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1.
J Pediatr ; 257: 113348, 2023 06.
Artículo en Inglés | MEDLINE | ID: mdl-36801212

RESUMEN

OBJECTIVES: To determine the incidence of seizure-like events in a cohort of infants born preterm as well as the prevalence of associated vital sign changes (heart rate [HR], respiratory rate, and pulse oximetry [SpO2]). STUDY DESIGN: We performed prospective conventional video electroencephalogram monitoring on infants born at 23-30 weeks of gestational age during the first 4 postnatal days. For detected seizure-like events, simultaneously captured vital sign data were analyzed during the pre-event baseline and during the event. Significant vital sign changes were defined as HR or respiratory rate >±2 SD from the infant's own baseline physiologic mean, derived from a 10-minute interval before the seizure-like event. Significant change in SpO2 was defined as oxygen desaturation during the event with a mean SpO2 <88%. RESULTS: Our sample included 48 infants with median gestational age of 28 weeks (IQR 26-29) and birth weight of 1125 g (IQR 963-1265). Twelve (25%) infants had seizure-like discharges with a total of 201 events; 83% (10/12) of infants had vital sign changes during these events, and 50% (6/12) had significant vital sign changes during the majority of the seizure-like events. Concurrent HR changes occurred the most frequently. CONCLUSIONS: Individual infant variability was observed in the prevalence of concurrent vital sign changes with electroencephalographic seizure-like events. Physiologic changes associated with preterm electrographic seizure-like events should be investigated further as a potential biomarker to assess the clinical significance of such events in the preterm population.


Asunto(s)
Oximetría , Convulsiones , Recién Nacido , Humanos , Lactante , Estudios Prospectivos , Edad Gestacional , Convulsiones/diagnóstico , Convulsiones/epidemiología , Peso al Nacer , Oxígeno
2.
Chirality ; 35(7): 418-426, 2023 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-36932926

RESUMEN

A great proportion of molecular crystals can be made to grow as twisted fibrils. Typically, this requires high crystallization driving forces that lead to spherulitic textures. Here, it is shown how micron size channels fabricated from poly(dimethylsiloxane) (PDMS) serve to collimate the circular polycrystalline growth fronts of optically banded spherulites of twisted crystals of three compounds, coumarin, 2,5-bis(3-dodecyl-2-thienyl)-thiazolo[5,4-d]thiazole, and tetrathiafulvalene. The relationships between helicoidal pitch, growth front coherence, and channel width are measured. As channels spill into open spaces, collimated crystals "diffract" via small angle branching. On the other hand, crystals grown together from separate channels whose bands are out of phase ultimately become a single in-phase bundle of fibrils by a cooperative mechanism yet unknown. The isolation of a single twist sense in individual channels is described. We forecast that such chiral molecular crystalline channels may function as chiral optical wave guides.

3.
Dev Psychopathol ; 35(1): 24-34, 2023 02.
Artículo en Inglés | MEDLINE | ID: mdl-36914286

RESUMEN

This study examined the intergenerational transmission of parental invalidation and whether parental difficulties in emotion regulation mediated the association between past experiences of invalidation and current invalidating parenting practices. We also aimed to investigate whether gender might influence the transmission of parental invalidation. We recruited a community sample of 293 dual-parent families (adolescent and their parents) based in Singapore. Parents and adolescents each completed measures of childhood invalidation, whereas parents additionally reported on their difficulties in emotion regulation. Results based on path analyses demonstrated that past parental invalidation experienced by fathers positively predicted current perceived invalidation by their children. The association between mothers' childhood invalidation and current invalidating practices was fully mediated by mothers' difficulties with emotion regulation. Further analyses revealed that parents' current invalidating behaviors were not predicted by their past experiences of paternal or maternal invalidation. These findings point to the importance of considering the family invalidating environment as a whole when examining the influence of past experienced parental invalidation on emotion regulation and invalidating behaviors of second-generation parents. Our study provides empirical support for the intergenerational transmission of parental invalidation and highlights the need to address childhood experiences of parental invalidation in parenting programs.


