(Amino)(aryl)carbenes: stable singlet carbenes featuring a spectator substituent

Several (amino)(aryl)carbenes have been shown to be stable at room temperature in solution and in the solid state. Electroneutrality of the carbene center is ensured by the amino group, which has both pi-donor and final sigma-acceptor electronic character. The aryl group remains a spectator substituent, as shown by single-crystal x-ray analysis and by its chemical behavior. Because only one electron-active substituent is needed, numerous stable carbenes will become accessible, which will open the way for new synthetic developments and applications in various fields.     

Stable versions of transient push-pull carbenes: extending lifetimes from nanoseconds to weeks

A (phosphanyl)(trifluoromethyl)carbene is shown to be stable for weeks in solution at temperatures up to -30 degrees C. Its chemical behavior exactly matches that of its transient congeners, even to the extent that subtle effects, such as the recently discovered weak pi interaction with aromatics, are observed. The influence of substituents on the structure of push-pull carbenes is demonstrated by a single-crystal x-ray diffraction study of a (phosphanyl)[2, 6-bis(trifluoromethyl)phenyl]carbene. The lifetime of these molecules makes them accessible to a wider range of standard techniques, allowing their chemical and physical behaviors to be studied in more detail than was previously possible.     

Facile splitting of hydrogen and ammonia by nucleophilic activation at a single carbon center

In possessing a lone pair of electrons and an accessible vacant orbital, singlet carbenes resemble transition metal centers and thus could potentially mimic their chemical behavior. Although singlet di(amino)carbenes are inert toward dihydrogen, it is shown that more nucleophilic and electrophilic (alkyl)(amino)carbenes can activate H2 under mild conditions, a reaction that has long been known for transition metals. However, in contrast to transition metals that act as electrophiles toward dihydrogen, these carbenes primarily behave as nucleophiles, creating a hydride-like hydrogen, which then attacks the positively polarized carbon center. This nucleophilic behavior allows these carbenes to activate NH3 as well, a difficult task for transition metals because of the formation of Lewis acid-base adducts.     

Cyclopropenylidenes: from interstellar space to an isolated derivative in the laboratory

Like many of the molecular species that have been detected in the interstellar medium, the singlet carbene cyclopropenylidene (C3H2) has been presumed to be too unstable to isolate in the laboratory. However, by appending pi-electron-donating amino groups to the triangular skeleton, we prepared a cyclopropenylidene derivative that is stable at room temperature. In contrast to previously isolated carbenes, this compound does not require a heteroatom adjacent to the electron-deficient carbon to confer stability. Despite the presence of amino groups, the geometric parameters of the cyclic skeleton, revealed by x-ray crystallography, are only slightly perturbed relative to those of the calculated structure of unsubstituted cyclopropenylidene. Stable cyclopropenylidene derivatives might thus serve as models for a better understanding of the formation of carbon-bearing molecules in the interstellar medium.     

Synthesis and characterization of a neutral tricoordinate organoboron isoelectronic with amines

Amines and boranes are the archetypical Lewis bases and acids, respectively. The former can readily undergo one-electron oxidation to give radical cations, whereas the latter are easily reduced to afford radical anions. Here, we report the synthesis of a neutral tricoordinate boron derivative, which acts as a Lewis base and undergoes one-electron oxidation into the corresponding radical cation. These compounds can be regarded as the parent borylene (H-B:) and borinylium (H-B(+.)), respectively, stabilized by two cyclic (alkyl)(amino)carbenes. Ab initio calculations show that the highest occupied molecular orbital of the borane as well as the singly occupied molecular orbital of the radical cation are essentially a pair and a single electron, respectively, in the p(π) orbital of boron.     

