Understanding the twist-bend nematic phase: the characterisation of 1-(4-cyanobiphenyl-4'-yloxy)-6-(4-cyanobiphenyl-4'--yl)hexane (CB6OCB) and comparison with CB7CB

The synthesis and characterisation of the nonsymmetric liquid crystal dimer, 1-(4-cyanobiphenyl-40-yloxy)-6- (4-cyanobiphenyl-40-yl)hexane (CB6OCB) is reported. An enantiotropic nematic (N)–twist-bend nematic (NTB) phase transition is observed at 109 1C and a nematic–isotropic phase transition at 153 1C. The NTB phase assignment has been confirmed using polarised light microscopy, freeze fracture transmission electron microscopy (FFTEM), 2H-NMR spectroscopy, and X-ray diffraction. The effective molecular length in both the NTB and N phases indicates a locally intercalated arrangement of the molecules, and the helicoidal pitch length in the NTB phase is estimated to be 8.9 nm. The surface anchoring properties of CB6OCB on a number of aligning layers is reported. A Landau model is applied to describe high-resolution heat capacity measurements in the vicinity of the NTB–N phase transition. Both the theory and heat capacity measurements agree with a very weak first-order phase transition. A complementary extended molecular field theory was found to be in suggestive accord with the 2H-NMR studies of CB6OCB-d2, and those already known for CB7CB-d4. These include the reduced transition temperature, TNTBN/TNI, the order parameter of the mesogenic arms in the N phase close to the NTB–N transition, and the order parameter with respect to the helix axis which is related to the conical angle for the NTB phase.Postprint (published version

Distinctive dielectric properties of nematic liquid crystal dimers

We provide an overview of the effect of the molecular structure on the dielectric properties of dimers exhibiting nematic and twist-bend nematic phases with special focus on how the conformational distribution changes are reflected by the dielectric behaviour. Nematic dimers show distinctive dielectric properties which differ from those of archetypical nematic liquid crystals, as for example, unusual temperature dependence of the static permittivity or dielectric spectra characterised by two low-frequency relaxation processes with correlated strengths. The interpretation of such characteristic behaviour requires that account is taken of the effect of molecular flexibility on the energetically favoured molecular shapes. The anisotropic nematic interactions greatly influence the conformational distribution. Dielectric behaviour can be used to track those conformational changes due to dependence of the averaged molecular dipole moment on the averaged molecular shape. Results for a number of dimers are compared and analysed on the basis of the influence of details of the molecular structure, using a recently developed theory for the dielectric properties of dimers.Postprint (author's final draft

Glass-Transition Dynamics of Mixtures of Linear Poly(Vinyl Methyl Ether) with Single-Chain Polymer Nanoparticles: Evidence of a New Type of Nanocomposite Materials

Single-chain polymer nanoparticles (SCNPs) obtained through chain collapse by intramolecular cross-linking are attracting increasing interest as components of all-polymer nanocomposites, among other applications. We present a dielectric relaxation study on the dynamics of mixtures of poly(vinyl methyl ether) (PVME) and polystyrene (PS)-based SCNPs with various compositions. Analogous dielectric measurements on a miscible blend of PVME with the linear precursor chains of the SCNPs are taken as reference for this study. Both systems present completely different behaviors: While the blend with the linear precursor presents dynamics very similar to that reported for PVME/PS miscible blends, in the PVME/SCNP mixtures there are an appreciable amount of PVME segments that are barely affected by the presence of SCNPs, which nearly vanishes only for mixtures with high SCNP content. Interestingly, in the frame of a simple two-phase system, our findings point towards the existence of a SCNP-rich phase with a constant PVME fraction, regardless of the overall concentration of the mixture. Moreover, the dynamics of the PVME segments in this SCNP-rich phase display an extreme dynamic heterogeneity, a signature of constraint effects.This research was funded by Eusko Jaurlaritza project code: IT-654-13 and the Ministerio de Economia y Competitividad project code: MAT2015-63704-P (MINECO/FEDER, UE)

