear gold(I) organometallic complexes containing mesityl ligands and bridging bidentate phosphanes [Au2(mes)2(μ‐LL)] (LL=dppe: 1,2‐bis(diphenylphosphano)ethane 1 a , and water‐soluble dppy: 1,2‐bis(di‐3‐pyridylphosphano)ethane 1 b ) with Ag+ and Cu+ lead to the formation of a family of heterometallic clusters with mesityl bridging ligands of the general formula [Au2M(μ‐mes)2(μ‐LL)][A] (M=Ag, A=ClO4?, LL=dppe 2 a , dppy 2 b ; M=Ag, A=SO3CF3?, LL=dppe 3 a , dppy 3 b ; M=Cu, A=PF6?, LL=dppe 4 a , dppy 4 b ). The new compounds were characterized by different spectroscopic techniques and mass spectrometry The crystal structures of [Au2(mes)2(μ‐dppy)] ( 1 b ) and [Au2Ag(μ‐mes)2(μ‐dppe)][SO3CF3] ( 3 a ) were determined by a single‐crystal X‐ray diffraction study. 3 a in solid state is not a cyclic trinuclear Au2Ag derivative but it gives an open polymeric structure instead, with the {Au2(μ‐dppe)} fragments “linked” by {Ag(μ‐mes)2} units. The very short distances of 2.7559(6) Å (Au? Ag) and 2.9229(8) Å (Au? Au) are indicative of gold–silver (metallophilic) and aurophilic interactions. A systematic study of their luminescence properties revealed that all compounds are brightly luminescent in solid state, at room temperature (RT) and at 77 K, or in frozen DMSO solutions with lifetimes in the microsecond range and probably due to the self‐aggregation of [Au2M(μ‐mes)2(μ‐LL)]+ units (M=Ag or Cu; LL=dppe or dppy) into an extended chain structure, through Au? Au and/or Au? M metallophilic interactions, as that observed for 3 a . In solid state the heterometallic Au2M complexes with dppe ( 2 a – 4 a ) show a shift of emission maxima (from ca. 430 to the range of 520‐540 nm) as compared to the parent dinuclear organometallic product 1 a while the complexes with dppy ( 2 b–4 b ) display a more moderate shift (505 for 1 b to a max of 563 nm for 4 b ). More importantly, compound [Au2Ag(μ‐mes)2(μ‐dppy)]ClO4 ( 2 b ) resulted luminescent in diluted DMSO solution at room temperature. Previously reported compound [Au2Cl2(μ‐LL)] (LL dppy 5 b ) was also studied for comparative purposes. The antimicrobial activity of 1–5 and Ag[A] (A=ClO4?, SO3CF3?) against Gram‐positive and Gram‐negative bacteria and yeast was evaluated. Most tested compounds displayed moderate to high antibacterial activity while heteronuclear Au2M derivatives with dppe ( 2 a – 4 a ) were the more active (minimum inhibitory concentration 10 to 1 μg mL?1). Compounds containing silver were ten times more active to Gram‐negative bacteria than the parent dinuclear compound 1 a or silver salts. Au2Ag compounds with dppy ( 2 b , 3 b ) were also potent against fungi. 相似文献
32.
Prousalis KP Polygenis DA Syrokou A Lamari FN Tsegenidis T 《Analytical and bioanalytical chemistry》2004,379(3):458-463
An efficient analytical method is presented involving effective sample clean-up with solid-phase extraction and HPLC-UV analysis for the simultaneous determination of carbendazim, thiabendazole, and o-phenylphenol residues in lemons. Sample preparation involves extraction with acetonitrile acidified with trifluoroacetic acid and an ethyl acetate/petroleum ether mixture. Purification of the crude extract was carried out with liquid–liquid partitioning after addition of an aqueous ammonia solution. Final clean-up was performed on polymeric reversed-phase cartridges pretreated with sodium dodecyl sulfate. Chromatographic analysis was performed on a reversed-phase HPLC column isocratically eluted with an acetonitrile/water/ammonia mixture and UV detection at 254 nm. The chromatographic method is repeatable, reproducible, and sensitive. Fungicide recoveries from lemon samples fortified at levels of 5 and 1 mg kg–1 were 81–85% for carbendazim, 96–98% for thiabendazole, and 81–106% for o-phenylphenol with coefficients of variation of 2.5–7.4%. Detection limits for carbendazim, thiabendazole, and o-phenylphenol in lemons were 0.21, 0.27, and 0.51 mg kg–1, respectively. 相似文献
33.
