Monitoring Epoxidized Soybean Oil Degradation Using Liquid Chromatography-Mass Spectrometry and In Silico Spectral Libraries.

Epoxidized soybean oil (ESO) is routinely used as a bioderived plasticizer and stabilizer in polyvinyl chloride (PVC), as it prolongs material integrity during dehydrochlorination. During this process, the epoxide moieties of ESO are progressively converted to chlorohydrins, which amplify ESO's inherent structural complexity. Past characterization efforts utilized separation-mass spectrometry (MS) analysis of the hydrolyzed acyl chains to simplify the complexity. However, this approach significantly increases the complexity of sample preparation and cannot directly monitor the chlorination of individual ESO species during aging. Here, we present a comprehensive LC-MS/MS data acquisition and in silico spectral library identification workflow optimized for intact ESO byproduct analysis. Detailed MS/MS fragmentation rules derived from synthesized standards were coupled with improved fragment ion intensity modeling capabilities to generate a high-fidelity spectral library for rapid ESO byproduct identification. Identification confidence was further bolstered by using retention time modeling to filter spurious MS/MS matches. Finally, we paired this informatic approach with an optimized extraction procedure and reversed-phase separation to generate a detailed timeline of more than 400 ESO species and byproducts during PVC thermal aging. These developments significantly improve our ability to detect, characterize, and understand ESO degradation in complex PVC formulations with new levels of molecular resolution.

The effects of prenatal PM2.5 oxidative potential exposure on feto-placental vascular resistance and fetal weight: A repeated-measures study.

BACKGROUND: Feto-placental hemodynamic deterioration is a critical contributing factor to fetal growth restriction. Whether PM2.5 oxidative potential (OP) affects feto-placental hemodynamics and what impact is on estimated fetal weight (EFW) have not been fully elucidated. We sought to evaluate the association of PM2.5 OP with EFW and to explore whether feto-placental vascular impedance hemodynamic change is a possible mediator in this association. METHODS: A repeated-measures study was conducted involving sixty pregnant women with at least 26 weeks of follow-up during pregnancy in Guangzhou, China, from September 2017 to October 2018. Daily filter-based PM2.5 samples were prospectively collected from ground monitors, and estimates of OP for PM2.5 and its metallic (OPv-metal) and non-metallic constituents (OPv-nonmental) were determined by dithiothreitol assay. Ultrasound data of fetal growth and umbilical arterial resistance, including estimated fetal weight (EFW), pulsatility index, resistance index, and systolic-to-diastolic ratio, were also obtained during gestation. Generalized estimating equations and polynomial distribution lag models were applied to analyze the associations of maternal exposure to PM2.5 OP with EFW and umbilical artery indices. Causal mediation analysis was used to evaluate the mediating role of umbilical arterial resistance. RESULTS: Prenatal exposure to ambient PM2.5 OP was significantly inversely associated with EFW. The magnitudes of effects of OPv-nonmetal on EFW were larger than those of OPv-metal. Significant mediation for the relationship between PM2.5-related OP and EFW by increased impedance in the umbilical artery was observed, with the estimated percent mediated ranging from 31% to 61%. The estimated percent mediated for OPv-nonmetal was higher than those for OPv-metal. CONCLUSIONS: Findings suggest that increased impedance in the umbilical artery may be one of the potential mediators of the relationship between PM2.5 oxidative potential exposure and low fetal weight.

Role of antenatal anxiety in the relationship between maternal exposure to nitrogen dioxide and small for gestational age: A birth cohort study.

BACKGROUND: Both Nitrogen dioxide (NO2) exposure and antenatal anxiety have individually been associated with small for gestational age (SGA). Little is known, however, about whether there is effect modification of antenatal anxiety on NO2-related SGA. METHODS: The prospective birth cohort study included 1823 mother-newborn pairs in Guangzhou, China, from January 2017 to April 2020. Exposure to NO2 during the pre-conceptional and prenatal periods was estimated using an inverse distance weighted method. Antenatal anxiety was assessed by Trait Anxiety Inventory. SGA was determined by the Chinese gestational age- and sex-specific birthweight standards. Cox proportional hazards regression models was used to estimate hazard ratios (HRs) and 95 % confidence intervals (CIs) for SGA as per 10 µg/m3 increase in NO2. Modifying effects of trait anxiety on NO2-related SGA were identified by stratified analyses, and three-dimensional response surface plots and two-dimensional heat maps. RESULTS: Each 10 µg/m3 increase in NO2 exposure during the third trimester was significantly associated with SGA risk among overall participants (HR = 1.221, 95 % CI: 1.014-1.471) and primipara (HR = 1.271, 95 % CI: 1.023-1.579). We found significant effect modification of anxiety level for NO2-related SGA in the third trimester (Pinteraction < 0.05). Pregnant women with higher levels of trait anxiety were more likely to deliver SGA newborns, particularly for those with high trait anxiety (HR = 1.781, 95 % CI: 1.007-2.945). Primiparous women were more susceptible. CONCLUSIONS: This study provides evidence that antenatal trait anxiety may modify the effects of maternal NO2 exposure on SGA risk. The third trimester could be a critical window of susceptibility.

