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In the present work, we addressed the relationship between parental leave policies and social norms. Using a pre-registered, cross-national approach, we examined the relationship between parental leave policies and the perception of social norms for the gender division of childcare. In this study, 19,259 students (11,924 women) from 48 countries indicated the degree to which they believe childcare is (descriptive norm) and should be (prescriptive norm) equally divided among mothers and fathers. Policies were primarily operationalized as the existence of parental leave options in the respective country. The descriptive and prescriptive norms of equal division of childcare were stronger when parental leave was available in a country - also when controlling for potential confounding variables. Moreover, analyses of time since policy change suggested that policy change may initially affect prescriptive norms and then descriptive norms at a later point. However, due to the cross-sectional nature of the data, drawing causal inferences is difficult., (© 2024 British Psychological Society.)

In urban areas, inhalation of fine particles from combustion sources such as diesel engines causes adverse health effects. For toxicity testing, a substantial amount of particulate matter (PM) is needed. Conventional sampling involves collection of PM onto substrates by filtration or inertial impaction. A major drawback to those methodologies is that the extraction process can modify the collected particles and alter their chemical composition. Moreover, prior to toxicity testing, PM samples need to be resuspended, which can alter the PM sample even further. Lastly, the choice of the resuspension medium may also impact the detected toxicological responses. In this study, we compared the toxicity profile of PM obtained from two alternative sampling systems, using in vitro toxicity assays. One system makes use of condensational growth before collection in water in an impinger - BioSampler (CG-BioSampler), and the other, a Dekati® Gravimetric Impactor (DGI), is based on inertial impaction. In addition, various methods for resuspension of DGI collected PM were compared. Tested endpoints included cytotoxicity, formation of cellular reactive oxygen species, and genotoxicity. The alternative collection and suspension methods affected different toxicological endpoints. The water/dimethyl sulfoxide mixture and cell culture medium resuspended particles, along with the CG-BioSampler sample, produced the strongest responses. The water resuspended sample from the DGI appeared least toxic. CG-BioSampler collected PM caused a clear increased response in apoptotic cell death. We conclude that the CG-BioSampler PM sampler is a promising alternative to inertial impaction sampling., (© 2024 The Authors. Journal of Applied Toxicology published by John Wiley & Sons Ltd.)

Proficient reading requires critical phonological processing skill that interacts with both genetic and environmental factors. However, the precise nature of the relationships between phonological processing and genetic and environmental factors are poorly understood. We analyzed data from the Genes, Reading and Dyslexia (GRaD) Study on 1419 children ages 8-15 years from African-American and Hispanic-American family backgrounds living in North America. The analyses showed that phonological awareness mediated the relationship between DCDC2-READ1 and reading outcomes when parental education and socioeconomic status was low. The association between READ1 and reading performance is complex, whereby mediation by phonological awareness was significantly moderated by both parental education and socioeconomic status. These results show the importance of home environment and phonological skills when determining associations between READ1 and reading outcomes. This will be an important consideration in the development of genetic screening for risk of reading disability., (© 2024. The Author(s).)

The Towards Gender Harmony (TGH) project began in September 2018 with over 160 scholars who formed an international consortium to collect data from 62 countries across six continents. Our overarching goal was to analyze contemporary perceptions of masculinity and femininity using quantitative and qualitative methods, marking a groundbreaking effort in social science research. The data collection took place between January 2018 and February 2020, and involved undergraduate students who completed a series of randomized scales and the data was collected through the SurveyMonkey or Qualtrics platforms, with paper surveys being used in rare cases. All the measures used in the project were translated into 22 languages. The dataset contains 33,313 observations and 286 variables, including contemporary measures of gendered self-views, attitudes, and stereotypes, as well as relevant demographic data. The TGH dataset, linked with accessible country-level data, provides valuable insights into the dynamics of gender relations worldwide, allowing for multilevel analyses and examination of how gendered self-views and attitudes are linked to behavioral intentions and demographic variables., (© 2024. The Author(s).)