Broadband Dielectric Spectroscopy Study of Biobased Poly(alkylene 2,5-furanoate)s’ Molecular Dynamics

Abstract Poly(2,5-alkylene furanoate)s are bio-based, smart, and innovative polymers that are considered the most promising materials to replace oil-based plastics. These polymers can be synthesized using ecofriendly approaches, starting from renewable sources, and result into final products with properties comparable and even better than those presented by their terephthalic counterparts. In this work, we present the molecular dynamics of four 100% bio-based poly(alkylene 2,5-furanoate)s, using broadband dielectric spectroscopy measurements that covered a wide temperature and frequency range. We unveiled complex local relaxations, characterized by the simultaneous presence of two components, which were dependent on thermal treatment. The segmental relaxation showed relaxation times and strengths depending on the glycolic subunit length, which were furthermore confirmed by high-frequency experiments in the molten region of the polymers. Our results allowed determining structure–property relations that are able to provide further understanding about the excellent barrier properties of poly(alkylene 2,5-furanoate)s. In addition, we provide results of high industrial interest during polymer processing for possible industrial applications of poly(alkylene furanoate)s.This research was funded by the European Union: EUSMI, H2020-INFRAIA-2016-1, PROJECT 731019, via proposals E171100043 and E171100040. The APC was funded by EUSMI. B.R.-H. and A.A. acknowledge funding from Basque Government (IT-1175-19). D.E.M.-T. acknowledges financial support via the postdoctoral fellowship “Juan de la Cierva–Incorporación” grant (IJCI-2017-31600, MCIU–Spain). G.G., M.S. and N.L. and A.M. acknowledge financial support via the framework COST Action FUR4Sustain, CA18220, supported by COST (European Cooperation in Science and Technology)

Miscibility studies of two twist-bend nematic liquid crystal dimers with different average molecular curvatures. A comparison between experimental data and predictions of a Landau mean-field theory for the NTB-N phase transition

We report a calorimetric study of a series of mixtures of two twist-bend liquid crystal dimers, the 1'',7''-bis(4-cyanobiphenyl)-4'-yl heptane (CB7CB) and 1''-(2',4-difluorobiphenyl-4'-yloxy)-9''-(4-cyanobiphenyl-4'-yloxy) nonane (FFO9OCB), the molecules of which have different effective molecular curvatures. High-resolution heat capacity measurements in the vicinity of the NTB-N phase transition for a selected number of binary mixtures clearly indicate a first order NTB-N phase transition for all the investigated mixtures, the strength of which decreases when the nematic range increases. Published theories predict a second order NTB-N phase transition, but we have developed a self-consistent mean field Landau model using two key order parameters: A symmetric and traceless tensor for the orientational order and a short-range vector field which is orthogonal to the helix axis and rotates around of the heliconical structure with an extremely short periodicity. The theory, in its simplified form, depends on two effective elastic constants and explains satisfactorily our heat capacity measurements and also predicts a first-order NTB-N phase transition. In addition, as a complementary source of experimental measurements, the splay (K1) and bend (K3) elastic constants in the conventional nematic phase for the pure compounds and some selected mixtures have been determined.Postprint (author's final draft

ENTRENAMIENTO CONDUCTUAL EN HABILIDADES DE COMUNICACIÓN SEXUAL EN LA PAREJA Y USO CORRECTO DEL CONDÓN

This study assessed the effects of sexual communication and condom use skills training on 50 sexually active college students’ consistent condom use. In vivo sexual communication and condom use skills postintervention assessments showed that intervention group participants acquired the skills trained and were significantly better than control group participant in openly talking about sex (pEl presente estudio evalúa los efectos de un entrenamiento conductual en habilidades de comunicación sexual en la pareja y uso correcto del condón sobre la consistencia en el uso del condón en una muestra de 50 estudiantes universitarios sexualmente activos. En la postevaluación de las variables medidas a través de la observación directa se encontró una ejecución significativamente más alta en el grupo de intervención que la obtenida en el grupo control en la habilidad para iniciar y mantener una conversación sobre sexualidad (

