Chemo-and Stereoselectivity of Nucleophilic Substitution in Mixed Phosphorus-Carboxylic Anhydrides

Abstract

Miwed phosphorus-carboxylic anhydrides have demonstrated both acylating and phosphorylating properties.[1] Here we report the reactivity of O,O-diethyl(O-2,4,6-trimethylbenzoyl) phosphates (1), and O-methyl (O-2,4,6-trimetyIbenzoyl) dimethylphosphonates (2)with nucleophiles in the presence of different strong organic bases (DBU, DMAP).     

Maximum Spin Polarization in Chromium Dimer Cations as Demonstrated by X‐ray Magnetic Circular Dichroism Spectroscopy

X‐ray magnetic circular dichroism spectroscopy has been used to characterize the electronic structure and magnetic moment of Cr₂⁺. Our results indicate that the removal of a single electron from the 4sσ_g bonding orbital of Cr₂ drastically changes the preferred coupling of the 3d electronic spins. While the neutral molecule has a zero‐spin ground state with a very short bond length, the molecular cation exhibits a ferromagnetically coupled ground state with the highest possible spin of S=11/2, and almost twice the bond length of the neutral molecule. This spin configuration can be interpreted as a result of indirect exchange coupling between the 3d electrons of the two atoms that is mediated by the single 4s electron through a strong intraatomic 3d‐4s exchange interaction. Our finding allows an estimate of the relative energies of two states that are often discussed as ground‐state candidates, the ferromagnetically coupled ¹²Σ and the low‐spin ²Σ state.     

TLC Analysis of Inhibitors of Cyclooxygenase and Videodensitometric Determination of Meloxicam and Tiaprofenic Acid

JPC – Journal of Planar Chromatography – Modern TLC - The cyclooxygenase inhibitors lornoxicam, meloxicam, piroxicam, and tiaprofenic acid have been separated by normal- and...     

Visible‐Light Photoactive,Highly Efficient Triplet Sensitizers Based on Iodinated Aza‐BODIPYs: Synthesis,Photophysics and Redox Properties

A series of novel iodinated NO₂‐substituted aza‐BODIPYs have been synthesized and characterized. Highly desirable photophysical and photochemical properties were induced in NO₂‐substituted aza‐BODIPYs by iodination of the pyrrole rings. In particular, high values of singlet oxygen quantum yields (Φ_Δ) ranging from 0.79 to 0.85 were measured. The photooxygenation process proceeds via a Type II mechanism under the experimental conditions applied. The compounds studied exhibited an absorption band within the so‐called “therapeutic window”, with λ_max located between 645 nm to 672 nm. They were non‐fluorescent at room temperature with excited singlet‐state lifetimes within the picosecond range as measured by femtosecond transient absorption. Nanosecond laser flash photolysis experiments revealed T₁→T_n absorption spanning from ca. 400 nm to ca. 500 nm and allowed determination of the triplet‐state lifetimes. The estimated triplet lifetimes (τ_T) in deaerated acetonitrile ranged between 2.74 μs and 3.50 μs. As estimated by CV/DPV measurements, all iodinated aza‐BODIPYs studied exhibited one irreversible oxidation and two quasi‐reversible reductions processes. Estimation of the E_HOMO gave the value of ?6.06 to ?6.26 eV while the E_LUMO was found to be located at ca. ?4.6 eV. Thermogravimetric (TGA) analysis revealed that iodinated aza‐BODIPYs were stable up to approximately 300 °C. All compounds studied exhibit high photostability in toluene solution.     

Defining rules of aromaticity: a unified approach to the Hückel, Clar and Randić concepts

The molecular structure of any system may be unambiguously described by its adjacency matrix, A, in which bonds are assigned entry a(ij) = 1 and non-bonded pairs of atoms entry a(ij) = 0. For π-electron-containing conjugated hydrocarbons, this matrix may be modified in order to represent one of the possible Kekulé structures by assigning entry 1 to double bonds and entry 0 to single bonds, leading to the Kekulé matrix K which can be obtained from the A matrix by subtracting 1 from elements a(pq) that represent single bonds in the Kekulé structure. The A and K matrices are the boundary cases of a general matrix A(ε), named perturbation matrix, in which from elements a(pq) that represent single bonds is subtracted a value ε∈<0,1> representing the magnitude of the perturbation. The determinant of the A(ε) matrix is unambiguously represented by an appropriate polynomial that, in turn, can be written in a form containing terms ±(1-ε)(N/2) that identify types of π-electron conjugated cycles (N is the corresponding number of π-electrons). If the sign before the term is (+), then the contribution is stabilizing, but if it is (-) the contribution is destabilizing. The approach shows why and how the Hückel rule works, how the Randi? conjugated circuits result from the analysis of canonical structures, and also how the Clar rule may be extended to include aromatic cycles larger than six-membered (aromatic sextet).     

Cutting process dynamics by nonlinear time series and wavelet analysis

We have modeled the dynamics of a cutting process by a two-degree-of-freedom mass-spring system with dry friction. Using nonlinear time series and wavelet analysis, we have investigated the vibrational instabilities of the system for different values of the cutting force. By constructing the phase portraits and calculating the Lyapunov exponents we have delineated the conditions for which a periodic or chaotic motion can occur. The results are verified by means of a time-scale representation of the wavelet power spectrum.     

EVIDENCE FOR PHYTOCHROME CONTROLLED ENDOMITOSIS AND CELL ELONGATION IN PISUM SATIVUM EPICOTYLS

Elongation and endomitosis were studied in the epicotyl cortex cells of germinating seeds of Pisum sativum cv. Rondo. One min of red light per 24 h is sufficient to fully inhibit endomitosis. Terminal far-red irradiation can reverse the red effect to the level established by far-red light alone. This justifies the conclusion that phytochrome is involved in the regulation of endomitotic DNA replication. Since far-red light alone inhibits endomitosis to about 50%, we conclude that very low levels of Pfr are required to influence the endomitotic cycle.     

On some properties ofJ-convex stochastic processes

Summary We present some results on the differentiability of convex stochastic processes. Furthermore, the stochastic version of a theorem onJ-convex functions majorized byJ-concave functions is given.     

Controlled spacing of cationic gold nanoparticles by nanocrown RNA

Using atomic force microscopy, we describe the linear arrangement of cationic gold nanoparticles directed by programmable self-assembling RNA ladders and demonstrate that the regular spacing of nanoparticles is controlled by the RNA architecture acting as nanocrown scaffoldings. Thus, precise positioning of molecular components can be accomplished with RNA not only through electrostatic but also via size and shape recognitions.     

Fractional quasiexcitons in incompressible electron liquids

A new kind of many-body excitonic state composed of fractionally charged constituents is introduced. The constituents are a trion (X^-) embedded in an incompressible electron liquid and Laughlin quasiholes (QH's). Laughlin electron–trion correlations lead to an effective trion charge of -e/3. This many-body excitation is called “quasiexciton” and denoted by to distinguish it from a normal trion. The can bind one or two (e/3)-charged QH's, giving a neutral or a positive . The energy spectra and photoluminescence from radiative quasiexciton decay are studied numerically and interpreted using a generalized composite Fermion model of the e–X^- fluid.