Xanthones comprise a large family of heterocycles displaying fascinating biological properties. Many synthetic protocols have been developed for the preparation of natural and nonnatural xanthone derivatives. Among them, condensation reactions between salicylic acid derivatives and phenol partners are highly desirable. Those reactions can be satisfactorily performed using Eaton's reagent (P 2 O 5 in CH 3 SO 3 H). Despite being highly effective with a variety of substrates, this approach presents limitations that depend on the electronic nature of the reaction precursors. The scope and limitations of the Eaton's reagent-mediated preparation of xanthones are herein presented and discussed. In short, this approach is limited to the utilization of very electron-rich phenol substrates (like phloroglucinol compounds), or to electron-rich phenol precursors (like resorcinol derivatives) via the isolation of benzophenone intermediates in this latter case. Electron-poor phenols are not amenable to this transformation with Eaton's reagent., Competing Interests: Conflicts of interest: There is no known conflict of interest., (© TÜBİTAK.)

Occurrence of chiral recognition in bimolecular photoinduced electron transfer (ET) is difficult to identify because of the predominant role of diffusion. To circumvent this problem, we apply a combination of ultrafast time-resolved fluorescence and transient electronic absorption to look for stereoselectivity in the initial, static stage of ET quenching, where diffusion is not relevant. The fluorophore and electron acceptor is a cationic hexahelicene, whereas the quencher has either stereocentered (tryptophan) or axial (binaphthol) chirality. We found that, in all cases, the quenching dynamics are the same, within the limit of error, for different diastereomeric pairs in polar and medium-polar solvents. The same absence of chiral effect is observed for the recombination of the radical pair, which results from the quenching. Molecular dynamics simulations suggest that the distribution of inter-reactant distance is independent of the chirality of the acceptor and the donor. Close contact resulting in large electronic coupling is predicted to be possible with all diastereomeric pairs. In this case, ET is an adiabatic process, whose dynamics do no longer depend on the coupling, but are rather controlled by high-frequency intramolecular modes.

A series of ferrocenyl-containing γ-hydroxy-γ-lactam tetramates were prepared in 2-3 steps through ring opening-ring closure (RORC) process of γ-ylidene-tetronate derivatives in the presence of ferrocenyl alkylamines. The compounds were screened in vitro for their antiplasmodial activity against chloroquine-sensitive (3D7) and chloroquine-resistant (W2) clones of P. falciparum, displaying activity in the range of 0.12-100 μM, with generally good resistance index. The most active ferrocene in these series exhibited IC 50 equal to 0.09 μM (3D7) and 0.12 μM (W2). The low cytotoxicity of the ferrocenyl-containing γ-hydroxy-γ-lactam tetramates against Human Umbilical Vein Endothelial (HUVEC) cell line demonstrated selective antiparasitic activity. The redox properties of these ferrocene-derived tetramates were studied and physico-biochemical studies evidenced that these derivatives can exert potent antimalarial activities via a mechanism distinct from ferroquine., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Masson SAS. All rights reserved.)

Synthesis, electronic and structural properties of a chiral NHC bearing a N-bonded cationic [4]helicene moiety are reported. This ligand is used to construct Au I , Au III and Rh I complexes exhibiting far-red (chir)optical properties regardless of the metal.

In one pot, tertiary alkyl amines are oxidized to enamines by cationic dioxa[6]helicene, which further reacts as electrophile and oxidant to form mono or bis donor-π-acceptor coupling products. This original and convergent synthetic approach provides a strong extension of conjugation yielding chromophores that absorb intensively in far-red or NIR domains (λ max up to 791 nm) and fluoresce in the NIR as well (λ max up to 887 nm). Intense ECD properties around 790 nm with a |Δϵ| value up to 60 M -1  cm -1 are observed., (© 2021 Wiley-VCH GmbH.)

A series of water-soluble helicene dyes generating intense electrochemiluminescence (ECL) signal in physiological conditions is reported. Those species were prepared using diaza [4] and [6]helicenes as structural cores modified with sulfonate groups in various positions. Such groups improve their water solubility and can induce a red-shifted emission. Efficient ECL up to the near-infrared is achieved in water, demonstrating a viable strategy for the design of new near-infrared ECL dyes for bioassays and microscopy.

