Interferometry of hyper-Rayleigh scattering by inhomogeneous thin films

The use of specific symmetry properties of the optical second-harmonic generation (the s,s-exclusion rule) has allowed us to observe high-contrast hyper-Rayleigh interference patterns in a completely diffuse light - an effect having no analog in case of linear (Rayleigh) scattering.Comment: 8 pages, 3 figure

Occupational and leisure time physical activity in contrasting relation to ambulatory blood pressure

Background: While moderate and vigorous leisure time physical activities are well documented to decrease the risk for cardiovascular disease, several studies have demonstrated an increased risk for cardiovascular disease in workers with high occupational activity. Research on the underlying causes to the contrasting effects of occupational and leisure time physical activity on cardiovascular health is lacking. The aim of this study was to examine the relation of objective and self-report measures of occupational and leisure time physical activity with 24-h ambulatory systolic blood pressure (BP). Methods: Results for self-reported physical activity are based on observations in 182 workers (60% male, mean age 51 years), while valid objective physical activity data were available in 151 participants. The usual level of physical activity was assessed by 5 items from the Job Content Questionnaire (high physical effort, lifting heavy loads, rapid physical activity, awkward body positions and awkward positions of head or arms at work) and one item asking about the general level of physical activity during non-working time. On a regular working day, participants wore an ambulatory BP monitor and an accelerometer physical activity monitor during 24 h. Associations were examined by means of Analysis of Covariance. Results: Workers with an overall high level of self-reported occupational physical activity as well as those who reported to often lift heavy loads at work had a higher mean systolic BP at work, at home and during sleep. However, no associations were observed between objectively measured occupational physical activity and BP. In contrast, those with objectively measured high proportion of moderate and vigorous leisure time physical activity had a significantly lower mean systolic BP during daytime, while no differences were observed according to self-reported level of leisure time physical activity. Conclusions: These findings suggest that workers reporting static occupational physical activities, unlike general physically demanding tasks characterized by dynamic movements of large muscle groups, are related to a higher daily systolic BP, while high objective levels of moderate and vigorous leisure time physical activity are related to lower daytime systolic BP. Ambulatory systolic BP may be a physiological explanatory factor for the contrasting effects of occupational and leisure time physical activity

Diquat Derivatives: Highly Active, Two-Dimensional Nonlinear Optical Chromophores with Potential Redox Switchability

In this article, we present a detailed study of structure−activity relationships in diquaternized 2,2′-bipyridyl (diquat) derivatives. Sixteen new chromophores have been synthesized, with variations in the amino electron donor substituents, π-conjugated bridge, and alkyl diquaternizing unit. Our aim is to combine very large, two-dimensional (2D) quadratic nonlinear optical (NLO) responses with reversible redox chemistry. The chromophores have been characterized as their PF_6^− salts by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. Their visible absorption spectra are dominated by intense π → π^* intramolecular charge-transfer (ICT) bands, and all show two reversible diquat-based reductions. First hyperpolarizabilities β have been measured by using hyper-Rayleigh scattering with an 800 nm laser, and Stark spectroscopy of the ICT bands affords estimated static first hyperpolarizabilities β_0. The directly and indirectly derived β values are large and increase with the extent of π-conjugation and electron donor strength. Extending the quaternizing alkyl linkage always increases the ICT energy and decreases the E_(1/2) values for diquat reduction, but a compensating increase in the ICT intensity prevents significant decreases in Stark-based β_0 responses. Nine single-crystal X-ray structures have also been obtained. Time-dependent density functional theory clarifies the molecular electronic/optical properties, and finite field calculations agree with polarized HRS data in that the NLO responses of the disubstituted species are dominated by ‘off-diagonal’ β_(zyy) components. The most significant findings of these studies are: (i) β_0 values as much as 6 times that of the chromophore in the technologically important material (E)-4′-(dimethylamino)-N-methyl-4-stilbazolium tosylate; (ii) reversible electrochemistry that offers potential for redox-switching of optical properties over multiple states; (iii) strongly 2D NLO responses that may be exploited for novel practical applications; (iv) a new polar material, suitable for bulk NLO behavior

Evolution of Linear Absorption and Nonlinear Optical Properties in V-Shaped Ruthenium(II)-Based Chromophores