Fundamental Difference in Reductive Lithiations with Preformed Radical Anions versus Catalytic Aromatic Electron‐Transfer Agents: N,N‐Dimethylaniline as an Advantageous Catalyst 下载免费PDF全文
Dr. Nicole Kennedy Prof. Peng Liu Prof. Theodore Cohen 《Angewandte Chemie (International ed. in English)》2016,55(1):383-386
The reductive lithiation of phenyl thioethers, or alkyl chlorides, by either preformed aromatic radical anions or by lithium metal and an aromatic electron‐transfer catalyst, is commonly used to prepare organolithiums. Revealed herein is that these two methods are fundamentally different. Reductions with radical anions occur in solution, whereas the catalytic reaction occurs on the surface of lithium, which is constantly reactivated by the catalyst, an unconventional catalyst function. The order of relative reactivity is reversed in the two methods as the dominating factor switches from electronic to steric effects of the alkyl substituent. A catalytic amount of N,N‐dimethylaniline (DMA) and Li ribbon can achieve reductive lithiation. DMA is significantly cheaper than alternative catalysts, and conveniently, the Li ribbon does not require the removal of the oxide coating when DMA is used as the catalyst. 相似文献
34.
Theodore D. Sideris Panayiotis V. Ioannou 《Phosphorus, sulfur, and silicon and the related elements》2013,188(5):1017-1030
The scope of ascorbic acid/iodine and triphenylphosphine/iodine in methanol for the direct reduction of arsenic(V) compounds having the As[dbnd]O group has been investigated. Ascorbic acid/iodine reduces arsonic acids, diphenylarsinic acid (but not dimethylarsinic acid), and triphenylarsine oxide. The rates of reduction depend on the electronic effects of the ligands bound to arsenic and on the hydrogen-bonding strength of the species, when present. When the As(V) compound has an [sbnd]NH 2 or an [sbnd]NH 3 + group, the reduction product reacts with a ketonic form of dehydroascorbic acid, giving condensation product(s). Triphenylphosphine/iodine reduced slowly the zwitterionic o-aminophenylarsonic acid but reduced faster the hydrochloric acid salt of the same acid. It reduced dimethylarsinic acid as well because the powerful electron-withdrawing Ph 3 P +coordinated to As[dbnd]O seems to outweigh the electronic and hydrogen bonding effects. 相似文献
35.
Ketones and aldehydes are conveniently and rapidly reduced to the corresponding alcohols in good yields using sodium borohydride under sealed-tube microwave conditions in either 95% ethanol or water. In purely aqueous systems, highly aliphatic substrates are sluggish, but this can be overcome by introducing sodium dodecyl sulfate (SDS) at the critical micelle concentration. With a 2:1 substrate/borohydride ratio and a reaction temperature of 100 °C, reduction is typically complete within 1 min in 95% ethanol and 5 min in water/SDS. The methodology is well suited for parallel and combinatorial synthetic approaches. 相似文献
36.
In practical applications, information about the accuracy or ‘fidelity’ of alternative surrogate systems may be ambiguous and difficult to determine. To address this problem, we propose to treat surrogate system fidelity level as a categorical factor in optimal response surface design. To design the associated experiments, we apply the Expected Integrated Mean Squared Error optimal design criterion, which takes into account both variance and bias errors. The performance of the proposed design was compared using three test cases to four types of alternatives using the Empirical Integrated Squared Error. Because of its ability to foster relatively accurate predictions, the proposed design is recommended in fidelity experimental design, particularly when the experimenters lack sufficient information about the fidelity levels of surrogate systems. The method was applied to the case of intraday trading optimization in which data were collected from the Taiwan Futures Exchange. We also calculated the implied volatility from the Merton's Jump‐diffusion model via the fast Fourier transform algorithm with three different models of varying fidelity levels. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
37.