Recent studies of co-occurring reading disorder (RD) and attention deficit/hyperactivity disorder (ADHD), and co-occurring RD and language impairment (LI), support a core disability plus co-occurrence model focused on language and attention. Genetic factors have been associated with poor reading performance. However, little is known about whether different genetic variants independently contribute to RD co-occurrence subtypes. We aimed to identify subgroups of struggling readers using a latent profile analysis (LPA) in a sample of 1,432 Hispanic American and African American youth. RD classes were then tested for association with variants of READ1, a regulatory element within the candidate RD risk gene, DCDC2 . Six groups were identified in the LPA using RD designation as a known-class variable. The three RD classes identified groups of subjects with neurocognitive profiles representing RD+ADHD, specific phonological deficit RD, and RD+LI. Genetic associations across RD subtypes were investigated against functional groupings of READ1. The RU1-1 group of READ1 alleles was associated with RD cases that were marked by deficits in both processing speed and attention (RD+ADHD). The DCDC2 microdeletion that encompasses READ1 was associated with RD cases showing a phonological deficit RD profile. These findings provide evidence for differential genetic contribution to RD subtypes, and that previously implicated genetic variants for RD may share an underlying genetic architecture across population groups for reading disorder.

A series of helical tetracenes and pentacenes was synthesized from cationic [6] and [4]helicene precursors. These colorful acenes fluoresce in the far red region. While [4]helicene-based pentacenes exhibit chiroptical properties mainly in the UV region, [6]helicene-derived tetracenes show enhanced ECD in the visible range, in addition to clear CPL responses. This difference is rationalized using first principles., Competing Interests: Authors declares no conflicts of interest., (This journal is © The Royal Society of Chemistry.)

The use of electronic cigarettes (E-cigs) is rapidly increasing. The latest generation of E-cigs is highly customizable, allowing for high heating coil temperatures. The aim of this study was to assess the toxic potential of a fourth-generation E-cig. Aerosols generated from E-liquid with (24 mg/mL) and without nicotine, using a fourth-generation E-cig, were chemically analysed and compared with cigarette smoke (K3R4F). Human lung epithelial cell lines and distal lung tissue explants were exposed to E-cig vapour extract (EVE) and cigarette smoke extract for 24 hours and assessed for viability, inflammation, oxidative stress and genotoxicity. E-cig aerosols contained measurable levels of volatile organic compounds, aldehydes and polycyclic aromatic hydrocarbons, in general, to a much lesser extent than cigarette smoke. Higher levels of certain carbonyls, e.g. formaldehyde, were detected in the E-cig aerosols. EVEs decreased cell viability of BEAS-2B cells, whereas little effect was seen in A549 cells and distal lung tissue. The nicotine-containing EVE caused a greater decrease in cell viability and significant increase in DNA damage than the nicotine-free EVE. Increased cytotoxicity, reactive oxygen species production and genotoxicity were seen with cells and tissue exposed to cigarette smoke extract compared with EVEs. Although E-cig aerosols were less toxic than cigarette smoke, it was not benign. Moreover, the EVE containing nicotine was more toxic than the nicotine-free EVE. More research is needed on the short- and long-term health effects of vaping and the usage of newly emerging E-cig devices to evaluate better the potential negative effects of E-cigs on human health., (© 2019 John Wiley & Sons, Ltd.)

Background: Rapid automatised naming (RAN) and rapid alternating stimulus (RAS) are reliable predictors of reading disability. The underlying biology of reading disability is poorly understood. However, the high correlation among RAN, RAS and reading could be attributable to shared genetic factors that contribute to common biological mechanisms., Objective: To identify shared genetic factors that contribute to RAN and RAS performance using a multivariate approach., Methods: We conducted a multivariate genome-wide association analysis of RAN Objects, RAN Letters and RAS Letters/Numbers in a sample of 1331 Hispanic American and African-American youth. Follow-up neuroimaging genetic analysis of cortical regions associated with reading ability in an independent sample and epigenetic examination of extant data predicting tissue-specific functionality in the brain were also conducted., Results: Genome-wide significant effects were observed at rs1555839 (p=4.03×10 -8 ) and replicated in an independent sample of 318 children of European ancestry. Epigenetic analysis and chromatin state models of the implicated 70 kb region of 10q23.31 support active transcription of the gene RNLS in the brain, which encodes a catecholamine metabolising protein. Chromatin contact maps of adult hippocampal tissue indicate a potential enhancer-promoter interaction regulating RNLS expression. Neuroimaging genetic analysis in an independent, multiethnic sample (n=690) showed that rs1555839 is associated with structural variation in the right inferior parietal lobule., Conclusion: This study provides support for a novel trait locus at chromosome 10q23.31 and proposes a potential gene-brain-behaviour relationship for targeted future functional analysis to understand underlying biological mechanisms for reading disability., Competing Interests: Competing interests: None declared., (© Author(s) (or their employer(s)) 2019. Re-use permitted under CC BY-NC. No commercial re-use. See rights and permissions. Published by BMJ.)

