Competing (1)πσ* mediated dynamics in mequinol: O-H versus O-CH(3) photodissociation pathways

Deactivation of excited electronic states through coupling to dissociative (1)πσ* states in heteroaromatic systems has received considerable attention in recent years, particularly as a mechanism that contributes to the ultraviolet (UV) photostability of numerous aromatic biomolecules and their chromophores. Recent studies have expanded upon this work to look at more complex species, which involves understanding competing dynamics on two different (1)πσ* potential energy surfaces (PESs) localized on different heteroatom hydride coordinates (O-H and N-H bonds) within the same molecule. In a similar spirit, the work presented here utilizes ultrafast time-resolved velocity map ion imaging to study competing dissociation pathways along (1)πσ* PESs in mequinol (p-methoxyphenol), localized at O-H and O-CH(3) bonds yielding H atoms or CH(3) radicals, respectively, over an excitation wavelength range of 298-238 nm and at 200 nm. H atom elimination is found to be operative via either tunneling under a conical intersection (CI) (298 ≥ λ ≥ 280 nm) or ultrafast internal conversion through appropriate CIs (λ ≤ 245 nm), both of which provide mechanisms for coupling onto the dissociative state associated with the O-H bond. In the intermediate wavelength range of 280 ≥ λ ≥ 245 nm, mediated H atom elimination is not observed. In contrast, we find that state driven CH(3) radical elimination is only observed in the excitation range 264 ≥ λ ≥ 238 nm. Interpretation of these experimental results is guided by: (i) high level complete active space with second order perturbation theory (CASPT2) calculations, which provide 1-D potential energy cuts of the ground and low lying singlet excited electronic states along the O-H and O-CH(3) bond coordinates; and (ii) calculated excitation energies using CASPT2 and the equation-of-motion coupled cluster with singles and doubles excitations (EOM-CCSD) formalism. From these comprehensive studies, we find that the dynamics along the O-H coordinate generally mimic H atom elimination previously observed in phenol, whereas O-CH(3) bond fission in mequinol appears to present notably different behavior to the CH(3) elimination dynamics previously observed in anisole (methoxybenzene).     

Understanding solvent effects in the selective conversion of fructose to 5-hydroxymethyl-furfural: a molecular dynamics investigation

Selective conversion of fructose to 5-hydroxymethyl-furfural (HMF) involves the participation of high-boiling solvents like dimethyl sulfoxide (DMSO). In order to replace DMSO with low-boiling solvents, it is imperative that we understand the effect of DMSO solvation in protecting (i) HMF from rehydration and humins formation reactions and (ii) fructose from side reactions, other than its dehydration to HMF. In the present work, molecular dynamics simulations of HMF and fructose in water and in water-DMSO mixtures are carried out using the OPLS-AA force field. Radial pair distribution functions, coordination numbers and the hydrogen-bond network between the HMF/fructose molecule and the solvent molecules are analysed. The local 3-dimensional picture of the arrangement of solvent molecules around the solute, which cannot be accessed from pair distribution functions, is also computed. We show preferential coordination of DMSO around HMF and explain how this could provide a shielding effect to the HMF molecule, thus protecting it from further rehydration to levulinic acid and formic acid and from humins formation. In the case of fructose, the presence of DMSO also reduces the number of water molecules in the immediate vicinity of fructose. Though fewer water molecules coordinate around fructose, they are bound strongly to it. Analysis of the local 3-dimensional arrangement of DMSO molecules suggests that it protects the fructose molecule from side reactions that would lead to condensation or reversion products. However, the presence of DMSO molecules does not hamper the water molecules coming into contact with the oxygen atom of the hydroxyl groups of fructose, which is required for a proton transfer from water to fructose, to initiate the dehydration reaction to HMF.     

Photosensitive, all-glass AgPO3/silicaphotonic bandgap fiber

Photonic bandgap (PBG) guidance is observed in a solid core photonic crystal fiber (PCF) consisting of silver metaphosphate (AgPO(3)) glass embedded into a silica cladding, realized by vacuum-assisted infiltration of the molten glass into the hollow channels of a commercial silica PCF. Morphologic analysis of the cladding microstructure by optical and scanning electron microscopy reveals the formation of highly homogeneous glass strands along the PCF length. The characteristic transmission spectrum of the fiber shows PBG guidance in the range between 350 and 1650 nm. The exposure of the cladding glass matrix, using 355 nm, 150 ps laser irradiation, allows photo-induced enhancement of the transmission-to-stop-band extinction ratio by ～60 dB/cm and bandwidth tuning. Numerical calculations of the transmission pattern of the fabricated AgPO(3)/silica bandgap fiber are in good agreement with experiments.     