Universal linker-free assembly of core-satellite hetero-superstructures.

Colloidal superstructures comprising hetero-building blocks often show unanticipated physical and chemical properties. Here, we present a universal assembly methodology to prepare hetero-superstructures. This straightforward methodology allows the assembly of building block materials varying from inorganic nanoparticles to living cells to form superstructures. No molecular linker is required to bind the building blocks together and thus the products do not contain any unwanted adscititious material. The Fourier transform infrared spectra, high resolution transmission electron microscopic images and nanoparticle adhesion force measurement results reveal that the key to self-organization is stripping surface ligands by adding non-polar solvents or neutralizing surface charge by adding salts, which allow us to tune the balance between van der Waals attraction and electrostatic repulsion in the colloid so as to trigger the assembling process. As a proof-of-concept, the superior photocatalytic activity and single-particle surface-enhanced Raman scattering of the corresponding superstructures are demonstrated. Our methodology greatly extends the scope of building blocks for superstructure assembly and enables scalable construction of colloidal multifunctional materials.

The formation of tonalitic and granodioritic melt from Venusian basalt.

The crust of Venus is composed of the low lying volcanic planitiae and the elevated, deformed tesserae. It is thought that the tesserae may be composed of silicic igneous rocks and that it may resemble proto-continental crust. The initial development of terrestrial continental crust is likely due to melting and deformation of primitive mafic crust via mantle-plume upwelling and collisional plate processes. Unlike Earth, the lithosphere of Venus is not divided into plates and therefore evolved continental crust, if present, developed primarily by melting of pre-existing mafic crust. Here, we report the results of high pressure equilibrium partial melting experiments using a parental composition similar to the basalt measured at the Venera 14 landing site in order to determine if silicic melts can be generated. It was found that at pressures of 1.5 GPa and 2.0 GPa and temperatures of 1080 °C, 1090 °C, and 1285 °C that tonalitic and granodioritic melts can be generated. The experimental results indicate that silicic rocks may be able to form in the crust of Venus providing the thermal regime is suitable and that the lower crust is basaltic. The implication is that the older, thicker regions of Venusian crust may be partially composed of silicic igneous rocks.

Growth and thermal maturation of the Toba magma reservoir.

The Toba volcanic system in Indonesia has produced two of the largest eruptions (>2,000 km3 dense-rock equivalent [DRE] each) on Earth since the Quaternary. U-Pb crystallization ages of zircon span a period of ∼600 ky before each eruptive event, and in the run-up to each eruption, the mean and variance of the zircons' U content decrease. To quantify the process of accumulation of eruptible magma underneath the Toba caldera, we integrated these observations with thermal and geochemical modeling. We show that caldera-forming eruptions at Toba are the result of progressive thermal maturation of the upper crustal magma reservoir, which grows and chemically homogenizes, by sustained magma influx at average volumetric rates between 0.008 and 0.01 km3/y over the past 2.2 My. Protracted thermal pulses related to magma-recharge events prime the system for eruption without necessarily requiring an increased magma-recharge rate before the two supereruptions. If the rate of magma input was maintained since the last supereruption of Toba at 75 ka, eruptible magma is currently accumulating at a minimum rate of ∼4.2 km3 per millennium, and the current estimate of the total volume of potentially eruptible magma available today is a minimum of ∼315 km3 Our approach to evaluate magma flux and the rate of eruptible magma accumulation is applicable to other volcanic systems capable of producing supereruptions and thereby could help in assessing the potential of active volcanic systems to feed supereruptions.

The Association of Social Support and Symptomatic Remission among Community-Dwelling Schizophrenia Patients: A Cross-Sectional Study.