Oxygen atoms of cationic dioxa and azaoxa [6]helicenes can be exchanged by amino groups to form azaoxa and diaza [6]helicenes respectively. The mild reaction conditions developed herein allow the construction of libraries of derivatives with sensitive and/or functionalized side chains. Using enantioenriched dioxa or azaoxa helicene precursors, these exchanges lead to either near racemization (es 3%) or to a remarkable enantiospecificity (es up to 97%). This unusual behavior is fully characterized via experimental and computational mechanistic evidence. Based on these investigations, the enantiospecificity of the first transformation can be improved to 57-61%., (This journal is © The Royal Society of Chemistry 2019.)

The causes that individuals attribute to reading outcomes shape future behaviors, including engagement or persistence with learning tasks. Although previous reading motivation research has examined differences between typical and struggling readers, there may be unique dynamics related to varying levels of reading and attention skills. Using latent profile analysis, we found 4 groups informed by internal attributions to ability and effort. Reading skills, inattention, and hyperactivity/impulsivity were investigated as functional correlates of attribution profiles. Participants were 1,312 youth (8-15 years of age) of predominantly African American and Hispanic racial/ethnic heritage. More adaptive attribution profiles had greater reading performance and lower inattention. The reverse was found for the least adaptive profile with associations to greater reading and attention difficulties. Distinct attribution profiles also existed across similar-achieving groups. Understanding reading-related attributions may inform instructional efforts in reading. Promoting adaptive attributions may foster engagement with texts despite learning difficulties and, in turn, support reading achievement., Competing Interests: Disclosure statement No potential conflict of interest was reported by the authors.

Children with poor reading comprehension despite typical word reading skills were examined using neuropsychological, genetic, and neuroimaging data collected from the Genes, Reading and Dyslexia Study of 1432 Hispanic American and African American children. This unexpected poor comprehension was associated with profound deficits in vocabulary, when compared to children with comprehension skills consistent with their word reading. Those with specific comprehension difficulties were also more likely to have RU2Short alleles of READ1 regulatory variants of DCDC2 , strongly associated with reading and language difficulties. Subjects with RU2Short alleles showed stronger resting state functional connectivity between the right insula/inferior frontal gyrus and the right supramarginal gyrus, even after controlling for potentially confounding variables including genetic ancestry and socioeconomic status. This multi-disciplinary approach advances the current understanding of specific reading comprehension difficulties, and suggests the need for interventions that are more appropriately tailored to the specific comprehension deficits of this group of children., Competing Interests: Yale University has applied for a patent covering the complex tandem repeat and microdeletion in READ1, also known as BV677278 (Inventor: J.R.G.). The remaining authors declare no competing interests.

The causal attributions that children make for success and failure have been associated with later reading motivation and ability perceptions, which have the potential to impact future task engagement. Few studies have investigated whether such attributions are domain specific, that is linked with the specific skill in question, or a general motivational set. Even fewer studies have examined these relationships among diverse racial and ethnic subgroups. The present study examined differences in success and failure attributions among children with and without reading delay (RD) and general language impairments (LI), in a predominately Hispanic and African American sample. Participants were 1311 children, 8 to 15 years old. Significant differences in ability attributions were observed between participants with and without RD and LI, with no additive effect for cases with co-occurring reading and language impairments. When reading and vocabulary were evaluated continuously, significant and substantial positive relationships were observed between skill and ability attributions in situations of success, and negative associations observed in situations of failure. Weaker relationships were observed for vocabulary, though vocabulary did function as a moderator in the relationship between reading skill and ability attributions, with stronger associations at higher vocabulary levels. Overall, the findings suggest that ability attributions for reading success and failure are linked with reading skill and/or deficits, and not with general language impairments.