Asunto(s)
Relaciones Intergeneracionales , Relaciones Padres-Hijo , Responsabilidad Parental , Adolescente , Femenino , Humanos , Masculino , Responsabilidad Parental/psicología , Modelos Psicológicos
4.
Dev Psychopathol ; : 1-11, 2023 Sep 13.
Artículo en Inglés | MEDLINE | ID: mdl-37702069

RESUMEN

This longitudinal study aimed to validate the biosocial theory of borderline personality disorder (BPD) by examining the transactional relationship between individual vulnerabilities and parental invalidation, and their links to BPD symptoms. We recruited a sample of 332 adolescents (mean age = 14.18 years; 58.3% female) residing in Singapore and administered self-report measures across three time-points (six months apart). Results from our path analytic model indicated that parental invalidation, impulsivity, and emotional vulnerability exhibited unique predictive associations with emotion dysregulation six months later. There was also a reciprocal prospective relationship between emotion regulation difficulties and BPD symptoms. Using random-intercepts cross-lagged panel models, we found partial evidence for a within-individual reciprocal relationship between parental invalidation and emotional vulnerability, and a unidirectional relationship of within-individual changes in impulsivity positively predicting changes in parental invalidation six months later. Overall, the study provided partial empirical support for the biosocial model in a Singaporean context.

5.
Pediatr Dermatol ; 39(2): 309-311, 2022 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-34888914

RESUMEN

Bethlem myopathy is a collagen VI-related myopathy. Collagen VI is primarily not only associated with the extracellular matrix of skeletal muscle, but is also found in the skin, blood vessels, and other organs. Dermatologic findings described for Bethlem myopathy include follicular hyperkeratosis and abnormal scar formation, although clinical and histopathologic photographs remain elusive in the literature. We present a case of atypical keratosis pilaris-like follicular lesions in a patient with Bethlem myopathy and provide histopathologic correlation to better characterize the development of skin lesions in this rare neuromuscular disease.


Asunto(s)
Colágeno Tipo VI , Contractura , Anomalías Múltiples , Colágeno Tipo VI/genética , Contractura/genética , Enfermedad de Darier , Cejas/anomalías , Humanos , Músculo Esquelético/patología , Distrofias Musculares/congénito , Mutación
6.
Chem Soc Rev ; 50(17): 9375-9390, 2021 Sep 07.
Artículo en Inglés | MEDLINE | ID: mdl-34231620

RESUMEN

Solution-processable organic materials for emerging electronics can generally be divided into two classes of semiconductors, organic small molecules and polymers. The theoretical thermodynamic limits of device performance are largely determined by the molecular structure of these compounds, and advances in synthetic routes have led to significant progress in charge mobilities and light conversion and light emission efficiencies over the past several decades. Still, the uncontrolled formation of out-of-equilibrium film microstructures and unfavorable polymorphs during rapid solution processing remains a critical bottleneck facing the commercialization of these materials. This tutorial review provides an overview of the use of nanoconfining scaffolds to impose order onto solution-processed semiconducting films to overcome this limitation. For organic semiconducting small molecules and polymers, which typically exhibit strong crystal growth and charge transport anisotropy along different crystallographic directions, nanoconfining crystallization within nanopores and nanogrooves can preferentially orient the fast charge transport direction of crystals with the direction of current flow in devices. Nanoconfinement can also stabilize high-performance metastable polymorphs by shifting their relative Gibbs free energies via increasing the surface area-to-volume ratio. Promisingly, such nanoconfinement-induced improvements in film and crystal structures have been demonstrated to enhance the performance and stability of emerging optoelectronics that will enable large-scale manufacturing of flexible, lightweight displays and solar cells.

