Selenium heterocycles XIV. 2,6-diaryltetrahydroselenopyran-4-ones

In our previous communications, we have reported that selenium heterocycles could be easily obtained either by using selenium dioxide (3) or by selenium (4). In continuation of our studies on the synthesis and chemistry of selenium heterocycles, it was of interest to use aluminum selenide as the precursor of selenium in the preparation of selenium heterocycles.     

Recent Developments in Colloidal Synthesis of CuInSe2 Nanoparticles

Ternary semiconductor nanocrystals, such as CuInSe₂, are of high interest for photovoltaic application due to their relatively low toxicity and unique properties. During the last decades great success has been achieved in the colloidal synthesis of binary nanoparticles, but for ternary compounds this research is still in an early stage of development. These materials are a challenge for synthetic chemistry, because the interaction between the three components (copper, indium, and selenium) plays a major role for the production of high quality material. The purpose of this Minireview is to provide a summary of the achievements in colloidal synthesis of CuInSe₂ nanoparticles—in particular, details of reaction mechanism and its characterization possibilities, which might be useful also for the colloidal synthesis of other multicomponent systems.     

Formation of volatile selenium species in synthetic seawater under light and dark experimental conditions

Experiments were performed in the laboratory on synthetic seawater spiked with different selenium species at trace levels to study the formation of volatile selenium compounds under dark or controlled simulated sunlight conditions. Spiking the reaction media with inorganic and organic selenium compounds demonstrated that several volatile selenium species could be formed under these simulated conditions. Selenoamino acids react to produce significant amounts of volatile selenium species in both light and dark conditions. Products formed include dimethyl selenide (DMSe), dimethyl selenyl sulphide (DMSeS) and dimethyl diselenide (DMDSe). Inorganic selenium oxyanions added to the synthetic reaction media did not form volatile species via abiotic reactions despite the presence of strong methylating agents. These results suggest that the formation of stable volatile species from bio‐organic selenium compounds can occur via abiotic reactions in the marine photic zone. Copyright © 2000 John Wiley & Sons, Ltd.     

抗坏血酸为还原剂制备Se纳米线(英)

0IntroductionOne鄄dimensionalnanostructuressuchasnanowires,nanorods,ornanotubeshavebeenthesub鄄jectofintensiveresearchduetotheirpotentialuseasactivecomponentsorinterconnectsinfabricatingnanoscaleelectronicorelectromechanicaldevices[1].Theyalsorepresentane…     

Cuprous Iodide Catalyzed Synthesis of Diaryl Selenide and Telluride from Organoboronic Acids with Diphenyl Diselenide and Ditelluride

Organoselenium and tellurium compounds have received much attention not only as synthetic reagents or intermediates in organic synthesis but also as promising donor molecules for conductive materials.[1] A number of synthetic methods have been reported to prepare organoselenium and tellurium derivatives. A convenient and general method to introduce a selenium or tellurium moiety into organic molecules is the reaction of a metal selenolate or tellurolate with appropriate electrophiles such as organic halides, acyl chlorides, epoxides, and α, β-enones.[2] However, it is difficult to synthesize the unsymmetrical diarylselenides and tellurides through the reaction of selenide anion with organic halides because of the less reactivity of aryl halides. To accomplish this purpose, the reaction (iodobenzene with phenylselenol)was generally carried out in the presence of catalysts, ligands and strong bases. But, the reaction needs longer time to accomplish and form the products in moderate yields.     

A Chemistry for Incorporation of Selenium into DNA‐Encoded Libraries

Conventional direct C?H selenylation suffers from simple selenation with limited atom economy and complicated reaction system. In this work, we designed benzoselenazolone as a novel bifunctional selenide reagent for both off‐ and on‐DNA C?H selenylation under rhodium(III) catalysis. We show that using benzoselenazolone allowed production of a series of selenylation products containing an adjacent aminoacyl group in a fast and efficient way, with high atom economy. The synthetic application of this method was demonstrated by taking advantage of the amide functionality as a nucleophile, directing group, and amide coupling partner. This work shows great potential in facilitating rapid construction of selenium‐containing DNA‐encoded chemical libraries (SeDELs), and lays the foundation for the development of selenium‐containing drugs.     