Introduction: The use of Swedish oral moist snuff, known as snus, has for a long time been limited to the Scandinavian countries. With declining cigarette sales in the western world, tobacco companies have looked to the development of alternative tobacco products. In 2006 snus products were launched in the US. Even though several studies have demonstrated negative health effects, snus is often depicted as harmless. The aim of the present study was to investigate acute vascular effects of snus as measured by arterial stiffness as well as blood pressure and heart rate., Methods: Two separate randomized double-blind crossover studies with the same study design were pooled for analysis. Twenty-nine healthy snus-users (17 females, 12 males) were included. Snus (Göteborgs Rapé) and tobacco free snus (Onico) were administered in a randomized order at two separate visits. Arterial stiffness, blood pressure and heart rate were measured at baseline as well as every five minutes for 40 minutes during exposure. Following snus removal, measurements continued for 30 minutes post exposure. Arterial stiffness was measured using pulse wave velocity (Vicorder) and pulse wave analysis (Sphygmocor)., Results: Compared to placebo, snus significantly increased systolic and diastolic blood pressure as well as heart rate, however, only in females (p = 0.004, p = 0.006 and p<0.001 respectively). No changes were seen in arterial stiffness measurements in either gender., Conclusion: We observed an increase in blood pressure and heart rate only in females, but not in males due to snus usage as compared to placebo. This novel finding was surprising and needs to be further investigated considering most of the earlier studies have mainly focused on male snus users and the increasing usage of snus among females.

Twelve cationic helicenes and one triangulene were tested for the specific labeling of mitochondria from algal cells. Octyl ester derivative 5 readily penetrates algal cells and gives rise to clear fluorescence patterns when it is used at concentrations in the μM range. Under these conditions, cell structures are well preserved and cell survival is not compromised. Cationic helicene compounds such as 5 provide new useful tools for examining the mitochondrial network and its dynamics including fission and fusion events.

The present study investigated the relation among reading skills and attributions, naming speed, and phonological awareness across a wide range of reading skill. Participants were 1,105 school-age children and youths from two understudied populations: African Americans and Hispanic Americans. Individual assessments of children ranging in age from 8 to 15 years were conducted for reading outcomes, cognitive and linguistic predictors of reading, and attributions for success and failure in reading situations. Quantile regressions were formulated to estimate these relations across the full skill span of each outcome. Reading-related attributions predicted contextual word recognition, sight word and decoding fluency, and comprehension skills. Attributions to ability in success situations were positively related to each outcome across the full span. On three reading outcomes, this relation strengthened at higher skill levels. Attributions to effort in success situations were consistently and negatively related to all reading outcomes. The results provide evidence that the strength of the relation between reading and attributions varies according to reading skill levels, with the strongest evidence for ability-based attributions in situations of reading success.

A strategy for late-stage electrophilic functionalizations of cationic helicenes is exposed. Thanks to strongly acidic conditions that permit reversible electrophilic substitutions, regioselective acylations, sulfonylations, or alkylations occur at the extremity(ies) of the helical cores. Extended [5] or [6]helicenes can then be generated from cationic [4]helicenes in successive one-pot elongation processes. Retention of configuration and excellent enantiospecificity (up to 99 %) are observed for the helicene growth in the enantiopure series., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Competent reading requires various skills beyond those for basic word reading (i.e., core language skills, rapid naming, phonological processing). Contributing "higher-level" or domain-general processes include information processing speed and executive functions (working memory, strategic problem solving, attentional switching). Research in this area has relied on largely Caucasian samples, with limited representation of children from racial or ethnic minority groups. This study examined contributions of executive skills to reading competence in 761 children of minority backgrounds. Hierarchical linear regressions examined unique contributions of executive functions (EF) to word reading, fluency, and comprehension. EF contributed uniquely to reading performance, over and above reading-related language skills; working memory contributed uniquely to all components of reading; while attentional switching, but not problem solving, contributed to isolated and contextual word reading and reading fluency. Problem solving uniquely predicted comprehension, suggesting that this skill may be especially important for reading comprehension in minority youth. Attentional switching may play a unique role in development of reading fluency in minority youth, perhaps as a result of the increased demand for switching between spoken versus written dialects. Findings have implications for educational and clinical practice with regard to reading instruction, remedial reading intervention, and assessment of individuals with reading difficulty.