7.
Soft Matter ; 17(6): 1642-1654, 2021 Feb 19.
Artículo en Inglés | MEDLINE | ID: mdl-33367403

RESUMEN

Organic solar cells (OSCs) containing an active layer consisting of a nanostructured blend of a conjugated polymer like poly(3-hexylthiophene) (P3HT) and an electron acceptor have the potential of competing against silicon-based photovoltaic panels. However, this potential is largely unfulfilled first due to interrelated production and stability issues of organic solar cells and second due to the unscalable nature of the generally employed spin coating process used for the fabrication of organic solar cells. Furthermore, alternatives to spin coating, especially relying on continuous polymer processing methods like extrusion and coating, cannot be readily applied due to the typically low shear viscosity and elasticity of polymer solutions making up the active layer. Recently, He et al. have reported that the gelation of P3HT with [6,6]-phenyl-C61-butyric acid methyl ester (PC60BM) under sub-ambient conditions can provide a new route to the processing of the active layers of bulk heterojunction solar cells. Furthermore, increases in power conversion efficiencies (PCEs) of the P3HT/PC60BM active layer were determined to be possible under certain shearing and thermal histories of the P3HT/PC60BM gels. Here oscillatory and steady torsional flows were used to investigate the gel formation dynamics of P3HT with a recently proposed non-fullerene acceptor o-IDTBR under sub-ambient conditions and compared with the gelation behavior of P3HT/PC60BM blends. The rheological material functions as well as the gel strengths defined on the basis of linear viscoelastic material functions, characterized via small-amplitude oscillatory shearing, were observed to be functions of the P3HT and o-IDTBR concentrations, the solvent used and the shearing conditions. Overall, the P3HT gels which formed upon quenching to sub-zero temperatures were found to be stable during small-amplitude oscillatory shear (linear viscoelastic range) but broke down even at the relatively low shear rates associated with steady torsional flows, suggesting that the shearing conditions used during the processing of gels of P3HT and blends of P3HT with small molecule acceptors can alter the gel structure, possibly leading to changes in the resulting active layer performance.

8.
Soft Matter ; 17(13): 3603-3608, 2021 Apr 07.
Artículo en Inglés | MEDLINE | ID: mdl-33416826

RESUMEN

For organic semiconductor crystals exhibiting anisotropic charge transport along different crystallographic directions, nanoconfinement is a powerful strategy to control crystal orientation by aligning the fast crystallographic growth direction(s) with the unconfined axis(es) of nanoconfining scaffolds. Here, design rules are presented to relate crystal morphology, scaffold geometry, and orientation control in solution-processed small-molecule crystals. Specifically, organic semiconductor triisopropylsilylethynyl pyranthrene needle-like crystals with a dimensionality of n = 1 and perylene platelike crystals with n = 2 were grown from solution within nanoconfining scaffolds comprising cylindrical nanopores with a dimensionality of m = 1, representing one unconfined dimension along the cylinder axis, and those comprising nanopillar arrays with a dimensionality of m = 2. For m = n systems, native crystal growth habits were preserved while the crystal orientation in n = m direction(s) was dictated by the geometry of the scaffold. For n≠m systems, on the other hand, orientation control was restricted within a single plane, either parallel or perpendicular to the substrate surface. Intriguingly, control over crystal shape was also observed for perylene crystals grown in cylindrical nanopores (n > m). Within the nanopores, crystal growth was restricted along a single direction to form a needle-like morphology. Once growth proceeded above the scaffold surface, the crystals adopted their native growth habit to form asymmetric T-shaped single crystals with concave corners. These findings suggest that nanoporous scaffolds with spatially-varying dimensionalities can be used to grow single crystals of complex shapes.

9.
Nanotechnology ; 30(40): 405704, 2019 Oct 04.
Artículo en Inglés | MEDLINE | ID: mdl-31207594

RESUMEN

Au nanorods (Au NRs) are promising candidates for sensing applications due to their tunable localized surface plasmon resonance wavelength. At temperatures above 250 °C, however, these structures are morphologically unstable and tend to evaporate. We herein report a novel refractory plasmonic nanocomposite system comprising Au NRs entrapped in anodized aluminum oxide (AAO) scaffolds that are stable up to 800 °C. Au NRs were synthesized in the cylindrical pores of sapphire-supported AAO via in situ electroless deposition on catalytic Au nanoparticles (Au NPs) anchored on the pore walls. The morphological characteristics and surface-enhanced Raman scattering (SERS) functionality of Au NRs before and after heat treatment were evaluated using SEM, XRD and Raman spectroscopy. Compared to unconfined Au NRs that evolved into spherical particles at temperatures below 250 °C and subsequently evaporated from the substrate surface, the morphology of Au NRs in AAO was preserved upon heat treatment at temperatures up to 800 °C. Furthermore, by tuning the AAO scaffolds thickness and pore diameter, the aspect ratio (AR) of the entrapped Au NRs was varied from 2.4 to 7.8. The SERS sensitivity of Au NRs in AAO was found to increase with decreasing AR when the incident light was parallel to the rod longitudinal axis, in close agreement with the calculated fourth power of the local electromagnetic field using the finite-difference time domain method.

