The Effect of varying Ground-state Aromaticity on the First Molecular Electronic Hyperpolarizabilites of Organic Donor-Acceptor Molecules

A series of compounds of the form 4-dimethylaminophenyl–polyene–acceptor, where the polyene ranges from nothing to all-trans-1,3,5-hexatriene and the acceptor is 2-nitrovinyl, formyl, or 2,2-dicyanovinyl has been prepared and their β values measured by solution electric-field-induced second-harmonic generation; these molecules, which lose only one aromatic resonance upon charge-transfer excitation, show enhanced β compared to bi-aromatic molecules with the same substitution and total conjugation length, such as 4-dimethylamino-4′-nitrostilbene (DANS), a well-known benchmark for high β organic molecules

The First Molecular Electronic Hyperpolarizabilities of Highly Polarizable Organic Molecules: 2,6-Di-tert-butylindoanilines

The first molecular hyperpolarizabilities (β) of a series of 2,6-di-tert-butylindoanilines, measured by electric-field-induced second harmonic generation are somewhat more sensitive to donor strength than was found for analogously substituted nitrostilbenes, and dimethylindoaniline has a β roughly twice that of its 2,6 di-tert-butylated analogue, measured in chloroform; solvatochromic measurements on the former compound suggest that this decrease in hyperpolarizability is consistent with a bound-solvent effect

Synthesis and First Hyperpolarizabilities of Acceptor-substituted β-apo-8’-Carotenal Derived Compounds

The synthesis and second-order nonlinear optical properties of acceptor-substituted biologically derived β-apo-8′-carotenal compounds are reported; electric field-induced second harmonic generation (EFISH) measurements give values of β(0) which are 2–6 times greater than for 4-N,N-dimethylamino-4′-nitrostilbene (DANS)

The dependence of the molecular first hyperpolarizabilities of merocyanines on ground-state polarization and length

We report here the dipole moment (µ) and first hyperpolarizability (β) determined by electric field-induced second harmonic generation, for several merocyanine dyes containing an 1,3,3-trimethylindoline heterocycle as a ‘donor’ in which the ‘acceptor’ end of the molecule and the polyene bridge length was systematically varied; dyes with hexamethine bridges gave positive β, while that with a dimethine bridge gave a negative β value

Experimental tests of reaction rate theory: Mu+H2 and Mu+D2

Copyright @ 1987 American Institute of Physics.Bimolecular rate constants for the thermal chemical reactions of muonium (Mu) with hydrogen and deuterium—Mu+H2→MuH+H and Mu+D2→MuD+D—over the temperature range 473–843 K are reported. The Arrhenius parameters and 1σ uncertainties for the H2 reaction are log A (cm3 molecule-1 s-1)=-9.605±0.074 and Ea =13.29±0.22 kcal mol-1, while for D2 the values are -9.67±0.12 and 14.73±0.40, respectively. These results are significantly more precise than those reported earlier by Garner et al. For the Mu reaction with H2 our results are in excellent agreement with the 3D quantum mechanical calculations of Schatz on the Liu–Siegbahn–Truhlar–Horowitz potential surface, but the data for both reactions compare less favorably with variational transition-state theory, particularly at the lower temperatures.NSERC (Canada) and the Petroleum Research Foundation of the Americal Chemical Society

Online Searching in PBL Tutorials

This study aims to explore how online searching plays a role during PBL tutorials in two undergraduate health sciences curricula, Medicine and Dentistry. Utilizing Interactional Ethnography (IE) as an organizing framework for data collection and analysis, and drawing on a critical theory of technology as an explanatory lens, enabled a textured understanding of student practices and beliefs regarding online searching during face-to-face PBL tutorials. Two event maps trace key transitions in learning regarding online searching in one cycle of problem-based learning in each program. From a critical perspective, analysis of students’ stimulated recall interviews indicated that the use of students’ personal mobile devices with online searching capacity is considered a dynamic pedagogically and socially constructed process. Online searching during the PBL process is also viewed as a “site-of-struggle” where there are challenges for first-year undergraduates when implementing such learning technologies in PBL tutorials

Optimizing the second-order optical nonlinearities of organic molecules: asymmetric cyanines and highly polarized polyenes

e recently reported that there is an optimal combination of donor and acceptor strengths for a given molecular length and bridge structure that maximizes (beta) . For this combination, there is the correct degree of bond length alternation and asymmetry in the molecule. Our recent findings suggest that molecules that can be viewed as asymmetric cyanines with relatively small amounts of bond length alternation are nearly optimal. In this manner, we have identified molecules with nonlinearities many times that of conventional chromophores for a given length. In this paper, we will present a new computational analysis that allows the correlation of bond length alternation with hyperpolarizabilities and will present EFISH data on simple donor-acceptor polyene chromophores

Oscillations of General Relativistic Multi-fluid/Multi-layer Compact Stars

We develop the formalism for determining the quasinormal modes of general relativistic multi-fluid compact stars in such a way that the impact of superfluid gap data can be assessed. Our results represent the first attempt to study true multi-layer dynamics, an important step towards considering realistic superfluid/superconducting compact stars. We combine a relativistic model for entrainment with model equations of state that explicity incorporate the symmetry energy. Our analysis emphasises the many different parameters that are required for this kind of modelling, and the fact that standard tabulated equations of state are grossly incomplete in this respect. To make progress, future equations of state need to provide the energy density as a function of the various nucleon number densities, the temperature (i.e. entropy), and the entrainment among the various components

Impact of an interatrial shunt device on survival and heart failure hospitalization in patients with preserved ejection fraction

Aims: Impaired left ventricular diastolic function leading to elevated left atrial pressures, particularly during exertion, is a key driver of symptoms and outcomes in heart failure with preserved ejection fraction (HFpEF). Insertion of an interatrial shunt device (IASD) to reduce left atrial pressure in HFpEF has been shown to be associated with short‐term haemodynamic and symptomatic benefit. We aimed to investigate the potential effects of IASD placement on HFpEF survival and heart failure hospitalization (HFH). Methods and results: Heart failure with preserved ejection fraction patients participating in the Reduce Elevated Left Atrial Pressure in Patients with Heart Failure study (Corvia Medical) of an IASD were followed for a median duration of 739 days. The theoretical impact of IASD implantation on HFpEF mortality was investigated by comparing the observed survival of the study cohort with the survival predicted from baseline data using the Meta‐analysis Global Group in Chronic Heart Failure heart failure risk survival score. Baseline and post‐IASD implant parameters associated with HFH were also investigated. Based upon the individual baseline demographic and cardiovascular profile of the study cohort, the Meta‐analysis Global Group in Chronic Heart Failure score‐predicted mortality was 10.2/100 pt years. The observed mortality rate of the IASD‐treated cohort was 3.4/100 pt years, representing a 33% lower rate (P = 0.02). By Kaplan–Meier analysis, the observed survival in IASD patients was greater than predicted (P = 0.014). Baseline parameters were not predictive of future HFH events; however, poorer exercise tolerance and a higher workload‐corrected exercise pulmonary capillary wedge pressure at the 6 months post‐IASD study were associated with HFH. Conclusions: The current study suggests IASD implantation may be associated with a reduction in mortality in HFpEF. Large‐scale ongoing randomized studies are required to confirm the potential benefit of this therapy