The physicochemical properties of cationic dioxa (1), azaoxa (2), and diaza (3) [6]helicenes demonstrate a much higher chemical stability of the diaza adduct 3 (pK R+ =20.4, Ered1/2 =-0.72 V) compared to its azaoxa 2 (pK R+ =15.2, Ered1/2 =-0.45 V) and dioxa 1 (pK R+ =8.8, Ered1/2 =-0.12 V) analogues. The fluorescence of these cationic chromophores is established, and ranges from the orange to the far-red regions. From 1 to 3, a bathochromic shift of the lowest energy transitions (up to 614 nm in acetonitrile) and an enhancement of the fluorescence quantum yields and lifetimes (up to 31 % and 9.8 ns, respectively, at 658 nm) are observed. The triplet quantum yields and circularly polarized luminescence are also reported. Finally, fine tuning of the optical properties of the diaza [6]helicene core is achieved through selective and orthogonal post-functionalization reactions (12 examples, compounds 4-15). The electronic absorption is modulated from the orange to the far-red spectral range (560-731 nm), and fluorescence is observed from 591 to 755 nm with enhanced quantum efficiency up to 70 % (619 nm). The influence of the peripheral auxochrome substituents is rationalized by first-principles calculations., (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

In this Letter we report on an efficient and short 2-3 steps synthesis of γ-hydroxy-γ-lactam derived-tetramates bearing a 7-chloro-4-aminoquinoline skeleton and their evaluation as potent antimalarials. These molecules were obtained through ring opening-ring closure (RORC) process of γ-ylidene-tetronate derivatives in the presence of 7-chloro-4-aminoquinoline-derived amines. In vitro antimalarial activity of these new γ-lactams was evaluated against Plasmodium falciparum clones of variable sensitivity (3D7 and W2) and they were found to be active in the range of 14-827nM with generally good resistance index. A preliminary SAR study is also presented to explain these results. Finally, the most active compounds did not show in vitro cytotoxicity when tested against Human Umbilical Vein Endothelial Cells (HUVEC) up to concentration of 50μM and they were stable at pH 7.4 for at least 48h., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Cationic hetero[6]helicenes 1+, 2+ and 3+ have been recently disclosed. Herein we report on their enantiomeric separation using high-performance liquid chromatography. Separation of the antipodes can be achieved in preparative scale on neutral adducts with Chiralcel OD-I or Chiralpak ID CSP. Selectivity factors of 1.90, 1.67, and 1.96 were obtained for 1-H, 2-H, and 3-H, respectively. Separation can also be performed on the carbenium ions on regular Chiralpak IA CSP using water-containing eluents, thus allowing for enantiomeric purity determinations in aqueous environments. Resolution of neutral and cationic helicenes is also achieved on more recently developed LARIHC columns. The versatility of the cyclofructan phases allows for baseline separations for both cases and their loading capabilities are demonstrated. Finally, the configurational stability of 1+, 2+, and 3+ was measured. For each replacement of an oxygen atom by an amino group, the racemization barrier increases significantly (ΔG‡ = 29.8, 36.3 and >37 kcal mol(-1) for 1+, 2+, and 3+ respectively)., (© 2016 Wiley Periodicals, Inc.)

Trianguleniums are fascinating conjugated hexacyclic cations that exhibit interesting electronic and optical properties. Herein, the electrogenerated chemiluminescence (ECL) emission of this family of fluorescent dyes is reported for the first time. Redox behavior and fluorescence properties of eight cationic triangulene luminophores with different heteroatom patterns in the core structure and various pending substituents were examined to rationalize the ECL. Clearly, the more electron-rich the carbocation, the more efficient the corresponding ECL; two very distinct classes of triangulenes can be drawn from these studies by using an ECL wall sufficiency formalism., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We report on the use of an alkoxyamine (AA) for fabrication of functional micropatterns with complex structures by UV mask lithography. The living character of the polymer surface and the vertical spatial control of the repolymerization reaction from few tens of nanometers to few micrometers were demonstrated. The impact of the main parameters governing the controlled polymerization and the reinitiation process activated by light or heat was investigated. Micropatterning is shown to be a powerful method to investigate the physicochemical molecular phenomena. It is possible to control the polymer microstructure thickness from few tens of nanometers to few micrometers. In the last section, some applications are provided showing the potential of the AA for generating covalently bonded hydrophilic/hydrophobic micropatterns or luminescent surfaces. This demonstrates the high versatility and interest of this route.