Mechanism of the rhodium porphyrin-catalyzed cyclopropanation of alkenes

The rhodium porphyrin-catalyzed cyclopropanation of alkenes by ethyl diazoacetate (EDA) is representative of a number of metal-mediated cyclopropanation reactions used widely in organic synthesis. The active intermediate in these reactions is thought to be a metal carbene complex, but evidence for the involvement of metal-olefin pi complexes has also been presented. Low-temperature infrared and nuclear magnetic resonance spectroscopies have been used to characterize a rhodium porphyrin-diazoalkyl adduct that results from the stoichiometric condensation of the catalyst and EDA. Optical spectroscopy suggests that this complex is the dominant steady-state species in the catalytic reaction. This compound decomposes thermally to provide cyclopropanes in the presence of styrene, suggesting that the carbene is indeed the active intermediate. Metal-alkene pi complexes have also been detected spectroscopically. Kinetic studies suggest that they mediate the rate of carbene formation from the diazoalkyl complex but are not attacked directly by EDA.     

Detection and Characterization of the Cumulene Carbenes H2C5 and H2C6

Two cumulene carbenes, H2C5 and H2C6, were detected in a supersonic molecular beam by Fourier transform microwave spectroscopy. Their rotational and leading centrifugal distortion constants were determined with high accuracy, such that the entire radio spectrum can now be calculated. Like the known carbenes H2C3 and H2C4, both molecules have singlet electronic ground states and linear carbon-chain backbones. They can be produced in sufficiently high concentrations in the laboratory that their electronic spectra, expected to lie in the visible, should be readily detectable by laser spectroscopy. The microwave spectra of other, more exotic isomers may be detectable as well.     

Atomic-scale structure and catalytic reactivity of the RuO(2)(110) surface

The structure of RuO(2)(110) and the mechanism for catalytic carbon monoxide oxidation on this surface were studied by low-energy electron diffraction, scanning tunneling microscopy, and density-functional calculations. The RuO(2)(110) surface exposes bridging oxygen atoms and ruthenium atoms not capped by oxygen. The latter act as coordinatively unsaturated sites-a hypothesis introduced long ago to account for the catalytic activity of oxide surfaces-onto which carbon monoxide can chemisorb and from where it can react with neighboring lattice-oxygen to carbon dioxide. Under steady-state conditions, the consumed lattice-oxygen is continuously restored by oxygen uptake from the gas phase. The results provide atomic-scale verification of a general mechanism originally proposed by Mars and van Krevelen in 1954 and are likely to be of general relevance for the mechanism of catalytic reactions at oxide surfaces.     

Divalent carbon intermediates: laser photolysis and spectroscopy

A brief review is given of the structures of an important class of reactive intermediates, divalent carbon species (carbenes). The electronic properties of carbenes force an unusual electronic character upon these species that, in turn, leads to intriguing physical and chemical properties. Because of the fleeting nature of carbenes, which are extraordinarily reactive, direct investigation of their structural and chemical behavior has presented a challenge to the experimentalist. The application of spectroscopic and ultrafast laser techniques has met this challenge. With the use of laser methods, along with conventional techniques, quantitative evaluation of the energetics, dynamics, and reactivities of a variety of carbenes has been possible.     

Interwoven metal-organic framework on a periodic minimal surface with extra-large pores

Interpenetration (catenation) has long been considered a major impediment in the achievement of stable and porous crystalline structures. A strategy for the design of highly porous and structurally stable networks makes use of metal-organic building blocks that can be assembled on a triply periodic P-minimal geometric surface to produce structures that are interpenetrating-more accurately considered as interwoven. We used 4,4',4"-benzene-1,3,5-triyl-tribenzoic acid (H(3)BTB), copper(II) nitrate, and N,N'-dimethylformamide (DMF) to prepare Cu(3)(BTB)(2)(H(2)O)(3).(DMF)(9)(H(2)O)(2) (MOF-14), whose structure reveals a pair of interwoven metal-organic frameworks that are mutually reinforced. The structure contains remarkably large pores, 16.4 angstroms in diameter, in which voluminous amounts of gases and organic solvents can be reversibly sorbed.     

