Anab initio investigation of Cu2Se and Cu4Se2

Summary Experimentally known copper selenium clusters show extraordinary geometrical features, especially short Cu-Cu distances. We report the first theoretical investigation of Cu₂Se and Cu₄Se₂. Various quantum chemical methods (SCF, MP2, CPF, CCSD, CCSD(T), LDF) are applied to determine the importance of dynamic electron correlation. We find that inclusion of correlation does not essentially change the electronic structure of the clusters but has a strong influence on geometries. To reduce the computational effort we apply effective core potentials (ECPs) in combination with small, but carefully optimized basis sets. The applicability of simple modellings of correlation energies for approximate inclusion of correlation effects in SCF geometry optimizations is tested.     

Synthesis of di-t-alkylamines

Di-$\text{t}$-alkylamines can be synthesized efficiently by a three-step process: (1) oxidation of a $\text{t}$-alkylamine to a $\text{t}$-alkylnitroso compound with peracetic acid in ethyl acetate (2) conversion of the $\text{t}$-alkylnitroso compound to a tri-$\text{t}$-alkylhydroxylamine by successive trapping of two $\text{t}$-butyl radicals and (3) sodium naphthalide reduction to the di-$\text{t}$-alkylamine.     

Review coupling of capillary electrochromatography to mass spectrometry

This review discusses the development of capillary electrochromatography (CEC) coupled to mass spectrometric (MS) detection over the last few years. Major topics addressed are instrumental setups employed and applications of this technology published in the recent literature. The instrumental section includes a discussion of the most commonly used interfaces for the hyphenation of CEC and MS as well as ionization techniques. Applications reviewed in this paper come from a variety of different fields such as the analysis of biomolecules like proteins, peptides, amino acids or carbohydrates, chiral separations or the analysis of pharmaceutical an their metabolites in a series of matrices.     

On the gas-phase reactivity of complexed OH+ with halogenated alkanes

OH(+) is an extraordinarily strong oxidant. Complexed forms (L--OH(+)), such as H(2)OOH(+), H(3)NOH(+), or iron-porphyrin-OH(+) are the anticipated oxidants in many chemical reactions. While these molecules are typically not stable in solution, their isolation can be achieved in the gas phase. We report a systematic survey of the influence on L on the reactivity of L--OH(+) towards alkanes and halogenated alkanes, showing the tremendous influence of L on the reactivity of L--OH(+). With the help of with quantum chemical calculations, detailed mechanistic insights on these very general reactions are gained. The gas-phase pseudo-first-order reaction rates of H(2)OOH(+), H(3)NOH(+), and protonated 4-picoline-N-oxide towards isobutane and different halogenated alkanes C(n)H(2n+1)Cl (n=1-4), HCF(3), CF(4), and CF(2)Cl(2) have been determined by means of Fourier transform ion cyclotron resonance measurements. Reaction rates for H(2)OOH(+) are generally fast (7.2x10(-10)-3.0x10(-9) cm(3) mol(-1) s(-1)) and only in the cases HCF(3) and CF(4) no reactivity is observed. In contrast to this H(3)NOH(+) only reacts with tC(4)H(9)Cl (k(obs)=9.2x10(-10)), while 4-CH(3)-C(5)H(4)N-OH(+) is completely unreactive. While H(2)OOH(+) oxidizes alkanes by an initial hydride abstraction upon formation of a carbocation, it reacts with halogenated alkanes at the chlorine atom. Two mechanistic scenarios, namely oxidation at the halogen atom or proton transfer are found. Accurate proton affinities for HOOH, NH(2)OH, a series of alkanes C(n)H(2n+2) (n=1-4), and halogenated alkanes C(n)H(2n+1)Cl (n=1-4), HCF(3), CF(4), and CF(2)Cl(2), were calculated by using the G3 method and are in excellent agreement with experimental values, where available. The G3 enthalpies of reaction are also consistent with the observed products. The tendency for oxidation of alkanes by hydride abstraction is expressed in terms of G3 hydride affinities of the corresponding cationic products C(n)H(2n+1) (+) (n=1-4) and C(n)H(2n)Cl(+) (n=1-4). The hypersurface for the reaction of H(2)OOH(+) with CH(3)Cl and C(2)H(5)Cl was calculated at the B3 LYP, MP2, and G3(m*) level, underlining the three mechanistic scenarios in which the reaction is either induced by oxidation at the hydrogen or the halogen atom, or by proton transfer.     