Cationic triangulenes and helicenes are highly stable carbocations with planar and helical conformations respectively. These moieties are effective dyes with original absorption and emission properties. Over the last decade, they have received greater attention and are considered as valuable tools for the development of innovative applications. In this review, the synthesis of these unique compounds is presented together with their core chemical and physical properties. Representative applications spanning from surface sciences to biology and chemistry are presented.

Background: Diesel exhaust inhalation causes cardiovascular dysfunction including impaired vascular reactivity, increased blood pressure, and arterial stiffness. We investigated the role of nitric oxide (NO) bioavailability in mediating these effects., Methods and Results: In 2 randomized double-blind crossover studies, healthy nonsmokers were exposed to diesel exhaust or filtered air. Study 1: Bilateral forearm blood flow was measured during intrabrachial infusions of acetylcholine (ACh; 5 to 20 μg/min) and sodium nitroprusside (SNP; 2 to 8 μg/min) in the presence of the NO clamp (NO synthase inhibitor N(G)-monomethyl-l-arginine (l-NMMA) 8 μg/min coinfused with the NO donor SNP at 90 to 540 ng/min to restore basal blood flow). Study 2: Blood pressure, arterial stiffness, and cardiac output were measured during systemic NO synthase inhibition with intravenous l-NMMA (3 mg/kg). Following diesel exhaust inhalation, plasma nitrite concentrations were increased (68±48 versus 41±32 nmol/L; P=0.006) despite similar l-NMMA-induced reductions in basal blood flow (-20.6±14.7% versus -21.1±14.6%; P=0.559) compared to air. In the presence of the NO clamp, ACh and SNP caused dose-dependent vasodilatation that was not affected by diesel exhaust inhalation (P>0.05 for both). Following exposure to diesel exhaust, l-NMMA caused a greater increase in blood pressure (P=0.048) and central arterial stiffness (P=0.007), but reductions in cardiac output and increases in systemic vascular resistance (P>0.05 for both) were similar to those seen with filtered air., Conclusions: Diesel exhaust inhalation disturbs normal vascular homeostasis with enhanced NO generation unable to compensate for excess consumption. We suggest the adverse cardiovascular effects of air pollution are, in part, mediated through reduced NO bioavailability., Clinical Trial Registration: URL: http://www.ClinicalTrials.gov. Unique identifiers: NCT00845767 and NCT01060930.

Miniature optical components at the wavelength scale remain today a theoretically opened challenging problem of great technological interest. Appart from refractive micro-optics, plasmonics have been proposed to realize micro lenses with properly designed planar metallic nano-patterns. We show in this paper that efficient light focusing at the diffraction limit with higher transmission can be obtained with micro-structures much easier to fabricate than nano ones, such as a simple micro-slit studied here as an example. Optical properties are attributed to diffraction and a quantitative excellent agreement between experiment and theory is obtained.

Air pollution is now recognized as an important independent risk factor for cardiovascular morbidity and mortality and may be responsible for up to 3 million premature deaths each year worldwide. The mechanisms underlying the observed effects are poorly understood but are likely to be multifactorial. Here, we review the acute and chronic effects of air pollution exposure on the cardiovascular system and discuss how these effects may explain the observed increases in cardiovascular morbidity and mortality., (© 2012 The Association for the Publication of the Journal of Internal Medicine.)