Schizophrenia is a mental disease that often leads to chronicity. Social support could reduce the severity of psychotic symptoms; therefore, its influence on remission should be examined. This study investigated the remission rates in community-dwelling schizophrenia patients and examined the association between social support and remission status. A cross-sectional study was conducted in 129 schizophrenia patients in Taiwan. Remission rates were evaluated, and the level of social support, clinical characteristics, sociodemographic variables, and healthy lifestyle status were compared between the remission and nonremission groups. The association between social support and remission was analyzed after adjusting for confounding factors. The mean illness duration is 12.9 years. More than 95% of the participants lived with their families, 63% were unemployed, and 43% achieved remission. Higher social support was observed in the remission group, and a significant correlation was observed between family domain of social support and remission status. Family support was a protective factor of symptomatic remission in community-dwelling schizophrenia patients in Taiwan. The results reflect the effects of a family-centered culture on patients during illness. Consequently, reinforcing family relationships and the capacity of families to manage the symptoms of patients and providing support to families are recommended.

Stability Assessment of a Polymeric Brominated Flame Retardant in Polystyrene Foams under Application-Relevant Conditions.

The flame retardant (FR) BLUEDGE polymeric flame retardant (PFR) has been in use since 2011 and was developed as a replacement FR for hexabromocyclododecane in polystyrene (PS)-based insulation foams. To better understand the degradation behavior of the PFR used within PS foams, we examined the degradation of PFR under application-relevant conditions. Thermo-oxidative and photolytic pathways represent the most relevant degradation pathways. Separately, both the thermal and oxidative degradations of PFR at ambient conditions were shown to be negligible based on kinetic models of thermogravimetric analysis data obtained at elevated temperatures; the models predict that it would take 100 years to degrade 1% of PFR at 50 °C and 1000 years at 20 °C. Photodegradation was shown to degrade PFR after accelerated ultraviolet (UV) aging/exposure. UV radiation did not significantly penetrate the foam insulation (<2000 µm); the degradation process took place primarily at the surface. The molecular weight of the polymer changed with degradation, but there was minimal loss of bromine from the foam with degradation. The data from the liquid chromatography-mass spectrometry analysis focused primarily on several small-molecule polar products formed, which included two brominated species. These species were predicted using computer-based modeling to be biodegradable, to not be persistent in the environment, and to exhibit a low toxicity to aquatic organisms.

Perceptions, clinical characteristics, and other factors associated with prolonged and high daily dose of benzodiazepine use among patients with anxiety or depressive disorders.

BACKGROUND: Benzodiazepines (BZDs) have been widely used to treat anxiety; however, the risk of adverse health effects caused by their long-term use is high. This study examined the factors associated with the duration and higher daily dose of BZDs use among a population with anxiety or depressive disorders. METHODS: A cross-sectional study design was used. Patients from a psychiatric outpatient department who had been prescribed BZDs were recruited. Data were collected from 250 patients. RESULTS: Nearly 94% of patients were long-term BZDs users. The mean duration of BZDs use was 5.5 years; and mean defined daily dose (DDD) of BZDs use, converted to diazepam milligram equivalent (DDD), was 1.53 DME-DDD. Patients who knew more about alternative treatments were less prone to use BZD longer. Patients aged 65 years or older and those with difficulty falling asleep were more prone to use BZDs longer. Patients who were currently taking BZDs at higher daily dose were those who felt more depressed, prescribed second generation antipsychotics, suffered from disrupted sleep, less aware of alternative treatments, had comorbid chronic physical illness, and were current smokers. LIMITATIONS: The cross-sectional study design limited its ability to confirm causal relationships. CONCLUSIONS: Long-term and excessive daily dose of BZDs use in patients with depressive or anxiety disorders needs to be noted. Providing information or program of non-pharmacological treatment in reducing anxiety and improving specific sleep disturbance is suggested. Elderly, suffering from depressive mood, had comorbid chronic physical illness need to be targeted for further intervention.

The changes of quality of life and their correlations with psychosocial factors following surgery among women with breast cancer from the post-surgery to post-treatment survivorship.