In this article, we describe a series of complexes with electron-rich cis-{Ru^(II)(NH_3)_4}^(2+) centers coordinated to two pyridyl ligands bearing N-methyl/arylpyridinium electron-acceptor groups. These V-shaped dipolar species are new, extended members of a class of chromophores first reported by us (Coe, B. J. et al. J. Am. Chem. Soc. 2005, 127, 4845−4859). They have been isolated as their PF_6− salts and characterized by using various techniques including ^1H NMR and electronic absorption spectroscopies and cyclic voltammetry. Reversible Ru^(III/II) waves show that the new complexes are potentially redox-switchable chromophores. Single crystal X-ray structures have been obtained for four complex salts; three of these crystallize noncentrosymmetrically, but with the individual molecular dipoles aligned largely antiparallel. Very large molecular first hyperpolarizabilities β have been determined by using hyper-Rayleigh scattering (HRS) with an 800 nm laser and also via Stark (electroabsorption) spectroscopic studies on the intense, visible d → π^* metal-to-ligand charge-transfer (MLCT) and π → π^* intraligand charge-transfer (ILCT) bands. The latter measurements afford total nonresonant β_0 responses as high as ca. 600 × 10^(−30) esu. These pseudo-C_(2v) chromophores show two substantial components of the β tensor, β_(zzz) and β_(zyy), although the relative significance of these varies with the physical method applied. According to HRS, β_(zzz) dominates in all cases, whereas the Stark analyses indicate that β_(zyy) is dominant in the shorter chromophores, but β_(zzz) and β_(zyy) are similar for the extended species. In contrast, finite field calculations predict that β_(zyy) is always the major component. Time-dependent density functional theory calculations predict increasing ILCT character for the nominally MLCT transitions and accompanying blue-shifts of the visible absorptions, as the ligand π-systems are extended. Such unusual behavior has also been observed with related 1D complexes (Coe, B. J. et al. J. Am. Chem. Soc. 2004, 126, 3880−3891)

systematic review and meta-analysis of published studies and unpublished individual participant data

Objective To quantify the association between long working hours and alcohol use. Design Systematic review and meta-analysis of published studies and unpublished individual participant data. Data sources A systematic search of PubMed and Embase databases in April 2014 for published studies, supplemented with manual searches. Unpublished individual participant data were obtained from 27 additional studies. Review methods The search strategy was designed to retrieve cross sectional and prospective studies of the association between long working hours and alcohol use. Summary estimates were obtained with random effects meta-analysis. Sources of heterogeneity were examined with meta-regression. Results Cross sectional analysis was based on 61 studies representing 333 693 participants from 14 countries. Prospective analysis was based on 20 studies representing 100 602 participants from nine countries. The pooled maximum adjusted odds ratio for the association between long working hours and alcohol use was 1.11 (95% confidence interval 1.05 to 1.18) in the cross sectional analysis of published and unpublished data. Odds ratio of new onset risky alcohol use was 1.12 (1.04 to 1.20) in the analysis of prospective published and unpublished data. In the 18 studies with individual participant data it was possible to assess the European Union Working Time Directive, which recommends an upper limit of 48 hours a week. Odds ratios of new onset risky alcohol use for those working 49-54 hours and ≥55 hours a week were 1.13 (1.02 to 1.26; adjusted difference in incidence 0.8 percentage points) and 1.12 (1.01 to 1.25; adjusted difference in incidence 0.7 percentage points), respectively, compared with working standard 35-40 hours (incidence of new onset risky alcohol use 6.2%). There was no difference in these associations between men and women or by age or socioeconomic groups, geographical regions, sample type (population based v occupational cohort), prevalence of risky alcohol use in the cohort, or sample attrition rate. Conclusions Individuals whose working hours exceed standard recommendations are more likely to increase their alcohol use to levels that pose a health risk

Long working hours and risk of coronary heart disease and stroke: a systematic review and meta-analysis of published and unpublished data for 603 838 individuals