We theoretically and experimentally demonstrate that the diffraction of microstructures based on silver nanowires leads to very efficient microfocusing effects. Pairs of parallel nanowires act as ultrasmall cylindrical microlenses with diffraction-limited resolution in the Fresnel region. This is a new diffraction scheme to make micron-sized optical lenses with higher transmittance than plasmonic microlens based on nano-aperture arrays. Calculations based on the scalar Rayleigh-Sommerfeld integral highlights the pure scalar diffractive contribution. Thus, the plasmon contribution is negligible in such micron-sized metallic geometry. We demonstrate that two-dimensional grids of nanowires can be used to fabricate dense arrays of microlenses, i.e. 10000x10000 DPI (dots per inch).

Visual cortical surface area varies two- to threefold between human individuals, is highly heritable, and has been correlated with visual acuity and visual perception. However, it is still largely unknown what specific genetic and environmental factors contribute to normal variation in the area of visual cortex. To identify SNPs associated with the proportional surface area of visual cortex, we performed a genome-wide association study followed by replication in two independent cohorts. We identified one SNP (rs6116869) that replicated in both cohorts and had genome-wide significant association (P(combined) = 3.2 × 10(-8)). Furthermore, a metaanalysis of imputed SNPs in this genomic region identified a more significantly associated SNP (rs238295; P = 6.5 × 10(-9)) that was in strong linkage disequilibrium with rs6116869. These SNPs are located within 4 kb of the 5' UTR of GPCPD1, glycerophosphocholine phosphodiesterase GDE1 homolog (Saccharomyces cerevisiae), which in humans, is more highly expressed in occipital cortex compared with the remainder of cortex than 99.9% of genes genome-wide. Based on these findings, we conclude that this common genetic variation contributes to the proportional area of human visual cortex. We suggest that identifying genes that contribute to normal cortical architecture provides a first step to understanding genetic mechanisms that underlie visual perception.

The use of a versatile N-heterocyclic carbene (NHC) gold(I) hydroxide precatalyst, [Au(OH)(IPr)], (IPr=N,N'-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) permits the in situ generation of the [Au(IPr)](+) ion by simple addition of a Brønsted acid. This cationic entity is believed to be the active species in numerous catalytic reactions. (1)H NMR studies in several solvent media of the in situ generation of this [Au(IPr)](+) ion also reveal the formation of a dinuclear gold hydroxide intermediate [{Au(IPr)}(2)(μ-OH)], which is fully characterized and was tested in gold(I) catalysis.

Experimental and computational analyses provide support for the existence of a metal-hydride-based mechanism for the ruthenium-mediated racemization of chiral alcohols.

Background: Biomass combustion contributes to the production of ambient particulate matter (PM) in rural environments as well as urban settings, but relatively little is known about the health effects of these emissions. The aim of this study was therefore to characterize airway responses in humans exposed to wood smoke PM under controlled conditions. Nineteen healthy volunteers were exposed to both wood smoke, at a particulate matter (PM2.5) concentration of 224 ± 22 μg/m3, and filtered air for three hours with intermittent exercise. The wood smoke was generated employing an experimental set-up with an adjustable wood pellet boiler system under incomplete combustion. Symptoms, lung function, and exhaled NO were measured over exposures, with bronchoscopy performed 24 h post-exposure for characterisation of airway inflammatory and antioxidant responses in airway lavages., Results: Glutathione (GSH) concentrations were enhanced in bronchoalveolar lavage (BAL) after wood smoke exposure vs. air (p = 0.025), together with an increase in upper airway symptoms. Neither lung function, exhaled NO nor systemic nor airway inflammatory parameters in BAL and bronchial mucosal biopsies were significantly affected., Conclusions: Exposure of healthy subjects to wood smoke, derived from an experimental wood pellet boiler operating under incomplete combustion conditions with PM emissions dominated by organic matter, caused an increase in mucosal symptoms and GSH in the alveolar respiratory tract lining fluids but no acute airway inflammatory responses. We contend that this response reflects a mobilisation of GSH to the air-lung interface, consistent with a protective adaptation to the investigated wood smoke exposure.

The activity of well-defined 16-electron ruthenium complexes bearing an N-heterocyclic carbene ligand in the racemization of chiral alcohols is reported. Mechanistic considerations are also presented.

The gold/silver-cocatalyzed conversion of aldoximes into primary amides is reported. The reaction, which proceeds under neat and acid-free conditions, allows for the conversion of a range of aldoximes, and is a rare example of cooperative catalysis involving well-defined gold species.