OBJECTIVES: This 14-month study aimed to examine the changes of quality of life following breast cancer surgery and associations of such changes with depression and anxiety levels, and protective factors (attachment styles in close relationship, and meaning in life) based on positive psychology theory. MATERIALS AND METHODS: Women with breast cancer were recruited within one week of completion of breast cancer surgery. They were asked to complete several questionnaires to measure the generic and breast cancer specific quality of life, depression and anxiety levels, attachment styles in close relationship, and meaning in life. Assessments were performed at baseline (T0), T1 (the 2nd month), T2 (the 5th month), T3 (the 8th month), and T4 (the 14th month). RESULTS: While the generic functions of quality of life improve after surgery, no significant changes of the breast-specific functions were found during the 14-month follow up period. While physical, role, and social functions improved immediately after surgery, the improvements of emotional and cognitive functions began to occur at the 5th and the 8th months after surgery. Depressive symptoms predicted almost all general and breast-specific QOL functions and symptoms. Avoidant and anxious attachment styles were associated with the negative scores for breast-specific functions and symptoms. CONCLUSION: Breast-specific functions, in particular body image and sexual function, remain unchanged with the passage of time following surgery. A psychological rehabilitation program aiming to reduce depressive symptoms and enhance secure attachment styles in close relationships needs to be established immediately following surgery and continue through the post-treatment survivorship stages.

Rapid and sensitive SERS detection of the cytokine tumor necrosis factor alpha (tnf-α) in a magnetic bead pull-down assay with purified and highly Raman-active gold nanoparticle clusters.

Tumor necrosis factor alpha (TNF-α) is a cytokine with significance in early diagnosis of cardiovascular diseases, obesity and insulin resistance. We demonstrate the proof of concept for a rapid and sensitive detection of TNF-α using a magnetic bead pull-down assay in combination with surface-enhanced Raman scattering (SERS). The use of purified and highly SERS-active small clusters of gold nanoparticles (AuNP) provides the high sensitivity of the assay with a limit of detection of ca. 1 pg/mL. Continuous density gradient centrifugation was employed for separating the very bright silica-encapsulated AuNP dimers and trimers from the significantly weaker AuNP monomers. Negative control experiments with other cytokines (IL-6, IL-8) and bovine serum albumin (BSA) confirm the high specificity of the assay, but indicate also space for future improvements by further reducing non-specific binding between proteins and the SERS nanotags. The multiplexing potential of this SERS-based detection scheme is exemplarily demonstrated by using a set of three spectrally distinct and highly SERS-active AuNP clusters with unique spectral barcodes. Graphical abstract ᅟ.

A longitudinal study of diurnal cortisol patterns and associated factors in breast cancer patients from the transition stage of the end of active cancer treatment to post-treatment survivorship.

OBJECTIVES: The aim of this study was to examine the changes in diurnal cortisol patterns and its associated factors among breast cancer patients over a 14-month follow up period. MATERIALS AND METHODS: A total of 85 breast cancer patients were recruited to participate in this study. Assessments were performed at baseline (T0), T1 (the 2nd month), T2 (the 5th month), T3 (the 8th month), and T4 (the 14th month). Salivary cortisol was measured and the following questionnaires were administered: BDI-II depression scale, European Organization for Research and Treatment of Cancer Core Cancer Quality of Life Questionnaire (EORTC QLQ-C30) and its breast cancer-specific complementary measure (EORTC QLQ-BR23). Patients were grouped into flat and steep groups, according to the median of the diurnal cortisol slopes at the time of the transition period. RESULTS: Breast cancer patients in the flatter slope group at transition period demonstrated steeper slopes over the course of recovery from treatment and those in the steeper slope group at transition period continued with steeper slopes over the course of recovery. The greater breast cancer-related symptoms (side-effects, symptoms relating to breast and arm, and hair loss) were associated with the changes in flatter diurnal cortisol slopes during14-month follow up period. CONCLUSION: Diurnal cortisol patterns in flatter slope group at the transition period appear to have a trend of recovery with the passage of time over the course of recovery from treatment. Management of breast cancer symptoms could improve dysregulation of diurnal cortisol patterns among survivors.

Assay of fluoride by a novel organic-inorganic mesoporous nano-sized sensor.

In this report, we prepared a novel mesoporous silica nanostructure for selective detection of fluoride through ultraviolet absorption and emission changes. In the sensing system, a silica coupling reagent (3-(triethoxysilyl)propyl isocyanate) linked 1-naphthylamine has been covalently grafted onto the mesopores of inorganic network. These specially designed nanospheres can recognize fluoride from other anions based on hydrogen bond interactions. This approach may provide new opportunities for designing related sensing systems with enhanced physical or chemical properties. Copyright © 2016 John Wiley & Sons, Ltd.

Flexible, High-Speed CdSe Nanocrystal Integrated Circuits.

We report large-area, flexible, high-speed analog and digital colloidal CdSe nanocrystal integrated circuits operating at low voltages. Using photolithography and a newly developed process to fabricate vertical interconnect access holes, we scale down device dimensions, reducing parasitic capacitances and increasing the frequency of circuit operation, and scale up device fabrication over 4 in. flexible substrates. We demonstrate amplifiers with ∼7 kHz bandwidth, ring oscillators with <10 µs stage delays, and NAND and NOR logic gates.

