Electronic optical response of molecules in intense fields: comparison of TD-HF, TD-CIS, and TD-CIS(D) approaches

Time-dependent Hartree-Fock (TD-HF) and time-dependent configuration interaction (TD-CI) methods with Gaussian basis sets have been compared in modeling the response of hydrogen molecule, butadiene, and hexatriene exposed to very short, intense laser pulses (760 nm, 3 cycles). After the electric field of the pulse returns to zero, the molecular dipole continues to oscillate due to the coherent superposition of excited states resulting from the nonadiabatic excitation caused by the pulse. The Fourier transform of this residual dipole gives a measure of the nonadiabatic excitation. For low fields, only the lowest excited states are populated, and TD-CI simulations using singly excited states with and without perturbative corrections for double excitations [TD-CIS(D) and TD-CIS, respectively] are generally in good agreement with the TD-HF simulations. At higher field strengths, higher states are populated and the methods begin to differ significantly if the coefficients of the excited states become larger than approximately 0.1. The response of individual excited states does not grow linearly with intensity because of excited state to excited state transitions. Beyond a threshold in the field strength, there is a rapid increase in the population of many higher excited states, possibly signaling an approach to ionization. However, without continuum functions, the present TD-HF and TD-CI calculations cannot model ionization directly. The TD-HF and TD-CIS simulations are in good accord because the excitation energies obtained by linear response TD-HF [also known as random phase approximation (RPA)] agree very well with those obtained from singly excited configuration interaction (CIS) calculations. Because CIS excitation energies with the perturbative doubles corrections [CIS(D)] are on average lower than the CIS excitation energies, the TD-CIS(D) response is generally stronger than TD-CIS.     

Numerical simulation of nonadiabatic electron excitation in the strong-field regime. 3. Polyacene neutrals and cations

The electron optical response for a series of linear polyacenes and their molecular ions (mono and dications) in strong laser fields was studied using time-dependent Hartree-Fock theory. The interactions of benzene, naphthalene, anthracene, and tetracene with pulsed fields at a frequency of 1.55 eV and intensities of 8.77 x 10(13), 3.07 x 10(13), 1.23 x 10(13), and 2.75 x 10(12) W/cm2, respectively, were calculated using the 6-31G(d,p) basis set. Nonadiabatic processes, including nonadiabatic time evolution of the dipole moment, L?wden charges, and occupation numbers, were studied. The nonadiabatic response increased with the length of the molecule and was greatest for the molecular monocations. The only exception was tetracene, in which the very strong response of the dication was due to a near resonance with the applied field. The intensity and frequency dependence of the dipole moment response for the monocations of naphthalene and anthracene was also calculated. As the intensity increased, the population of higher-energy excited-states increased, and as the frequency increased, the excitation volume increased in good agreement with the Dykhne approximation.     

First seconds in a building's life-in situ synchrotron X-ray diffraction study of cement hydration on the millisecond timescale

Setting cement: highly dynamic hydration processes that occur during the first seconds of cement hydration were studied by time-resolved synchrotron X-ray diffraction. Polycarboxylate ether additives were found to influence the formation of the initial crystalline hydration products on a molecular level.     

Linearly polarized gluons and the Higgs transverse momentum distribution

We study how gluons carrying linear polarization inside an unpolarized hadron contribute to the transverse momentum distribution of Higgs bosons produced in hadronic collisions. They modify the distribution produced by unpolarized gluons in a characteristic way that could be used to determine whether the Higgs boson is a scalar or a pseudoscalar particle.     

Investigations on mechanical properties of PI-PS multigraft copolymers

The stress-strain behaviour of multigraft copolymers consisting of a polyisoprene (PI) backbone and grafted polystyrene (PS) arms have been characterized by applying models of rubber elasticity such as Mooney-Rivlin, slip-tube and the extended non-affine tube model. Additionally, the range of low deformation has been investigated by relaxation tests for determining the stress relaxation. Multigraft copolymers show high strain at break and low residual strain caused by the large number of physical cross links resulting from several grafted PS side chains. From the model fits the material parameters and of the slip-tube model, representing the influence of chemical cross links and entanglements effects, respectively, and the n_e/T_e-value (n_e - number of statistical segments between two successive entanglements, T_e - Langley trapping factor) of the extended non-affine tube model, are used to describe the tensile behaviour of these thermoplastic elastomers. The PS content was considered as filler phase taking into account the effect of hydrodynamic amplification. The influence of functionality and the number of branch points per molecule on the strain at break and the tensile strength is explained by the model parameters describing the stress-strain curve at low to medium (?400%, slip-tube, Mooney-Rivlin) and low to high (?900%, extended non-affine tube) elongations. It was observed that for the material with a spherical morphology is increasing with the number of branch points β (each branch point consists of a PI backbone segment, depending on the functionality one, two or four grafted PS arms). For cylindrical and lamellar morphologies the was decreasing with increasing β, which could be reconfirmed by applying the extended non-affine tube model where the n_e/T_e-parameter is increasing with β.     

Tri-partite complex for axonal transport drug delivery achieves pharmacological effect

Background

Targeted delivery of pharmaceutical agents into selected populations of CNS (Central Nervous System) neurons is an extremely compelling goal. Currently, systemic methods are generally used for delivery of pain medications, anti-virals for treatment of dermatomal infections, anti-spasmodics, and neuroprotectants. Systemic side effects or undesirable effects on parts of the CNS that are not involved in the pathology limit efficacy and limit clinical utility for many classes of pharmaceuticals. Axonal transport from the periphery offers a possible selective route, but there has been little progress towards design of agents that can accomplish targeted delivery via this intraneural route. To achieve this goal, we developed a tripartite molecular construction concept involving an axonal transport facilitator molecule, a polymer linker, and a large number of drug molecules conjugated to the linker, then sought to evaluate its neurobiology and pharmacological behavior.

Results

We developed chemical synthesis methodologies for assembling these tripartite complexes using a variety of axonal transport facilitators including nerve growth factor, wheat germ agglutinin, and synthetic facilitators derived from phage display work. Loading of up to 100 drug molecules per complex was achieved. Conjugation methods were used that allowed the drugs to be released in active form inside the cell body after transport. Intramuscular and intradermal injection proved effective for introducing pharmacologically effective doses into selected populations of CNS neurons. Pharmacological efficacy with gabapentin in a paw withdrawal latency model revealed a ten fold increase in half life and a 300 fold decrease in necessary dose relative to systemic administration for gabapentin when the drug was delivered by axonal transport using the tripartite vehicle.

Conclusion

Specific targeting of selected subpopulations of CNS neurons for drug delivery by axonal transport holds great promise. The data shown here provide a basic framework for the intraneural pharmacology of this tripartite complex. The pharmacologically efficacious drug delivery demonstrated here verify the fundamental feasibility of using axonal transport for targeted drug delivery.     

Phenanthroline‐Catalyzed Stereoretentive Glycosylations

Carbohydrates are essential moieties of many bioactive molecules in nature. However, efforts to elucidate their modes of action are often impeded by limitations in synthetic access to well‐defined oligosaccharides. Most of the current methods rely on the design of specialized coupling partners to control selectivity during the formation of glycosidic bonds. Reported herein is the use of a commercially available phenanthroline to catalyze stereoretentive glycosylation with glycosyl bromides. The method provides efficient access to α‐1,2‐cis glycosides. This protocol has been performed for the large‐scale synthesis of an octasaccharide adjuvant. Density‐functional theory calculations, together with kinetic studies, suggest that the reaction proceeds by a double S_N2 mechanism.