New reaction of 1H-pyrazoles with selenium dioxide: one-pot synthesis of bis(1H-pyrazol-4-yl)selenides

A novel reaction between 3- and 3,5-substituted pyrazoles with selenium dioxide proceeds with formation of bis(3R,5R′-1H-pyrazol-4-yl)selenides in high yield. On this basis, an efficient one-pot synthetic procedure has been developed. In the case of the unsubstituted pyrazole a selenonium compound has been obtained. The identity and structure of the isolated selenium derivatives have been confirmed by spectral methods and their molecular structures investigated by X-ray analysis.     

离子缔合物二级散射光谱的分析应用: 硒(IV)-碘化物-罗丹明B体系

从硒(IV)-碘化物-罗丹明B反应体系的研究中, 发现了离子缔合物水溶液的两种二级散射光谱现象。研究了它们的光谱特征、影响因素和适宜条件, 确定了二级散射强度与溶液中离子缔合物浓度的关系, 提出了利用二级散射光谱测定痕量硒的高灵敏分析方法。对反应机理和二级散射变化的原因也进行了初步的探讨。     

One-pot assembling of selenazolines from elemental selenium,alkenes and acetonitrile

A new method for assembling 1,3-selenazolines by the iodine- mediated reaction of the simplest building blocks such as elemental selenium, alkenes and acetonitrile has been discovered. A proposed mechanism includes the addition of the intermediate selenium iodides to alkene with subsequent solvent interception by the formed seleniranium ion.     

Selective formation of unsymmetric ureas by selenium-catalyzed oxidative–reductive carbonylation with CO

A series of unsymmetric ureas containing substituted groups have been synthesized via selenium-catalyzed selective oxidative–reductive carbonylation of amines and nitro compounds with CO instead of phosgene in one-pot reaction. These catalytic reactions are important from both synthetic and industrial points of view, because not only the reactions can be proceeded with high selectivity of higher than 99% towards desired unsymmetric ureas, but also there exists a phase-transfer process of the selenium catalyst in the reaction, so that the after-treatment of the catalysts and products from the reaction systems can be easily separated by simple phase separation.     

Proposed reaction mechanisms for selenium UV photolysis vapor generation by computational methods

The production of volatile analyte species by UV photolysis in the presence of low-molecular-weight organic acids as an alternative to chemical vapor generation has been of recent interest. The mechanism of this process is not well understood. Proposed mechanisms often involve photolytic cleavage of the organic acid as the initial step. Evidence suggests that this may not be the dominant route for UV photolysis vapor generation. In this work computational methods were applied to determine a possible alternative mechanism in the absence of free-radical production. The proposed mechanism specifically focused on selenium vapor generation. An energetically favored mechanism was found for UV photolysis of inorganic selenium in the presence of formic and acetic acids which is consistent with previously reported experimental results.     

Synthesis, reactivity and structural studies of selenide bridged carboranyl compounds

Reaction of the lithium salt Li[1-R-1,2-closo-C(2)B(10)H(10)] with selenium under mild conditions, followed by hydrolysis gave the diselenide compound (1-Se-2-R-1,2-closo-C(2)B(10)H(10))(2) in contrast to the well-reported mercapto compounds 1-SH-2-R-1,2-closo-C(2)B(10)H(10) obtained using a similar synthetic procedure. Details for the preparation and X-ray structural characterisation of the new compounds (2-Me-1,2-closo-C(2)B(10)H(10))(2)Se, (1-Se-2-R-1,2-closo-C(2)B(10)H(10))(2) (R = Me, Ph, ) are specified. To further explore the mechanism of the dimerization reaction, the complex [Au(1-Se-2-Me-1,2-closo-C(2)B(10)H(10))(PPh(3))] was synthesized, confirming the existence of the intermediate Li[1-Se-2-R-1,2-closo-C(2)B(10)H(10)] at the early stages of the reaction before selenium oxidation. Theoretical calculations and cyclic voltammetry (CV) studies were carried out to compare the bonding nature of the sulfur and the selenium analog compounds. It was determined that diselenides have a higher tendency to reduce with respect to the disulfides and all chalcogen atoms were found to be positively charged.     