连南茶树资源的生化成分多样性分析

[目的]分析广东连南茶树种质资源生化成分的多样性,为茶树新品种选育提供科学依据.[方法]检测广东连南县45份茶树资源的氨基酸、茶多酚、生物碱、酚氨比等主要生化成分指标,鉴定评价其遗传多样性.[结果]连南茶树资源的生化成分存在丰富的多样性和变异性,其中,变异系数最大的是可可碱含量(146.39%),其次是儿茶素没食子酸酯(CG)和表儿茶素没食子酸酯(ECG)含量,分别为115.71%和108.20%,变异系数最小的是水浸出物含量,为12.14%.通过主成分分析,发现第一主成分和第二主成分的累计贡献率分别为77.284%和93.441%,包含所有性状的大部分信息.综合比较结果表明,可从45份茶树资源中筛选出一批生化成分特异的资源,其中,高氨基酸资源(>5.00%)4份,高茶多酚资源(>34.00%)14份,低咖啡碱资源(<1.00%)2份;在高水浸出物资源中,儿茶素总量和酯型儿茶素含量较高的资源有12份(涡水茶树群体中有10份,黄连茶树群体中有2份).[结论]广东连南茶树资源生化成分多样性丰富,变异系数大,具有丰富的遗传多样性和明显的地域独特性;筛选出的13份高茶多酚资源及其他特殊资源可作为茶叶深加工和育种的基础材料.     

Boryllithium: isolation, characterization, and reactivity as a boryl anion

Nucleophilic, anionic boryl compounds are long-sought but elusive species. We report that reductive cleavage of the boron-bromine bond in N,N'-bis(2,6-diisopropylphenyl)-2-bromo-2,3-dihydro-1H-1,3,2-diazaborole by lithium naphthalenide afforded the corresponding boryllithium, which is isoelectronic with an N-heterocyclic carbene. The structure of the boryllithium determined by x-ray crystallography was consistent with sp(2) boron hybridization and revealed a boron-lithium bond length of 2.291 +/- 0.006 angstroms. The structural similarity between this compound and the calculated free boryl anion suggests that the boron atom has an anionic charge. The (11)B nuclear magnetic resonance spectrum also supports the boryl anion character. Moreover, the compound behaves as an efficient base and nucleophile in its reactions with electrophiles such as water, methyl trifluoromethanesulfonate, 1-chlorobutane, and benzaldehyde.     

Hot hydrogen atoms: initiators of reactions of interest in interstellar chemistry and evolution

Photochemically generated hot hydrogen atoms initiate reactions with simple molecular substrates including methane to produce organic alcohols, amines, acids, amino acids, and other compounds. The typical quantum yields for the formation of amino acids are 2 x 10(-5) to 4 x 10(-5). Hot hydrogen atoms may be important initiators of reactions in interstellar space and in planetary atmospheres.     

A stable aminyl radical metal complex

Metal-stabilized phenoxyl radicals appear to be important intermediates in a variety of enzymatic oxidations. We report that transition metal coordination also supports an aminyl radical, resulting in a stable crystalline complex: [Rh(I)(trop2N.)(bipy)]+OTf- (where trop is 5-H-dibenzo[a,d]cycloheptene-5-yl, bipy is 2,2'-bipyridyl, OTf- is trifluorosulfonate). It is accessible under mild conditions by one-electron oxidation of the amide complex [Rh(I)(trop2N)(bipy)], at a potential of -0.55 volt versus ferrocene/ferrocenium. Both electron paramagnetic resonance spectroscopy and density functional theory support 57% localization of the unpaired spin at N. In reactions with H-atom donors, the Rh-coordinated aminyl behaves as a nucleophilic radical.     

Free energy and temperature dependence of electron transfer at the metal-electrolyte interface

The rate constant of the electron-transfer reaction between a gold electrode and an electroactive ferrocene group has been measured at a structurally well-defined metal-electrolyte interface at temperatures from 1 degrees to 47 degrees C and reaction free energies from -1.0 to +0.8 electron volts (eV). The ferrocene group was positioned a fixed distance from the gold surface by the self-assembly of a mixed thiol monolayer of (eta(5)C(5)H(5))Fe(eta(5)C(5)H(4))CO(2)(CH(2))(16)SH and CH(3)(CH(2))(15)SH. Rate constants from 1 per second (s(-1)) to 2 x 10(4) s(-1) in 1 molar HClO(4) are reasonably fit with a reorganization energy of 0.85 eV and a prefactor for electron tunneling of 7 x 10(4) s(-1) eV(-1). Such self-assembled monolayers can be used to systematically probe the dependence of electron-transfer rates on distance, medium, and spacer structure, and to provide an empirical basis for the construction of interfacial devices such as sensors and transducers that utilize macroscopically directional electron-transfer reactions.     