10.
Langmuir ; 34(41): 12412-12418, 2018 10 16.
Artículo en Inglés | MEDLINE | ID: mdl-30247913

RESUMEN

Aspherical cubic hematite colloids with cylindrical arms protruding from each face, referred to as "hexapods", were assembled via negative dielectrophoresis and then manipulated using an applied magnetic field. Upon application of an ac electric field, the hexapods aligned in close-packed linear chains parallel to the field direction. The chains then aggregated to the center of the device, with adjacent chains separated by distances approximately equal to twice the arm length. The resulting open packing structure exhibited cmm plane group symmetry due to the obstruction of arms, with a high density of incorporated defects. Subsequent application of a magnetic field to the dielectrophoresis (DEP)-assembled structure was found to anneal the colloidal crystal by reorienting the hexapods to align their intrinsic magnetic dipoles with the magnetic field direction. During reorganization, the colloidal packing density was found to decrease by more than 10% at both the center and edges of the crystal, accompanied by a significant loss of ordering, prior to redensification of the 2D lattice with fewer defects. Reorganization at the edge was 1.5 times faster than at the center, consistent with the need for cooperative colloidal motion to remove defects at the centers of the crystals.

12.
J Emerg Med ; 54(6): 835-843, 2018 06.
Artículo en Inglés | MEDLINE | ID: mdl-29550284

RESUMEN

BACKGROUND: Children with slipped capital femoral epiphysis (SCFE) are often seen by an array of medical professionals prior to diagnosis. Patients with mild slips, slips with knee pain, or bilateral slips can occasionally present a diagnostic challenge that increases the risk of a delay in diagnosis and associated complications. OBJECTIVES: This study introduces a new radiographic parameter, which we refer to as the S-sign, and analyzes its diagnostic utility on a frog-leg lateral radiograph. METHODS: Twenty observers reviewed the radiographs from 35 patients with SCFE using Klein's line on anteroposterior pelvis radiographs and the S-sign on frog-leg lateral radiographs to diagnose an SCFE. Analysis included diagnostic outcomes and intraobserver and interobserver reliability. RESULTS: The S-sign was more accurate at identifying an SCFE compared with Klein's line (92.4% vs. 79.2%, respectively). Sensitivity and specificity was greater for the S-sign compared with Klein's line (89.0% and 95.2% vs. 68.3% and 89.0%, respectively). A combination of the S-sign and Klein's line yielded a sensitivity of 96.5% and a specificity of 85.0%. The combination of tests was more diagnostic for an SCFE, compared with using the Klein's line, which was statistically significant (p < 0.001). CONCLUSIONS: With increased awareness of the S-sign and a usage of the combined test, clinicians can more reliably and accurately diagnose an SCFE. Clinicians are more likely to diagnose an SCFE using the combined test, compared with solely relying on Klein's line, which we found to be statistically significant.


Asunto(s)
Radiografía/métodos , Epífisis Desprendida de Cabeza Femoral/diagnóstico , Adolescente , Niño , Servicio de Urgencia en Hospital/organización & administración , Femenino , Fémur/diagnóstico por imagen , Fémur/lesiones , Humanos , Masculino , Radiografía/tendencias , Reproducibilidad de los Resultados , Estudios Retrospectivos , Sensibilidad y Especificidad , Epífisis Desprendida de Cabeza Femoral/diagnóstico por imagen
13.
Soft Matter ; 13(34): 5724-5730, 2017 Aug 30.
Artículo en Inglés | MEDLINE | ID: mdl-28758660

RESUMEN

Reversible solid-state phase transitions between open- and close-packed structures in two-dimensional colloidal crystals comprising 1.8 µm dimpled spherical colloids were observed using negative dielectrophoresis. These asymmetrically-shaped colloids adopted lattices with cmm plane group symmetry and a packing fraction, ϕ, of 0.68 at low electric field strengths. At high electric field strengths, the close-packed p6m symmetry was observed, with ϕ = 0.90. The transition between open and close-packed structures was found to be reversible, depending on the applied electric field strength and frequency. Finite Fourier transform analysis and COMSOL simulations revealed the existence of repulsive interactions between colloids perpendicular to the electric field lines due to a concentration of the electric field at the edges of the dimpled regions of the colloids. The repulsive interactions resulted in a stretching of the hexagonal lattice perpendicular to the electric field lines, the magnitude of which depended on the electric field strength. By screening the colloids from the electric field in local potential wells, the entropically favored close-packed hexagonal lattice with ϕ = 0.91 was recovered.

