Linear‐dendritic block copolymer hosts for the encapsulation of electro‐optic chromophores via H‐Bonding

Linear‐dendritic block copolymer hosts were synthesized by end‐functionalizing poly(methylmethacrylate) with dendrons that acted as hydrogen‐bonding acceptors for nonlinear optical chromophores. Second harmonic generation experiments indicate that the d₃₃ coefficients and maximum chromophore loading are increased in linear‐dendritic block copolymer hosts over comparable homopolymer hosts. Transmission electron microscopy shows 5–10 nm chromophore domains, confirming the effective spatial dispersion of the chromophores. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5017–5026, 2009     

Cyclopolymerization of N,N′-methylene bisacrylamide initiated by S2O82−–Fe2+ redox system

Polymerization of the symmetrical nonconjugated diolefin, N,N′-methylene bisacrylamide, was carried out using peroxodisulphate ion -Fe²⁺ as redox initiator. The rate of polymerization is found to depend on [M]^3/2 and [S₂O₈^2?]^1/2 and independent of [Fe²⁺] over a range. A polymerization mechanism involving cyclopolymerization in the propagation step is suggested. Evidence in favor of the cyclopolymerization mechanism is discussed. Evaluation of the rate parameters indicates that the deactivation of the primary radical SO₄^? by Fe²⁺ ion is a factor to be reckoned with.     

Quantitative determination of tri-n-butyl phosphate by fluorescent X-ray spectrometry through inorganic association with an actinide

Tri-n-butyl phosphate (TBP) continues to be the most widely used solvent in nuclear fuel extraction, refining and reprocessing units for the extraction of actinides and their separation from fission products. An X-ray fluorescence spectrometric method (XRFS) for the determination of TBP content with an X-ray detectable element is presented. The method involves formation of an ion association complex of uranium with TBP-kerosene mixture in 3M nitric acid. The analytes uranium and bromine used as internal ratio elements in organic extract are excited by a primary X-ray beam from a rhodium tube. The solvent concentration is determined from the ratioed characteristic intensities of uranium and bromine. The procedure permits the determination of organic solvent in the range 0.5 to 5.0% with a relative standard deviation of 0.1%.     

An ab initio and DFT study on the hydrolysis of carbonyl dichloride

Hydrolysis of carbonyl dichloride or phosgene (Cl₂CO) in gas phase has been investigated at Hartree–Fock, density functional and ab initio levels of theory. The effects of basis sets on the energetics of the reaction have also been explored. Calculations reveal that initially carbonyl dichloride and water form a weak complex and this complex can react further in two ways. In Path 1, water adds on to carbonyl dichloride across carbonyl bond in a concerted fashion to give dichloromethane diol, and this diol decomposes to form chloro formic acid by syn-1,2-elimination of HCl and forms CO₂ and HCl as final products. Path 2 is the concerted addition of water across carbon chlorine bond and elimination of HCl in a single step leading to the formation of chloro formic acid directly. This second path that skips the formation of dichloromethane diol is observed to be very low lying and hence is kinetically favored. Addition of second water molecule to the reacting system is found to catalyze the reaction by stabilizing the complex, intermediate and transition states and reduces the activation energy to 24.6 kcal mol⁻¹ compared to 29.9 kcal mol⁻¹ for a single water molecule.     

Role of Magnetic Exchange Interactions in the Magnetization Relaxation of {3d–4f} Single‐Molecule Magnets: A Theoretical Perspective

Combined density functional and ab initio calculations are performed on two isomorphous tetranuclear {Ni₃^IIILn^III} star‐type complexes [Ln=Gd ( 1 ), Dy ( 2 )] to shed light on the mechanism of magnetic exchange in 1 and the origin of the slow magnetization relaxation in complex 2 . DFT calculations correctly reproduce the sign and magnitude of the J values compared to the experiments for complex 1 . Acute ?Ni?O?Gd bond angles present in 1 instigate a significant interaction between the 4f_xyz orbital of the Gd^III ion and 3d orbital of the Ni^II ions, leading to rare and strong antiferromagnetic Ni???Gd interactions. Calculations reveal the presence of a strong next‐nearest‐neighbour Ni???Ni antiferromagnetic interaction in complex 1 leading to spin frustration behavior. CASSCF+RASSI‐SO calculations performed on complex 2 suggest that the octahedral environment around the Dy^III ion is neither strong enough to stabilize the m_J |±15/2〉 as the ground state nor able to achieve a large ground‐state–first‐excited‐state gap. The ground‐state Kramers doublet for the Dy^III ion is found to be the m_J |±13/2〉 state with a significant transverse anisotropy, leading to very strong quantum tunneling of magnetization (QTM). Using the POLY_ANISO program, we have extracted the J_NiDy interaction as ?1.45 cm^?1. The strong Ni???Dy and next‐nearest‐neighbour Ni???Ni interactions are found to quench the QTM to a certain extent, resulting in zero‐field SMM behavior for complex 2 . The absence of any ac signals at zero field for the structurally similar [Dy(AlMe₄)₃] highlights the importance of both the Ni???Dy and the Ni???Ni interactions in the magnetization relaxation of complex 2 . To the best of our knowledge, this is the first time that the roles of both the Ni???Dy and Ni???Ni interactions in magnetization relaxation of a {3d–4f} molecular magnet have been established.     

Oblate versus Prolate Electron Density of Lanthanide Ions: A Design Criterion for Engineering Toroidal Moments? A Case Study on {LnIII6} (Ln=Tb,Dy, Ho and Er) Wheels

We report four new complexes based on a {Ln^III₆} wheel structure, three of which possess a net toroidal magnetic moment. The four examples consist of {Tb^III₆} and {Ho^III₆} wheels, which are rare examples of non Dy^III based complexes possessing a toroidal magnetic ground state, and a {Dy^III₆} complex which improves its toroidal structure upon lowering the crystallographic symmetry from trigonal (R ) to triclinic (P ). Notably the toroidal moment is lost for the trigonal {Er^III₆} analogue. This suggests the possibility of utilizing the popular concept of oblate and prolate electron density of the ground state M_J levels of lanthanide ions to engineer toroidal moments.     

Analysis of algorithms for an online version of the convoy movement problem

In the convoy movement problem (CMP), a set of convoys must be routed from specified origins to destinations in a transportation network, represented by an undirected graph. Two convoys may not cross each other on the same edge while travelling in opposing directions, a restriction referred to as blocking. However, convoys are permitted to follow each other on the same edge, with a specified headway separating them, but no overtaking is permitted. Further, the convoys to be routed are distinguished based on their length. Particle convoys have zero length and are permitted to traverse an edge simultaneously, whereas convoys with non-zero length have to follow each other, observing a headway. The objective is to minimize the total time taken by convoys to travel from their origins to their destinations, given the travel constraints on the edges. We consider an online version of the CMP where convoy demands arise dynamically over time. For the special case of particle convoys, we present an algorithm that has a competitive ratio of 3 in the worst case and (5/2) on average. For the particle convoy problem, we also present an alternate, randomized algorithm that provides a competitive ratio of (√13?1). We then extend the results to the case of convoys with length, which leads to an algorithm with an O(T+CL) competitive ratio, where T={Max _e t(e)}/{Min _e t(e)}, C is the maximum congestion (the number of distinct convoy origin–destination pairs that use any edge e) and L={Max _c L(c)}/{Min _c L(c)}; here L(c)>0 represents the time-headway to be observed by any convoy that follows c and t(e) represents the travel time for a convoy c on edge e.