E-1,2-Dichlorovinyl ethers as irreversible protease inhibitors

The synthesis of a novel motif for threonine protease inhibition is described. The desired E-1,2-dichlorovinyl ethers are obtained from alcohols and trichloroethylene as single diastereomers. Aqueous treatment at pH 11 unmasks the hidden α-chloroacetate, which is required for the reaction with the active site of the protease.     

Five-membered OsC3N heterocycles from osmium azavinylidenes as precursors

The azavinylidene osmium complex [(mes)Os(=N=CPh₂(PⁱPr₃)]PF₆ (3; MES = 1.3.5-C₆H₃Me₃), which was prepared in two steps from [(mes)OsCl₂(PⁱPr₃], CH₃CO₂Na/KPF₆ and HN=CPh₂, has been shown to react with trifluoracetic acid to give the isomeric heterocycle [(mes) ₆H₄)(Pⁱ Pr₃)]PF₆ (4) in almost quantitative yield. With CF₃CO₂D, the monodeuterated compound 4-d₄,containing a N---D unit in the five-membered ring, is obtained. An analogue of 4 with the composition [(mes) ₆H₄)(PMe₃)]X(X = PF₆ 14a, SbF₆ 14b) has been made both from [(mes)Os(=N=CPh₂)(PMe₃)]PF₆ 12 and CF₃CO₂H and from [(mes)OsCl(NH= CPh₂(PMe3)]SbF6 (13) and CF₃CO₂Ag. The reaction of 4 with NaH or KO^tBu gives the uncharged heterocycle [(mes) ₆ H₄)(PⁱPr₃)] (15), while treatment of [(mes)OsCl ₂(NH=CPh2)] (19) with NaS^tBu gives the related complex [(mes) ₆H₄)(S^t Bu)] (20). The crystal structure of 4 has been determined. kw]Osmium; Azavinylidene; Cyclometallation; Crystal structure; Arene complexes     

The quenching of CdSe quantum dots photoluminescence by gold nanoparticles in solution

The photoluminescence (PL) of CdSe quantum dots (QD) in aqueous media has been studied in the presence of gold nanoparticles (NP) with different shapes. The steady state PL intensity of CdSe QD (1.5-2 nm in size) is quenched in the presence of gold NP. Picosecond bleach recovery and nanosecond time-resolved luminescence measurements show a faster bleach recovery and decrease in the lifetime of the emitting states of CdSe QD in the presence of quenchers. Surfactant-capped gold nanorods (NR) with aspect ratio of 3 and surfactant-capped and citrate-capped nanospheres (NS) of 12 nm diameter were used as quenchers in order to study the effect of shape and surface charge on the quenching rates. The Stern-Volmer kinetics model is used to examine the observed quenching behavior as a function of the quencher concentration. It was found that the quenching rate of NR is more than 1000 times stronger than that of NS with the same capping material. We also found that the quenching rate decreases as the length of the NR decreases, although the overlap between the CdSe emission and the NR absorption increases. This suggests that the quenching is a result of electron transfer rather than long-range (Forster-type) energy transfer processes. The quenching was attributed to the transfer of electron with energies below the Fermi level of gold to the trap holes of CdSe QD. The observed large difference between NR and NS quenching efficiencies was attributed to the presence of the [110] facets only in the NR, which have higher surface energy.     

Effect of the Media on the Quantum Yield of Singlet Oxygen (O2(1Δg)) Production by 9H‐Fluoren‐9‐one: Solvents and Solvent Mixtures

We have investigated the effect of a series of 18 solvents and mixtures of solvents on the production of singlet molecular oxygen (O₂(¹Δ_g), denoted as ¹O₂) by 9H‐fluoren‐9‐one (FLU). The normalized empirical parameter E derived from E_T(30) has been chosen as a measure of solvent polarity using Reichardt's betaine dyes. Quantum yields of ¹O₂ production (Φ_Δ) decrease with increasing solvent polarity and protic character as a consequence of the decrease of the quantum yield of intersystem crossing (Φ_ISC). Values of Φ_Δ of unity have been found in alkanes. In nonprotic solvents of increasing polarity, Φ_ISC and, therefore, Φ_Δ decrease due to solvent‐induced changes in the energy levels of singlet and triplet excited states of FLU. This compound is a poor ¹O₂ sensitizer in protic solvents, because hydrogen bonding considerably increases the rate of internal conversion from the singlet excited state, thus diminishing Φ_Δ to values much lower than those in nonprotic solvents of similar polarity. In mixtures of cyclohexane and alcohols, preferential solvation of FLU by the protic solvent leads to a fast decrease of Φ_Δ upon addition of increasing amounts of the latter.     