14.
J Pers ; 85(3): 409-422, 2017 06.
Artículo en Inglés | MEDLINE | ID: mdl-26919690

RESUMEN

The developmental trajectories of maladaptive perfectionism, along with their consequences and origins, were examined in middle childhood. A sample of Singaporean children and their parents (N = 302) were recruited for a longitudinal study when the children were 7 years old. Subsequent follow-up assessments were made at ages 8, 9, and 11. A multimethod approach was adopted where parent reports, child reports, and observational data on a dyadic interaction task were obtained. Using latent class growth modeling, four distinct classes were obtained for critical self-oriented perfectionism (SOP-C), whereas two classes emerged for socially prescribed perfectionism (SPP). Children with high and/or increasing SOP-C and SPP trajectories constituted 60% and 78% of the sample, respectively. For both SOP-C and SPP, trajectories with high initial status were associated with higher internalizing and externalizing symptoms. Parental intrusiveness and negative parenting predicted high and/or increasing SOP-C trajectories, whereas the child temperament dimension of surgency predicted high SPP trajectory. Both SOP-C and SPP trajectories tended to co-occur, suggesting a mutually reinforcing process. This study yields important findings that help advance current understanding of the emergence and developmental pathways of maladaptive perfectionism in children.


Asunto(s)
Desarrollo Infantil , Mecanismos de Defensa , Perfeccionismo , Personalidad , Niño , Femenino , Humanos , Estudios Longitudinales , Masculino , Temperamento
15.
JAMA ; 316(20): 2094-2103, 2016 Nov 22.
Artículo en Inglés | MEDLINE | ID: mdl-27893130

RESUMEN

Importance: During hospitalization for hematopoietic stem cell transplantation (HCT), patients receive high-dose chemotherapy before transplantation and experience significant physical and psychological symptoms and poor quality of life (QOL). Objective: To assess the effect of inpatient palliative care on patient- and caregiver-reported outcomes during hospitalization for HCT and 3 months after transplantation. Design, Setting, and Participants: Nonblinded randomized clinical trial among 160 adults with hematologic malignancies undergoing autologous/allogeneic HCT and their caregivers (n = 94). The study was conducted from August 2014 to January 2016 in a Boston hospital; follow-up was completed in May 2016. Interventions: Patients assigned to the intervention (n=81) were seen by palliative care clinicians at least twice a week during HCT hospitalization; the palliative intervention was focused on management of physical and psychological symptoms. Patients assigned to standard transplant care (n=79) could be seen by palliative care clinicians on request. Main Outcomes and Measures: Primary: change in patient QOL from baseline to week 2; secondary: patient-assessed mood, fatigue, and symptom burden scores at baseline, 2 weeks, and 3 months after HCT and caregiver-assessed QOL and mood at baseline and 2 weeks after HCT. Results: Among 160 enrolled patients (mean age, 60 [SD, 13.3] years; 91 women [56.9%]; median hospital stay, 21 days) and 94 caregivers, 157 (98.1%) and 89 (94.7%), respectively, completed 2-week follow-up, and 149 patients (93.1%) completed 3-month follow-up. Patients in the intervention group reported a smaller decrease in QOL from baseline to week 2 (mean baseline score, 110.26; week 2 score, 95.46; mean change, -14.72) compared with patients in the control group (mean baseline score, 106.83; week 2 score, 85.42; mean change, -21.54; difference between groups, -6.82; 95% CI, -13.48 to -0.16; P = .045). Among the secondary outcomes, from baseline to week 2, patients in the intervention group vs those in the control group had less increase in depression (mean, 2.43 vs 3.94; mean difference, 1.52; 95% CI, 0.23-2.81; P = .02), lower anxiety (mean, -0.80 vs 1.12; mean difference, 1.92; 95% CI, 0.83-3.01; P < .001), no difference in fatigue (mean, -10.30 vs -13.65; mean difference, -3.34; 95% CI, -7.25 to 0.56; P = .09), and less increase in symptom burden (mean, 17.35 vs 23.14; mean difference, 5.80; 95% CI, 0.49-11.10; P = .03). At 3 months after HCT, intervention patients vs control patients had higher QOL scores (mean, 112.00 vs 106.66; mean difference, 5.34; 95% CI, 0.04-10.65; P = .048) and less depression symptoms (mean, 3.49 vs 5.19; mean difference, -1.70; 95% CI, -2.75 to -0.65; P = .002) but no significant differences in anxiety, fatigue, or symptom burden. From baseline to week 2 after HCT, caregivers of patients in the intervention group vs caregivers of patients in the control group reported no significant differences in QOL or anxiety but had a smaller increase in depression (mean, 0.25 vs 1.80; mean difference, 1.55; 95% CI, 0.14-2.96; P = .03). Conclusions and Relevance: Among adults at a single institution undergoing HCT for hematologic malignancy, the use of inpatient palliative care compared with standard transplant care resulted in a smaller decrease in QOL 2 weeks after transplantation. Further research is needed for replication and to assess longer-term outcomes and cost implications. Trial Registration: clinicaltrials.gov Identifier: NCT02207322.