Selenomethionine content of candidate reference materials.

Selenium has been identified as an antioxidant of importance in the diet. Accurate determination of its chemical forms depends on the availability of suitable reference materials (RMs). Two candidate reference materials for determination of selenomethionine (Semet) in food-related materials, a standard wheat gluten sample (NIST RM 8418 Wheat Gluten) and a commercial selenium enriched yeast, have been examined by use of a gas chromatography-isotope dilution mass spectrometry (IDMS) procedure, after treatment of the matrix with 0.1 mol L(-1) hydrochloric acid containing stannous chloride, addition of CNBr, and extraction with chloroform. This procedure results in cleavage of the CH3Se group to form volatile CH3SeCN. Addition of isotopically enriched 74Semet to an analytical sample enables estimation of the naturally occurring protein-bound 80Semet by IDMS without a protein-digestion process. We found that the Wheat Gluten RM contains a significant amount of Semet as a portion of its assigned value of 2.58 microg Se(total g(-1). Commercial selenium yeast tablets are labeled as containing an elevated level of "organic selenium", usually as Semet. The sample we investigated contained 210 microg Se(total) g(-1) sample as determined separately by IDMS, measuring elemental selenium after digestion. 73% of this total (153 +/- 21 microg Se(semet) g(-1); n = 23) was present as Semet. Thus, these two materials contain significant amounts of their total selenium content as Semet and would be good candidates for further study and characterization as reference materials for determining this important food component. The CNBr reaction used will also enable the determination of Se-(methyl)selenocysteine, the biological role of which is of recent interest. In addition to matrix RMs for Semet, it is important to have standard materials of the pure substance. We have examined a sample of a candidate standard material of selenomethionine being prepared by the USP. It was confirmed that this material is pure selenomethionine.     

A facile spectrophotometric method for the determination of selenium.

A rapid and sensitive spectrophotometric method is described for the determination of trace amounts of selenium using Variamine Blue (VB) as a chromogenic reagent. The proposed method is based on the reaction of selenium with potassium iodide in an acidic medium to liberate iodine, which oxidizes Variamine Blue to form a violet-colored species having an absorption maximum at 546 nm. Beer's law is obeyed in the range 2-20 g of selenium in a final volume of 10 ml. The molar absorptivity and Sandell's sensitivity were found to be 2.6 x 10(4) l mol-1 cm-1 and 0.003 microgram cm-2, respectively. The optimum reaction conditions and other analytical parameters were evaluated. The effect of interfering ions on the determination is described. The proposed method has been successfully applied to the determination of selenium in real samples of water, soil, plant materials, human hair, and synthetic samples of cosmetics and pharmaceutical preparations.     

Carbothermal chemical vapor deposition route to Se one-dimensional nanostructures and their optical properties

A simple and practical carbothermal chemical vapor deposition route has been developed for the growth of trigonal phase selenium nanowires and nanoribbons. In detail, the mixture of active carbon and selenium was heated for the chemical reaction to occur, followed by thermal evaporation and decomposition into elemental selenium. The as-prepared sample was characterized by X-ray diffraction, transmission electron microscopy, high-resolution electron microscopy, UV-vis absorption, and photoluminescence. The results show that trigonal Se nanowires have uniform diameters ranging from 20 to 60 nm and grow along the [001] direction, with the same growth direction found for nanoribbons. Spectral measurements suggest a large blue shift and two types of electron transition activity. The influences of experimental conditions on morphologies and growth processes are also discussed. This synthetic method should be able to be extended to grow other one-dimensional chalcogens and chalcogenides nanostructures.     