马铃薯Y病毒广东分离物HC-Pro基因的克隆和序列分析

利用RT-PCR法对广东烟草样品的马铃薯Y病毒(Potato virus Y,PVY)辅助成分蛋白质(Helpercomponent proteinase,HC-Pro)基因进行了克隆,并对其进行了序列分析。测序结果表明广东PVY HC-Pro(命名为PVY-HC-GD)基因(用PVY-HC-GD表示)全长1 395 bp,编码465个氨基酸。与已报道的PVY HC-Pro基因核苷酸序列相比发现,PVY-HC-GD与PVY NTN株系(PVYNTN)(AB331517)的PVYHC-Pro基因核苷酸序列相似性最高,达99.6%。而氨基酸序列比较表明,PVY-HC-GD与PVY N株系(PVYN)(AM268435)的PVY HC-Pro氨基酸序列相似性最高,为99.1%。进一步将PVY-HC-GD的核苷酸和其编码的氨基酸序列与其他报道的同源基因比对构建了系统关系树,结果显示广东烟草样品中PVY-HC-GD与PVYNTN PVY HC-Pro亲缘关系最近。     

"Hemoglobin alpha2beta2-121ys" chemical identification in an egyptian family

Stuidy of the amino acid composition and amino-terminal residue in the abnormal peptide of an electrophoretically slow hemoglobin revealed that the globin's structure was alpha(2)beta(2)(121 Lys) (Obeta). This hemoglobin had been provisionally classified as Hb E or as a new heemoglobin. The clinical significance of this abnormality is not yet defined.     

Explosive molecular ionic crystals

In ionic crystals of the form M(+)X(-), certain covalently bonded anion groups X(-) are particularly associated with instability. The heavier metal cations M(+) enhance this. Very sensitive explosives occur within the extended azide family, where X(-) = CNO(-), N(3)(-), NCO(-), or NCS(-) (an isoelectronic set of unsaturated linear triatomic anions). Another such family are the globular oxyanions X(-) = ClO(2)(-), ClO(3)(-), ClO(4)(-), NO(3)(-), and MnO(4)(-). Mishandling of NH(4)NO(3) or NH(4)ClO(4) has caused major disasters. An irreversible cyclic mechanism is proposed for such decomposition, involving mechanoelectronic band-gap excitation and coalescence of X with X(-). From an intracrystalline ion-molecule collision complex, the singly charged dianion X(2)(-), exothermic reactions proceed with high yield.     

Catalysis of the olivine to spinel transformation by high clinoenstatite

Although enstatite is a major constituent of the Earth's upper mantle and subducting lithosphere, most kinetic studies of olivine phase transformations have typically involved single-phase polycrystalline aggregates. Transmission electron microscopy investigations of olivine to spinel and modified spinel (beta phase) reactions in the (Mg, Fe)(2)SiO(4)-(Mg,Fe)SiO(3) system show that transformation of olivine in the stability field of spinel plus phase begins with coherent nucleation of spinel on high-clinoenstatite grains. These observations demonstrate that high clinoenstatite can catalyze the transformation by enhancing nucleation kinetics and therefore imply that secondary phases can influence reaction kinetics during high-pressure mineral transformations.     

Phenylalanine and tyrosine synthesis under primitive earth conditions

Phenylacetylene can be synthesized in substantial yields from various hydrocarbons by high temperatures, electric discharges, and ultraviolet light. Phenylacetylene is hydrated to phenylacetaldehyde by way of both nucleophilic and radical additions of H(2)S followed by hydrolysis of the thtioaldehyde. The addition of NH(3) and HCN to phenylacetaldehyde yields phenylalanine nitrile which is hydrolyzed to phenylalanine. A small yield of tyrosine is obtained from the radical addition of H(2)S to phenylacetylene. This sequence of reactions is a possible mechanism for the synthesis of these amino acids on the primitive earth.