Background: Long working hours might increase the risk of cardiovascular disease, but prospective evidence is scarce, imprecise, and mostly limited to coronary heart disease. We aimed to assess long working hours as a risk factor for incident coronary heart disease and stroke. / Methods: We identified published studies through a systematic review of PubMed and Embase from inception to Aug 20, 2014. We obtained unpublished data for 20 cohort studies from the Individual-Participant-Data Meta-analysis in Working Populations (IPD-Work) Consortium and open-access data archives. We used cumulative random-effects meta-analysis to combine effect estimates from published and unpublished data. / Findings: We included 25 studies from 24 cohorts in Europe, the USA, and Australia. The meta-analysis of coronary heart disease comprised data for 603 838 men and women who were free from coronary heart disease at baseline; the meta-analysis of stroke comprised data for 528 908 men and women who were free from stroke at baseline. Follow-up for coronary heart disease was 5·1 million person-years (mean 8·5 years), in which 4768 events were recorded, and for stroke was 3·8 million person-years (mean 7·2 years), in which 1722 events were recorded. In cumulative meta-analysis adjusted for age, sex, and socioeconomic status, compared with standard hours (35–40 h per week), working long hours (≥55 h per week) was associated with an increase in risk of incident coronary heart disease (relative risk [RR] 1·13, 95% CI 1·02–1·26; p=0·02) and incident stroke (1·33, 1·11–1·61; p=0·002). The excess risk of stroke remained unchanged in analyses that addressed reverse causation, multivariable adjustments for other risk factors, and different methods of stroke ascertainment (range of RR estimates 1·30–1·42). We recorded a dose–response association for stroke, with RR estimates of 1·10 (95% CI 0·94–1·28; p=0·24) for 41–48 working hours, 1·27 (1·03–1·56; p=0·03) for 49–54 working hours, and 1·33 (1·11–1·61; p=0·002) for 55 working hours or more per week compared with standard working hours (ptrend<0·0001). / Interpretation: Employees who work long hours have a higher risk of stroke than those working standard hours; the association with coronary heart disease is weaker. These findings suggest that more attention should be paid to the management of vascular risk factors in individuals who work long hours. / Funding: Medical Research Council, Economic and Social Research Council, European Union New and Emerging Risks in Occupational Safety and Health research programme, Finnish Work Environment Fund, Swedish Research Council for Working Life and Social Research, German Social Accident Insurance, Danish National Research Centre for the Working Environment, Academy of Finland, Ministry of Social Affairs and Employment (Netherlands), US National Institutes of Health, British Heart Foundation

Physical Activity Status in Patients With Coronary Heart Disease: Results From the Cross-Sectional EUROASPIRE Surveys.

BACKGROUND: The study aim was to assess the physical activity levels as well as the intention to become physically active in patients with stable coronary heart disease (CHD) with a special focus on the association with their risk profile. METHODS: Analyses are based on the cross-sectional EUROASPIRE IV surveys. Information was available on 8966 patients in EUROASPIRE III and on 7998 patients in EUROASPIRE IV. Physical activity level according to patients risk profile and their medical management was assessed, the intention to become physically active was investigated and a time trend analysis was performed. RESULTS: A better cardiovascular risk profile as well as receiving physical activity advice or weight loss advice was associated with better physical activity levels. The physical activity status improved significantly over time, the proportion of patients reporting vigorous physical activity for at least 20 minutes ≥ 3 times/week increased from 14.1% to 20.2% (P < .001). Similarly, a significantly greater proportion of patients are in the maintenance stage (36.6% vs. 27.4%) and a smaller proportion in the precontemplation stage (43.2% vs. 52.3%). CONCLUSION: Although an increase was seen in the proportion of patients being adequately physical active, physical activity levels remain suboptimal in many CHD patients

Computational De Novo Design and Characterization of a Protein That Selectively Binds a Highly Hyperpolarizable Abiological Chromophore

This work reports the first example of a single-chain protein computationally designed to contain four α-helical segments and fold to form a four-helix bundle encapsulating a supramolecular abiological chromophore that possesses exceptional nonlinear optical properties. The 109-residue protein, designated SCRPZ-1, binds and disperses an insoluble hyperpolarizable chromophore, ruthenium(II) [5-(4\u27-ethynyl-(2,2\u27;6\u27,2″-terpyridinyl))-10,20-bis(phenyl)porphinato]zinc(II)-(2,2\u27;6\u27,2″-terpyridine)(2+) (RuPZn) in aqueous buffer solution at a 1:1 stoichiometry. A 1:1 binding stoichiometry of the holoprotein is supported by electronic absorption and circular dichroism spectra, as well as equilibrium analytical ultracentrifugation and size exclusion chromatography. SCRPZ-1 readily dimerizes at micromolar concentrations, and an empirical redesign of the protein exterior produced a stable monomeric protein, SCRPZ-2, that also displayed a 1:1 protein:cofactor stoichiometry. For both proteins in aqueous buffer, the encapsulated cofactor displays photophysical properties resembling those exhibited by the dilute RuPZn cofactor in organic solvent: femtosecond, nanosecond, and microsecond time scale pump-probe transient absorption spectroscopic data evince intensely absorbing holoprotein excited states having large spectral bandwidth that penetrate deep in the near-infrared energy regime; the holoprotein electronically excited triplet state exhibits a microsecond time scale lifetime characteristic of the RuPZn chromophore. Hyper-Rayleigh light scattering measurements carried out at an incident irradiation wavelength of 1340 nm for these holoproteins demonstrate an exceptional dynamic hyperpolarizabilty (β1340 = 3100 × 10(-30) esu). X-ray reflectivity measurements establish that this de novo-designed hyperpolarizable protein can be covalently attached with high surface density to a silicon surface without loss of the cofactor, indicating that these assemblies provide a new approach to bioinspired materials that have unique electro-optic functionality