Albumin-mediated selenium transfer by a selenotrisulfide relay mechanism

In this study, we demonstrated a human serum albumin (HSA)-mediated selenium transfer; the selenium exported from red blood cells (RBCs) was bound to HSA through the selenotrisulfide and then transferred into the hepatocyte. After the treatment of the RBCs with selenite, the selenium efflux from the RBCs occurred in an HSA concentration-dependent manner. Pretreatment of HSA with iodoacetamide almost completely inhibited the selenium efflux from the RBC to the HSA solution. The selenium efflux experiment was carried out in an HSA solution (45 mg/mL), and subsequently the HSA solution was subjected to gel permeation chromatographic separation. The peak fraction of the selenium content was consistent with that of the HSA. The selenium bound to HSA in this solution was completely eliminated by a treatment with penicillamine (Pen), which resulted in the generation of penicillamine selenotrisulfide, PenSSeSPen. The selenium efflux from the RBCs was also occurred in a Pen solution, and PenSSeSPen was observed in the resulting Pen solution. The selenium exported from the RBC was thought to bind to the HSA via a selenotrisulfide linkage with its single free thiol. A model of the selenium-bound HSA was prepared by the reaction of the HSA with PenSSeSPen. The selenium from PenSSeSPen can bind to HSA by a thiol exchange between Pen and the free thiol of HSA, which produces the selenotrisulfide-containing HSA (HSA-SSeSPen). When HSA-SSeSPen was incubated with isolated rat hepatocytes, the selenium content in the hepatocytes increased along with its decrease in the incubation medium. To verify the results from the model experiments using HSA-SSeSPen, we conducted the HSA-mediated selenium transfer experiment from RBC treated with selenite to the hepatocytes. The selenotrisulfide-containing HSA was able to transport the selenium into the hepatocyte. Overall, the selenium transfer from the RBC to the hepatocytes involves a relay mechanism of thiol exchange that occurs between the selenotrisulfide and thiol compounds (selenotrisulfide relay mechanism: R-SSeS-R + HSA-SH --> HSA-SSeS-R + R'-SH --> R-SSeS-R').     

Copper(I)-catalyzed highly efficient synthesis of benzoselenazoles and benzotellurazoles

A simple and practical useful synthetic method of 1,3-benzoselenazoles having a heteroatom substituent such as NRR', OR, and SR groups at the 2-position was developed by the copper(I)-catalyzed reaction of 2-bromophenyl (1) or 2-iodophenyl (2) isocyanides with selenium and heteroatom nucleophiles. In addition, the synthesis of 2-amino-1,3-benzotellurazoles is also described.     

Synthesis of Unsymmetric Ureas by Selenium-Catalyzed Oxidative-Reductive Carbonylation with CO

Unsymmetric, substituted ureas that contain the peptide bond (NHCONH), many of which possess biological activities, are widely used as herbicides, agrochemicals and pharmaceuticals. [1,2] A series of unsymmetric ureascontaining substituted groups have been synthesized via selenium-catalyzed selective oxidative-reductive carbonylation of amines and nitro compounds with CO instead of phosgene in one-pot reaction. [3,4] These catalytic reactions are important from both synthetic and industrial points of view, because not only the reactions can be proceeded with high selectivity of higher than 99% towards desired unsymmetric ureas, but also there exists a phase-transfer process of the selenium catalyst in thereaction, so that the after-treatment of the catalysts and products from the reaction systems can be easily separated by simple phase separation.     

液/液界面生长法制备一维纳米硒

采用均相反应界面生长法制备了一维结构的纳米硒。在制备过程中,初始硒纳米粒子首先在均相反应液中生成,然后加入与该反应液不互溶的溶剂,使其形成液液界面,硒纳米粒子聚集在界面上生长为一维结构。用扫描电镜、透射电镜、X射线粉末衍射等测试技术对样品进行了表征,并讨论了界面生长的机理及其影响因素。     

Thiol–Ene Click Chemistry

Following Sharpless′ visionary characterization of several idealized reactions as click reactions, the materials science and synthetic chemistry communities have pursued numerous routes toward the identification and implementation of these click reactions. Herein, we review the radical‐mediated thiol–ene reaction as one such click reaction. This reaction has all the desirable features of a click reaction, being highly efficient, simple to execute with no side products and proceeding rapidly to high yield. Further, the thiol–ene reaction is most frequently photoinitiated, particularly for photopolymerizations resulting in highly uniform polymer networks, promoting unique capabilities related to spatial and temporal control of the click reaction. The reaction mechanism and its implementation in various synthetic methodologies, biofunctionalization, surface and polymer modification, and polymerization are all reviewed.