Asunto(s)
Neoplasias Hematológicas/terapia , Trasplante de Células Madre Hematopoyéticas , Cuidados Paliativos , Calidad de Vida , Adulto , Anciano , Ansiedad , Cuidadores , Depresión , Fatiga , Femenino , Trasplante de Células Madre Hematopoyéticas/efectos adversos , Trasplante de Células Madre Hematopoyéticas/métodos , Hospitalización , Humanos , Pacientes Internos , Masculino , Persona de Mediana Edad , Comodidad del Paciente , Resultado del Tratamiento
16.
Langmuir ; 31(38): 10411-7, 2015 Sep 29.
Artículo en Inglés | MEDLINE | ID: mdl-26343786

RESUMEN

Two-dimensional colloidal crystals confined within electric field traps on the surface of a dielectrophoretic cell undergo reversible phase transitions that depend on the strength of the applied AC electric field. At low field strengths, the particles adopt a two-dimensional hexagonal close-packed lattice with p6m plane group symmetry and the maximum achievable packing fraction of φ = 0.91. Higher electric field strengths induce dipoles in the particles that provoke a phase transition to structures that depend on the number of particles confined in the trap. Whereas traps containing N = 24 particles transform to a square-packed lattice with p4m symmetry and φ = 0.79 is observed, traps of the same size containing N = 23 particles can also pack in a lattice with p2 symmetry and φ = 0.66. Traps with N = 21, 22, and 25 particles exhibit a mixture of packing structures, revealing the influence of lateral compressive forces, in addition to induced dipole interactions, in stabilizing loosely packed arrangements. These observations permit construction of a phase diagram based on adjustable parameters of electric field strength (0-750 V/cm) and particle number (N = 21-25).

17.
Chem Mater ; 36(2): 881-891, 2024 Jan 23.
Artículo en Inglés | MEDLINE | ID: mdl-38282684

RESUMEN

Helicoidal crystallites in rhythmically banded spherulites manifest spectacular optical patterns in small molecules and polymers. It is shown that concentric optical bands indicating crystallographic orientations typically lose coherence (in-phase twisting) with growth from the center of nucleation. Here, coherence is shown to increase as the twist period decreases for seven molecular crystals grown from the melt. This dependence was correlated to crystallite fiber thickness and length, as well as crystallite branching frequency, a parameter that was extracted from scanning electron micrographs, and supported by numerical simulations. Hole mobilities for 2,5-didodecyl-3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (DPP-C12) measured by using organic field-effect transistors demonstrated that more incoherent boundaries between optical bands in spherulites lead to higher charge transport for films with the same twist period. This was rationalized by combining our growth model with electrodynamic simulations. This work illustrates the emergence of complexity in crystallization processes (spherulite formation) that arises in the extra variable of helicoidal radial twisting. The details of the patterns analyzed here link the added complexity in crystal growth to the electronic and optical properties of the thin films.

18.
Chem Mater ; 36(12): 5976-5985, 2024 Jun 25.
Artículo en Inglés | MEDLINE | ID: mdl-38947980

RESUMEN

A previously unreported polymorph of 5,11-bis(triisopropylsilylethynyl)anthradithiophene (TIPS ADT), Form II, crystallizes from melt-processed TIPS ADT films blended with 16 ± 1 wt % medium density polyethylene (PE). TIPS ADT/PE blends that initially are crystallized from the melt produce twisted TIPS ADT crystals of a metastable polymorph (Form IV, space group P1̅) with a brickwork packing motif distinct from the slipstack packing by solution-processed TIPS ADT crystals (Form I, space group P21/c) at room temperature. When these films were cooled to room temperature and subsequently annealed at 100 °C, near a PE melting temperature of 110 °C, Form II crystals nucleated and grew while consuming Form IV. The growth rate and orientations of Form II crystals were predetermined by the twisting pitch and growth direction of the original banded spherulites in the melt-processed films of the blends. Notably, the Form IV → II transition was not observed during thermal annealing of neat TIPS ADT films without PE. The presence of the mobile PE phase during thermal annealing of TIPS ADT/PE blend films increases the diffusion rate of TIPS ADT molecules, and the rate of nucleation of Form II. Form IV crystals are more conductive but less emissive compared to Form II crystals.