Juan M. Venegas Zisheng Zhang Theodore O. Agbi William P. McDermott Anastassia Alexandrova Ive Hermans 《Angewandte Chemie (International ed. in English)》2020,59(38):16527-16535
Boron‐containing materials, and in particular boron nitride, have recently been identified as highly selective catalysts for the oxidative dehydrogenation of alkanes such as propane. To date, no mechanism exists that can explain both the unprecedented selectivity, the observed surface oxyfunctionalization, and the peculiar kinetic features of this reaction. We combine catalytic activity measurements with quantum chemical calculations to put forward a bold new hypothesis. We argue that the remarkable product distribution can be rationalized by a combination of surface‐mediated formation of radicals over metastable sites, and their sequential propagation in the gas phase. Based on known radical propagation steps, we quantitatively describe the oxygen pressure‐dependent relative formation of the main product propylene and by‐product ethylene. Free radical intermediates most likely differentiate this catalytic system from less selective vanadium‐based catalysts. 相似文献
38.
Theodore Tyrikos-Ergas Eric T. Sletten Jhih-Yi Huang Peter H. Seeberger Martina Delbianco 《Chemical science》2022,13(7):2115
Sulfated glycans are involved in many biological processes, making well-defined sulfated oligosaccharides highly sought molecular probes. These compounds are a considerable synthetic challenge, with each oligosaccharide target requiring specific synthetic protocols and extensive purifications steps. Here, we describe a general on resin approach that simplifies the synthesis of sulfated glycans. The oligosaccharide backbone, obtained by Automated Glycan Assembly (AGA), is subjected to regioselective sulfation and hydrolysis of protecting groups. The protocol is compatible with several monosaccharides and allows for multi-sulfation of linear and branched glycans. Seven diverse, biologically relevant sulfated glycans were prepared in good to excellent overall yield.Well-defined sulfated oligosaccharides are important synthetic targets. We present an on resin approach for the synthesis of sulfated glycans with a broad reaction scope that overcomes previous limitations associated with on resin synthesis. 相似文献
39.
Chun M. Lau Kannappan Thangaraj Govindarajulu Kumar Vayalakkavoor T. Ramakrishnan Edwin D. Stevens Joseph H. Boyer Ieva R. Politzer Theodore G. Pavlopoulos 《Heteroatom Chemistry》1990,1(3):195-209
The conversion of 3-methyl-4-benzyl-4-chloro-2-pyrazolin-5-one 10b was catalyzed by a mixture of potassium fluoride and alumina to give syn-(methyl, benzyl)bimane 6 (62%) without detectable formation of the anti isomer, A6 [a 1 : 1 mixture (87%) of the isomers 6 and A6 was obtained when the catalyst was potassium carbonate]. In a similar reaction syn-(methyl,carboethoxymethyl)bimane 7 (15%) with the anti isomer A7 (36%) was obtained from 3-methyl-4-carboethoxymethyl-4-chloro-2-pyrazolin-5-one 10c . syn-(Methyl, β-acetoxyethyl)bimane 8 (70%) was obtained from 3-methyl-4-β-acetoxyethyl-4-chloro-2-pyrazolin-5-one 10d (potassium carbonate catalysis) and was converted by hydrolysis to syn-(methyl, β-hydroxyethyl)bimane 9 (40%). Acetyl nitrate (nitric acid in acetic anhydride) converted anti-(amino,hydrogen)bimane 11 to anti-(amino,nitro)bimane 15 (91%), anti-(methyl,hydrogen)bimane 13 to anti-(methyl,nitro)(methyl,hydrogen)bimane 16 (57%), and degraded syn-(methyl,hydrogen)bimane 12 to an intractable mixture. Treatment with trimethyl phosphite converted syn-(bromomethyl,methyl)bimane 17 to syn-(dimethoxyphosphinylmethyl,methyl)bimane 18 (78%) that was further converted to syn-(styryl,methyl)bimane 19 (29%) in a condensation reaction with benzaldehyde. Treatment with acryloyl chloride converted