Amber‐Woody Scent: Alcohols with Divergent Structure Present Common Olfactory Characteristics and Sharp Enantiomer Differentiation

Only one out of the four possible trans isomers of the important perfumery alcohol Norlimbanol^® ( 1 ) possesses a very strong amber‐woody smell, the isomer 1A with (1′R,3S,6′S) absolute configuration. Its enantiomer 1B is almost odorless and devoid of amber‐woody character, whereas the diastereoisomers 1C and 1D are considerably weaker and perceptible only by the most‐sensitive persons. The same is true for a whole series of perceptual analogs of 1 , including β‐alkoxy alcohols. These ethers belong to two structural classes: [(2,2,6‐trimethylcyclohexyl)oxy]‐ (see 3, 4 , and 16 ) or {[2‐(tert‐butyl)cyclohexyl]oxy}alkan‐2‐ol derivatives (see 19 and 20 ; Table). A superimposition model allowing for good overlap of the respective hydroxylated side chains offers a tentative explanation for the shared perceptual characteristics of the two classes (Fig. 5). The lipophilic cyclohexane moieties present only a minimal overlap in this model, suggesting that quite larger molecules might possess the same smell. (S)‐Configured β‐alkoxy alcohols can conveniently be obtained on a larger scale by enantioselective reduction of the corresponding ketones (Scheme 9).     

Square-wave adsorptive stripping voltammetry of menadione (vitamin K(3))

Menadione (vitamin K₃) undergoes a reversible two-electron transfer involving the quinone structure in acidic medium. As demonstrated by using cyclic voltammetry, the reduced form is more strongly adsorbed than the oxidized one. Stripping voltammetry of an adsorbed layer has been applied to the determination of this molecule after preconcentration of the reduced compound and scanning the potential towards less negative values. Adsorption, which is highly effective when stirring is used, approaches an equilibrium process in quiescent solution, as evidenced by a loss of part of the adsorbed material when stirring is stopped. A square-wave mode has been selected owing to its high sensitivity (the current is 20 times that for the differential pulse mode), but also to its high scan-rate, which minimizes the slow desorption process occurring during the scan. A concentration range from 2 × 10⁻¹⁰ to 5 × 10⁻⁷ M is easily investigated, the detection limit being 1.3 × 10⁻¹⁰ M. The influence of several operational parameters has also been considered.     

C-H activation of alkanes on Rh+ n (n=1-30) clusters: size effects on dehydrogenation

The rate coefficients for the dehydrogenation of ethane, propane, and isobutane with cationic rhodium atoms Rh+ and clusters Rh+ n of up to 30 atoms were measured under single-collision conditions in a Fourier-transform ion cyclotron resonance mass spectrometer. The reaction rates are cluster size dependent and parallel for all the three alkanes. While the reactions proceed close to the theoretical collision rates for a large number of clusters, characteristic minima are observed for Rh+ (5/6/9/19/28). The degree of dehydrogenation varies with the cluster size with maxima for 10< or =n< or =15 for the three alkanes and for n=3 and 2-4 in the cases of ethane and propane, respectively. However, complete dehydrogenation is only observed for the reaction of Rh+ 11 with propane. Dehydrogenation is remarkably selective and no other neutral products than H2 are observed. The results are interpreted in terms of likely cluster geometries.     

Synthesis and characterization of water-soluble phenylene-vinylene-based singlet oxygen sensitizers for two-photon excitation

[reaction: see text] The synthesis and characterization of water-soluble singlet oxygen sensitizers with a phenylene-vinylene motif is presented. The principal motivation for this study was to better understand specific features of a water-soluble molecule that influence the photosensitized production of singlet oxygen upon nonlinear, two-photon excitation of that molecule. To achieve water solubility, sensitizers were synthesized with ionic as well as nonionic substituents. In the ionic approach, salts of N-methylated pyridine, benzothiazole, and 1-methyl-piperazine moieties were used, as were aryl-substituted sulfonic acid moieties. In the nonionic approach, aryl-substituted triethylene glycol moieties were used. Selected photophysical properties of the compounds synthesized were determined, including singlet oxygen quantum yields. Of the molecules examined, the most efficient singlet oxygen sensitizers had triethylene glycol units as the functional group that imparted water solubility. Molecules containing the ionic moieties did not make singlet oxygen in appreciable yield nor did they efficiently fluoresce. Rather, for these latter molecules, rapid charge-transfer-mediated non-radiative processes appear to dominate excited state deactivation.