Bragg grating recording in low-defect optical fibers using ultraviolet femtosecond radiation and a double-phase mask interferometer

The fabrication of Bragg reflectors in fluorine depressed cladding silicate glass and SMF-28 fibers by employing a double-phase mask interferometer and 248 nm, 500 fs laser radiation is demonstrated here. The maximum refractive index changes obtained were of the order of 6 x 10(-4) for pulse intensities of 220 GW/cm(2) and accumulated energy densities of 3.5 kJ/cm(2). The Bragg gratings fabricated in the F-doped fiber endured temperatures greater than 700 degrees C, while those inscribed in the standard telecom fiber demarcated at 900 degrees C. The experimental results presented depict that the combination of the two phase mask interferometer and the 248 nm photon at sub-TW/cm(2) intensities constitute an efficient route in the fabrication of Bragg gratings in low-defect silicate glass optical fibers.     

Intramolecular thiomaleimide [2 + 2] photocycloadditions: stereoselective control for disulfide stapling and observation of excited state intermediates by transient absorption spectroscopy

Thiomaleimides undergo efficient intermolecular [2 + 2] photocycloaddition reactions and offer applications from photochemical peptide stapling to polymer crosslinking; however, the reactions are limited to the formation of the exo head-to-head isomers. Herein, we present an intramolecular variation which completely reverses the stereochemical outcome of this photoreaction, quantitatively generating endo adducts which minimise the structural disturbance of the disulfide staple and afford a 10-fold increase in quantum yield. We demonstrate the application of this reaction on a protein scaffold, using light to confer thiol stability to an antibody fragment conjugate. To understand more about this intriguing class of [2 + 2] photocycloadditions, we have used transient absorption spectroscopy (electronic and vibrational) to study the excited states involved. The initially formed S₂ (π₁π*) excited state is observed to decay to the S₁ (n₁π*) state before intersystem crossing to a triplet state. An accelerated intramolecular C–C bond formation provides evidence to explain the increased efficiency of the reaction, and the impact of the various excited states on the carbonyl vibrational modes is discussed.

Tethered bromomaleimides are described which undergo thiol conjugation and rapid regio- and stereoselective photocycloadditions to serve as disulfide staples; with the excited state intermediates observed by transient absorption spectroscopies.     

On killing characteristic classes by cobordism

Let M be an n-dimensional, differential, compact and closed manifold and let c be a characteristic class of degree greater or equal to (n+1)/2. We will prove that if the class c anihilates all the characteristic numbers of M, where it enters as a factor, then the manifold M is cobordant to a manifold in which the class c is zero. Also, we will examine the case of manifolds with an extra structure.     

Vector and parallel computing for matrix balancing

Estimating the entries of a large matrix to satisfy a set of internal consistency relations is a problem with several applications in economics, urban and regional planning, transportation, statistics and other areas. It is known as theMatrix Balancing Problem. Matrix balancing applications arising from the estimation of telecommunication or transportation traffic and from multi-regional trade flows give rise to huge optimization problems. In this report, we show that the RAS algorithm can be specialized for vector and parallel computing and used for the solution of very large problems. The algorithm is specialized for vector computations on a CRAY X-MP and is parallelized on an Alliant FX/8. A variant of the algorithm — developed here for its potential parallelism — turns out to be more efficient than the original algorithm even when implemented serially. We use the algorithms to estimate disaggregated input/output tables and a multi-regional trade flow table of the U.S. The larger problem solved has approximately 12 000 constraints and over 370 000 nonlinear variables. This is the first of two papers that aim at the solution of very large matrix balancing problems. Zenios [20] is using the same algorithm for the same models on a massively parallel Connection Machine CM-2.Research partially supported by NSF grants ECS-8718971 and CCR-8811135, and AFOSR grant 89-0145. Computing resources were made available through the ACRF at Argonne National Laboratory and CRAY Research, Inc.     

Vectorization and multitasking of nonlinear network programming algorithms

Vector supercomputers are designed with two levels of parallelism in order to achieved computational efficiency: low level parallelism through vector operations and high level parallelism with multiple independent processors. These innovations have a significant impact on the development of algorithms for network optimization.In this paper a framework for the vectorization and multitasking of optimization software is developed. It is then applied on the primal truncated Newton algorithm for nonlinear generalized network problems. The vectorization and multitasking of the algorithm is discussed and illustrated with computational experiments with the software system NLPNETG on the CRAY series of vector multiprocessors.