Twist, tilt, and orientational order at the nematic to twist-bend nematic phase transition of 1 '',9 ''-bis(4-cyanobiphenyl-4 '-yl) nonane: A dielectric, H-2 NMR, and calorimetric study

The nature of the nematic-nematic phase transition in the liquid crystal dimer 1 '',9 ''-bis(4-cyanobiphenyl-4'-yl) nonane (CB9CB) has been investigated using techniques of calorimetry, dynamic dielectric response measurements, and H-2 NMR spectroscopy. The experimental results for CB9CB show that, like the shorter homologue CB7CB, the studied material exhibits a normal nematic phase, which on cooling undergoes a transition to the twist-bend nematic phase (N-TB), a uniaxial nematic phase, promoted by the average bent molecular shape, in which the director tilts and precesses describing a conical helix. Modulated differential scanning calorimetry has been used to analyze the nature of the N-TB-N phase transition, which is found to be weakly first order, but close to tricritical. Additionally broadband dielectric spectroscopy and H-2 magnetic resonance studies have revealed information on the structural characteristics of the recently discovered twist-bend nematic phase. Analysis of the dynamic dielectric response in both nematic phases has provided an estimate of the conical angle of the heliconical structure for the N-TB phase. Capacitance measurements of the electric-field realignment of the director in initially planar aligned cells have yielded values for the splay and bend elastic constants in the high temperature nematic phase. The bend elastic constant is small and decreases with decreasing temperature as the twist-bend phase is approached. This behavior is expected theoretically and has been observed in materials that form the twist-bend nematic phase. H-2 NMR measurements characterize the chiral helical twist identified in the twist-bend nematic phase and also allow the determination of the temperature dependence of the conical angle and the orientational order parameter with respect to the director.Postprint (author's final draft

Mammographic density and breast cancer in women from high risk families

Introduction: Mammographic density (MD) is one of the strongest determinants of sporadic breast cancer (BC). In this study, we compared MD in BRCA1/2 mutation carriers and non-carriers from BRCA1/2 mutation-positive families and investigated the association between MD and BC among BRCA1/2 mutation carriers per type of mutation and tumor subtype. Methods: The study was carried out in 1039 female members of BRCA1 and BRCA2 mutation-positive families followed at 16 Spanish Genetic Counseling Units. Participants' density was scored retrospectively from available mammograms by a single blinded radiologist using a 5-category scale (75 %). In BC cases, we selected mammograms taken prior to diagnosis or from the contralateral breast, whereas, in non-cases, the last screening mammogram was evaluated. MD distribution in carriers and non-carriers was compared using ordinal logistic models, and the association between MD and BC in BRCA1/2 mutation carriers was studied using logistic regression. Huber-White robust estimators of variance were used to take into account correlations between family members. A similar multinomial model was used to explore this association by BC subtype. Results: We identified and scored mammograms from 341 BRCA1, 350 BRCA2 mutation carriers and 229 non-carriers. Compared to non-carriers, MD was significantly lower among BRCA2 mutation carriers (odds ratio (OR) =0.71; P-value=0.04), but not among BRCA1 carriers (OR=0.84; P-value=0.33). MD was associated with subsequent development BC (OR per category of MD=1.45; 95 % confidence interval=1.18-1.78, P-value<0.001), with no significant differences between BRCA1 and BRCA2 mutation carriers (P-value=0.48). Finally, no statistically significant differences were observed in the association of MD with specific BC subtypes. Conclusions: Our study, the largest to date on this issue, confirms that MD is an independent risk factor for all BC subtypes in either BRCA1 and BRCA2 mutation carriers, and should be considered a phenotype risk marker in this context