Core excitations of naphthalene: vibrational structure versus chemical shifts

High-resolution x-ray photoelectron emission (XPS) and near-edge x-ray absorption fine structure (NEXAFS) spectra of naphthalene are analyzed in terms of the initial state chemical shifts and the vibrational fine structure of the excitations. Carbon atoms located at peripheral sites experience only a small chemical shift and exhibit rather similar charge-vibrational coupling, while the atoms in the bridging positions differ substantially. In the XPS spectra, C-H stretching modes provide important contributions to the overall shape of the spectrum. In contrast, the NEXAFS spectrum contains only vibrational progressions from particular C-C stretching modes. The accuracy of ab initio calculations of absolute electronic transition energies is discussed in the context of minute chemical shifts, the vibrational fine structure, and the state multiplicity.     

Hexa-Coordinated Silicon Complexes Derived from Regioisomeric Aminotriphenylethanols and Their use as Dopants for Liquid Crystals

Abstract

Tridentate imine ligands that are obtained from the chiral, regioisomeric amino alcohols 2-amino-1,1,2-triphenyethanol and 2-amino-1,2,2-triphenylethanol serve for the formation of bis-chelated silicon complexes. Whereas the complex based on the former amino alcohol is obtained as a diastereomeric mixture, the complex that is derived from 2-amino-1,2,2-triphenylethanol forms in a completely diastereoselective manner, and its configuration is determined as (A,R,R), according to a crystal structure analysis. The new silicon complexes are found to be efficient dopants for the conversion of nematic liquid crystals into cholesteric phases.

GRAPHICAL ABSTRACT     

General Discussion on Thermal and Photodegradation and Stabilization

Indole-containing bifunctional monomers (diacids, dialcohols, and dialdehydes) were synthesized by using as the basic nucleus two indoles attached by a tetraethylene glycol chain. These monomers were used for the preparation of polyesters, poly-amides, and polyazomethines.     

Modern methods of identifying and determining ginsenosides

Ginsenosides are the main bioactive compounds of the Panax plant genus. Ginseng and its analogues are widely used to produce traditional medicines in China, Korea, Japan, United States, and the Russian Far East. For more than 40 years, many researchers developed methods of identifying and determining and ginsenosides in plant tissues, extracts, and commercial products. Various extraction methods were used to isolate these compounds from plant materials. The separation of ginsenosides was conducted with methods such as gas chromatography, thin-layer chromatography, and high-performance liquid chromatography (HPLC). The HPLC method was used predominantly. Spectrophotometric and fluorescent monitoring and, later, light scattering and mass-spectrometry coupled with HPLC were used to determine ginsenosides. The most recent variants of these methods are presented in this review, together with a critical evaluation of the published results.     

Factoriality for the reductive Zassenhaus variety and quantum enveloping algebra

Let U(g)$U(\mathfrak{g})$ be the enveloping algebra of a finite dimensional reductive Lie algebra g$\mathfrak{g}$ over an algebraically closed field of prime characteristic. Let _U?,P(s:)$U_{?,P}(\mathfrak{s}:)$ be the simply connected quantum enveloping algebra at the root of unity ?  , of a complex semi-simple finite dimensional Lie algebra s:$\mathfrak{s}:$. We show, by similar proofs, that the centers of both are factorial. While the first result was established by R. Tange [32] (by different methods), the second one confirms a conjecture in [4]. We also provide a general criterion for the factoriality of the centers of enveloping algebras in prime characteristic.     

Catalytic Borylation of SCF3‐Functionalized Arenes by Rhodium(I) Boryl Complexes: Regioselective C?H Activation at the ortho‐Position

An unprecedented reaction pathway for the borylation of SCF₃‐containing arenes using [Rh(Bpin)(PEt₃)₃] (pin=pinacolato) is reported. Catalytic processes were developed and the functionalizations proceed under mild reaction conditions. The C H activations occur with a unique regioselectivity for the position ortho to the SCF₃ group, which apparently serves as directing group. Borylated SCF₃ compounds can serve as versatile building blocks.