Redox Non‐Innocence and Isomer‐Specific Oxidative Functionalization of Ruthenium‐Coordinated β‐Ketoiminate

This article deals with isomeric ruthenium complexes [Ru^III(L^R)₂(acac)] (S=1/2) involving unsymmetric β‐ketoiminates (AcNac) (L^R=R‐AcNac, R=H ( 1 ), Cl ( 2 ), OMe ( 3 ); acac=acetylacetonate) [R=para‐substituents (H, Cl, OMe) of N‐bearing aryl group]. The isomeric identities of the complexes, cct (cis‐cis‐trans, blue, a ), ctc (cis‐trans‐cis, green, b ) and ccc (cis‐cis‐cis_, pink, c ) with respect to oxygen (acac), oxygen (L) and nitrogen (L) donors, respectively, were authenticated by their single‐crystal X‐ray structures and spectroscopic/electrochemical features. One‐electron reversible oxidation and reduction processes of 1 – 3 led to the electronic formulations of [Ru^III(L)(L ^? )(acac)]⁺ and [Ru^II(L)₂(acac)]^? for 1 ⁺‐ 3 ⁺ (S=1) and 1^? – 3^? (S=0), respectively. The triplet state of 1 ⁺‐ 3 ⁺ was corroborated by its forbidden weak half‐field signal near g≈4.0 at 4 K, revealing the non‐innocent feature of L. Interestingly, among the three isomeric forms ( a – c in 1 – 3 ), the ctc ( b in 2 b or 3 b ) isomer selectively underwent oxidative functionalization at the central β‐carbon (C?H→C=O) of one of the L ligands in air, leading to the formation of diamagnetic [Ru^II(L)(L ′ )(acac)] (L ′ =diketoimine) in 4 / 4′ . Mechanistic aspects of the oxygenation process of AcNac in 2 b were also explored via kinetic and theoretical studies.     

Reactions of oxidizing radicals with 2- and 3-aminopyridines: a pulse radiolysis study

Reactions of OH radicals and some one-electron oxidants with 2-aminopyridine (2-AmPy) and 3-aminopyridine (3-AmPy) were studied in aqueous solutions using pulse radiolysis technique. The OH adduct of 2-AmPy at pH 9 has an absorption maximum at 360 nm along with a weak absorption band in the visible region and was found to be reactive with oxygen. The rate constant for its reaction with O₂ was determined to be 1.0×10⁸ dm³ mol⁻¹ s⁻¹. At pH 4 also, the OH adduct of 2-AmPy has an absorption band at 360 nm. However, there are differences in the absorption at other wavelengths. From the plot of ΔOD vs. pH at 340 nm, the pK_a of the OH adduct was determined to be 6.5. Among the specific oxidants, only SO₄^−√ radicals were able to oxidize 2-AmPy. In the case of 3-aminopyridine (3-AmPy), the transient species formed by OH radical reaction at pH 9 has an absorption maximum at 410 nm with shoulder bands on both the sides. Its absorption spectrum at pH 4 was different indicating the existence of a pK value for the OH adduct. pK_a of 3-AmPy-OH radical adduct species was evaluated to be 5.7. This adduct species was also found to be reactive with oxygen (k=7.6×10⁶ dm³ mol⁻¹ s⁻¹). Specific one-electron oxidants like N₃^√, Br₂^−√ C₂^−√ and SO₄^−√ were able to oxidize 3-AmPy indicating that it is easier to oxidize 3-AmPy as compared to 2-AmPy.     

Optimal non-linear dimension reduction scheme for classical molecular dynamics

The optimal creation of a reduced space that effectively captures the long timescale dynamics of a non-linear molecular system over a range of frequencies is described. The technique builds on a previously developed subspace method based on linear constant projective transformation of the original full space. The present work attempts to propose transformation that are spatially dependent thereby leading to an effective subspace for better representing the dynamics of interests. The algorithm seeks out an optimal transformation consistent with desired low frequency motion in a rather general way. The method is demonstrated for a six-dimensional nonlinear system reduced to two-dimensions. Superior performance is found in evaluating ensemble-averaged classical dynamical properties.     

Kinematical separation of α-n final-state interaction at 50 MeV incident energy

A kinematically complete experiment has been performed to study the α-n final-state interaction (FSI) in the α + d ↦α + p + n break-up reaction at 50 MeV incident energy for the alpha-particles. For this, we have chosen four pairs of correlation angles for the outgoing alpha and protons. These are ( θ_α = 18^°, θ_p = 42^°), ( θ_α = 20^°, θ_p = 45^°), ( θ_α = 22^°, θ_p = 42^°) and ( θ_α = 22^°, θ_p = 47^°), selected kinematically where the allowed phase spaces are in favor of the α-n final-state interaction. Our experimental data show strong α-n FSI in all the selected configurations. Also, the FSI is found to be stronger at the lower alpha-particle energy when two FSI peaks appear in the same configuration. Received: 17 June 2002 / Accepted: 3 October 2002 / Published online: 4 February 2003 RID="a" ID="a"e-mail: dey_s2001@yahoo.com; Present address: 445 Waupelani Drive, Apt. F3, State College, PA 16801, USA. Communicated by M. Gar?on     