19.
Cryst Growth Des ; 24(2): 613-626, 2024 Jan 17.
Artículo en Inglés | MEDLINE | ID: mdl-38250542

RESUMEN

The performance of crystalline organic semiconductors depends on the solid-state structure, especially the orientation of the conjugated components with respect to device platforms. Often, crystals can be engineered by modifying chromophore substituents through synthesis. Meanwhile, dissymetry is necessary for high-tech applications like chiral sensing, optical telecommunications, and data storage. The synthesis of dissymmetric molecules is a labor-intensive exercise that might be undermined because common processing methods offer little control over orientation. Crystal twisting has emerged as a generalizable method for processing organic semiconductors and offers unique advantages, such as patterning of physical and chemical properties and chirality that arises from mesoscale twisting. The precession of crystal orientations can enrich performance because achiral molecules in achiral space groups suddenly become candidates for the aforementioned technologies that require dissymetry.

20.
Toxicol Appl Pharmacol ; 272(3): 852-62, 2013 Nov 01.
Artículo en Inglés | MEDLINE | ID: mdl-23899529

RESUMEN

Natural compounds containing vanilloid and Michael acceptor moieties appear to possess anti-cancer and chemopreventive properties. The ginger constituent shogaol represents one such compound. In this study, the anti-cancer potential of a synthetic novel shogaol analog 3-phenyl-3-shogaol (3-Ph-3-SG) was assessed by evaluating its effects on signaling pathways. At non-toxic concentrations, 3-Ph-3-SG suppressed cancer cell invasion in MDA-MB-231 and MCF-7 breast carcinoma cells through inhibition of PMA-activated MMP-9 expression. At similar concentrations, 3-Ph-3-SG reduced expression of the inflammatory mediators nitric oxide (NO), inducible nitric oxide synthase (iNOS), cyclooxygenase-2 (COX-2) and prostanglandin-E2 (PGE2) in RAW 264.7 macrophage-like cells. Inhibition of cancer cell invasion and inflammation by 3-Ph-3-SG were mediated through suppression of the nuclear factor-kappaB (NF-κB) signaling pathway. The 3-Ph-3-SG also demonstrated cytoprotective effects by inducing the antioxidant response element (ARE)-driven genes NAD(P)H quinone oxidoreductase-1 (NQO1) and heme oxygenase-1 (HO-1). Cytoprotection by 3-Ph-3-SG was achieved at least partly through modification of cysteine residues in the E3 ubiquitin ligase substrate adaptor Kelch-like ECH-associated protein 1 (Keap1), which resulted in accumulation of transcription factor NF-E2 p45-related factor 2 (Nrf2). The activities of 3-Ph-3-SG were comparable to those of 6-shogaol, the most abundant naturally-occurring shogaol, and stronger than those of 4-hydroxyl-null deshydroxy-3-phenyl-3-shogaol, which attested the importance of the 4-hydroxy substituent in the vanilloid moiety for bioactivity. In summary, 3-Ph-3-SG is shown to possess activities that modulate stress-associated pathways relevant to multiple steps in carcinogenesis. Therefore, it warrants further investigation of this compound as a promising candidate for use in chemotherapeutic and chemopreventive strategies.


Asunto(s)
Catecoles/farmacología , Citoprotección/efectos de los fármacos , Péptidos y Proteínas de Señalización Intracelular/fisiología , Factor 2 Relacionado con NF-E2/fisiología , FN-kappa B/fisiología , Invasividad Neoplásica/prevención & control , Animales , Catecoles/química , Catecoles/uso terapéutico , Citoprotección/fisiología , Regulación hacia Abajo/efectos de los fármacos , Regulación hacia Abajo/fisiología , Células HEK293 , Humanos , Inflamación/metabolismo , Inflamación/patología , Inflamación/prevención & control , Proteína 1 Asociada A ECH Tipo Kelch , Células MCF-7 , Ratones , Invasividad Neoplásica/patología , Extractos Vegetales/química , Extractos Vegetales/farmacología , Extractos Vegetales/uso terapéutico , Transducción de Señal/efectos de los fármacos , Transducción de Señal/fisiología
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