syn-(hydroxymethyl,methyl)bimane 20 to its acrylate ester 21 (22%). Stoichiometric bromination of syn-(methyl,methyl)bimane 1 gave a monobromo derivative that was converted in situ by treatment with potassium acetate to syn-(acetoxymethyl,methyl)(methyl,methyl)bimane 47 . N-Amino-μ-amino-syn-(methylene,methyl)bimane 24 (68%) was obtained from a reaction between the dibromide 17 and hydrazine. Derivatives of the hydrazine 24 included a perchlorate salt and a hydrazone 25 derived from acetone. Dehydrogenation of syn-(tetramethylene)bimane 26 by treatment with dichlorodicyanobenzoquinone (DDQ) gave syn-(benzo,tetramethylene)bimane 27 (58%) and syn-(benzo)bimane 28 (29%). Bromination of the bimane 26 gave a dibromide 29 (92%) that was also converted by treatment with DDQ to syn-(benzo)bimane 28 . Treatment with palladium (10%) on charcoal dehydrogenated 5, 6, 10, 11-tetrahydro-7H,9H-benz [6, 7] indazol [1, 2a]benz[g]indazol-7,9-dione 35 to syn-(α-naphtho)bimane 36 (71%). The bimane 35 was prepared from 1,2,3,4-tetrahydro-1-oxo-2-naphthoate 37 by stepwise treatment with hydrazine to give 1,2,4,5-tetrahydro-3H-benz[g]indazol-3-one 38 , followed by chlorine to give 3a-chloro-2,3a,4,5-tetrahydro-3H-benz[g]indazol-3-one 39 , and base. Dehydrogenation over palladium converted the indazolone 34 to 1H-benz[g] indazol-3-ol 36 . Helicity for the hexacyclic syn-(α-naphtho)bimane 36 was confirmed by an analysis based on molecular modeling. The relative efficiencies (RE) for laser activity in the spectral region 500–530 nm were obtained for 37 syn-bimanes by reference to coumarin 30 (RE 100): RE > 80 for syn-bimanes 3, 5, 18 , and μ-(dicarbomethoxy)methylene-syn-(methylene,methyl)bimane 22 : RE 20–80: for syn-bimanes 1,2,4,20,24,26 , and μ-thia-syn-(methylene,methyl)bimane 50 : and RE 0-20 for 26 syn-bimanes. The bimane dyes tended to be more photostable and more water-soluble than coumarin 30. The diphosphonate 18 in dioxane showed laser activity at 438 nm and in water at 514 nm. Presumably helicity, that was demonstrated by molecular modeling, brought about a low fluorescence intensity for syn-(α-naphtho)bimane 36 , Φ0.1, considerably lower than obtained for syn-(benzo)bimane 28 , Φ0.9. 相似文献
40.
Theodore Garavaglia 《International Journal of Theoretical Physics》1984,23(3):251-294
A covariant formulation is developed and used to derive cross sections for the analysis of experiments in which polarized electrons (muons) are scattered from spin-zero and from polarized spin-1/2 targets. The analysis is based upon the single virtual photon representation of the electromagnetic interaction, initially, neither high-energy nor low-energy approximations are made so that one may derive results in which the orientation of the polarization vectors of the interacting particles changes as a result of the scattering. The general formulation is valid for all polarization configurations for the electron and nucleon in deep inelastic scattering, and for all polarization configurations for the initial and final state particles in elastic scattering. From the general covariant results, specific cross sections are derived for deep inelastic scattering as well as elastic scattering of electrons on muons, nucleons, and spin zero targets. In the latter case, the actual polarization vector for the scattered electron is determined. In the other cases discussed, this vector may be obtained from the cross sections. In addition, a method is presented for defining covariant cross sections, and this method is used to obtain results in the center-of-mass system as well as the laboratory system. Furthermore, explicit cross sections for virtual photon absorption are derived. Finally, in the appendices, an alternative method for the evaluation of traces is given as well as a discussion of the relativistic limit. 相似文献