Nanoparticle Size‐Fractionation through Self‐Standing Porous Covalent Organic Framework Films

Covalent organic frameworks (COFs) have attracted attention due to their ordered pores leading to important industrial applications like storage and separation. Combined with their modular synthesis and pore engineering, COFs could become ideal candidates for nanoseparations. However, the fabrication of these microcrystalline powders as continuous, crack‐free, robust films remains a challenge. Herein, we report a simple, slow annealing strategy to construct centimeter‐scale COF films ( Tp‐Azo and Tp‐TTA ) with micrometer thickness. The as‐synthesized films are porous (SA_BET=2033 m² g^?1 for Tp‐Azo ) and chemically stable. These COFs have distinct size cut‐offs (ca. 2.7 and ca. 1.6 nm for Tp‐Azo and Tp‐TTA , respectively), which allow the size‐selective separation of gold nanoparticles. Unlike, other conventional membranes, the durable structure of the COF films allow for excellent recyclability (up to 4 consecutive cycles) and easy recovery of the gold nanoparticles from the solution.     

Ultrafast photoinduced electron transfer in the micelle and the gel phase of a PEO-PPO-PEO triblock copolymer

Ultrafast photoinduced electron transfer (PET) from N,N-dimethylaniline (DMA) to coumarin dyes is studied in the micelle and the gel phase of a triblock copolymer, (PEO)(20)-(PPO)(70)-(PEO)(20) (Pluronic P123) by picosecond and femtosecond emission spectroscopies. The rate of PET in a P123 micelle and gel is found to be nonexponential and faster than the slow components of solvation dynamics. In a P123 micelle and gel, PET occurs on multiple time scales ranging from a subpicosecond time scale to a few nanoseconds. In the gel phase, the highest rate constant (9.3 x 10(9) M(-1) s(-1)) of ET for C152 is about two times higher than that (3.8 x 10(9) M(-1) s(-1)) observed in micelle phase. The ultrafast components of electron transfer (ET) exhibits a bell shaped dependence with the free energy change which is similar to the Marcus inversion. Possible reasons for slower PET in P123 micelle compared to other micelles and relative to P123 gel are discussed.     

Crystallization and structural relaxation in quasicrystalline Al6CuMg4

We report here electron microscopic, differential scanning calorimetric (DSC) and X-ray diffraction studies on the phase transition in Al₆CuMg₄ alloy. Structural analysis of the transformed crystalline phase suggests that some of the lattice sites, which define the vertices of triacontahedron - the basic volume element of three dimensional Penrose tiling for this system - are fractionally occupied. We also observed that the specific heat of the as grown quasicrystalline alloy reduces gradually from 1.08J/gm. K at 330K to the Dulong Petit value 0.84J/gm. K around 420K, due to structural relaxation of the quasicrystalline phase.     

Intermediates involved in serotonin oxidation catalyzed by Cu bound Aβ peptides

The degradation of neurotransmitters is a hallmark feature of Alzheimer''s disease (AD). Copper bound Aβ peptides, invoked to be involved in the pathology of AD, are found to catalyze the oxidation of serotonin (5-HT) by H₂O₂. A combination of EPR and resonance Raman spectroscopy reveals the formation of a Cu(ii)–OOH species and a dimeric, EPR silent, Cu₂O₂ bis-μ-oxo species under the reaction conditions. The Cu(ii)–OOH species, which can be selectively formed in the presence of excess H₂O₂, is the reactive intermediate responsible for 5-HT oxidation. H₂O₂ produced by the reaction of O₂ with reduced Cu(i)–Aβ species can also oxidize 5-HT. Both these pathways are physiologically relevant and may be involved in the observed decay of neurotransmitters as observed in AD patients.

The mononuclear copper hydroperoxo species (Cu(ii)–OOH) of Cu–Aβ is the active oxidant responsible for serotonin oxidation by Cu–Aβ in the presence of physiologically relevant oxidants like O₂ and H₂O₂, which can potentially cause oxidative degradation of neurotransmitters, a marker of Alzheimer''s disease.     

Kinetics and mechanism of the reactions of platinum(II)‐dipicolinate and platinum(II)‐glycylglycine with oxalate ion

The kinetics of the reactions of [Pt(dipic)(H₂O)] and [Pt(digly)(H₂O)] (where H₂dipic = pyridine‐2,6‐dicarboxylic acid and H₂digly = glycylglycine) with oxalate ion were studied at 25°C in aqueous medium by UV–vis spectroscopy at I = 0.1 mol dm^?3 over an wide range of pH. A probable associative pathway may involve a five‐coordinate intermediate leading to the formation of an unidentate oxalate species, which converts to bidentate chelate in subsequent fast steps. The products are isolated and characterized by CHN analysis, IR, and ¹H NMR spectra. The kinetic data from pH variation experiments are fitted by a computer program to a sequence of reactions and the different rate constants are evaluated. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 327–333, 2003