Habitual sleep-wake behaviors and lifestyle as predictors of diurnal cortisol patterns in young breast cancer survivors: a longitudinal study.

OBJECTIVE: This study aimed to identify predictors of changes in diurnal cortisol patterns during the 8-month follow up period for young breast cancer survivors. Among the potential predictors were tumor size, lymph node metastasis, changes in sleep problems, habitual time of awakening and bedtime, physical activity levels, body mass index (BMI), and depressive levels across 8 months. METHODS: The participants were 62 breast cancer women who were aged 40 years and below, and had completed active breast cancer treatment. The longitudinal data were collected at four points: baseline assessment (T0) and three follow-ups after baseline: T1 (in the 2nd month), T2 (in the 5th month), and T3 (in the 8th month). The participants collected their salivary cortisol at home at six time points: upon waking, 30 and 45min after waking, and at 1200h, 1700h, and 2100h. They also completed several questionnaires: the Medical Outcomes Study Sleep scale; the Beck Depression Inventory-II, physical activity levels on a 10-point scale, time of going to bed, time of awakening, and total sleep hours. RESULTS: This study found that the main predictors of changes toward flatter diurnal cortisol patterns during the 8-month follow ups were greater tumor sizes, increases of BMI scores, and habitually later times of awakening. CONCLUSIONS: While greater tumor sizes represent biological vulnerability of disruption of cortisol circadian rhythm, maintaining an appropriate BMI and good sleep habits could be a protective factor for normal cortisol regulation, which likely helps to reduce early mortality in young breast cancer survivors.

Engineering charge injection and charge transport for high performance PbSe nanocrystal thin film devices and circuits.

We study charge injection and transport in PbSe nanocrystal thin films. By engineering the contact metallurgy and nanocrystal ligand exchange chemistry and surface passivation, we demonstrate partial Fermi-level pinning at the metal-nanocrystal interface and an insulator-to-metal transition with increased coupling and doping, allowing us to design high conductivity and mobility PbSe nanocrystal films. We construct complementary nanocrystal circuits from n-type and p-type transistors realized from a single nanocrystal material by selecting the contact metallurgy.

Low-frequency (1/f) noise in nanocrystal field-effect transistors.

We investigate the origins and magnitude of low-frequency noise in high-mobility nanocrystal field-effect transistors and show the noise is of 1/f-type. Sub-band gap states, in particular, those introduced by nanocrystal surfaces, have a significant influence on the 1/f noise. By engineering the device geometry and passivating nanocrystal surfaces, we show that in the linear and saturation regimes the 1/f noise obeys Hooge's model of mobility fluctuations, consistent with transport of a high density of accumulated carriers in extended electronic states of the NC thin films. In the subthreshold regime, the Fermi energy moves deeper into the mobility gap and sub-band gap trap states give rise to a transition to noise dominated by carrier number fluctuations as described in McWhorter's model. CdSe nanocrystal field-effect transistors have a Hooge parameter of 3 × 10(-2), comparable to other solution-deposited, thin-film devices, promising high-performance, low-cost, low-noise integrated circuitry.

The partner's insecure attachment, depression and psychological well-being as predictors of diurnal cortisol patterns for breast cancer survivors and their spouses.

The purpose of this study was to explore whether stress from individual's and partner's depression, anxiety, sleep disturbances, insecure attachment and meaning in life were predictors of diurnal cortisol patterns in breast cancer survivors and their spouses. Thirty-four couple dyads participated in this eight-month follow-up study. The breast cancer survivors and their spouses completed the Medical Outcomes Study Sleep scale, the Beck Depression Inventory-II, the State Trait Anxiety Inventory, the Experiences in Close Relationships-Revised scale and the Meaning in Life Questionnaire, and they collected salivary cortisol at home at the time of awakening, 30 and 45 min after waking and at 1200 h, 1700 h and 2100 h. Diurnal cortisol slopes of survivors and spouses are positively correlated. But the factors associated with diurnal cortisol patterns are different between survivors and spouses. For survivors, neither survivor individuals' nor spouses' psychosocial factors were the predictors of survivors' diurnal cortisol patterns. For spouses, the survivors' higher anxious attachment style was the main predictor of spouses' flatter diurnal cortisol patterns. In conclusion, for spouses, psychophysiological stress responses are mainly influenced by breast cancer survivors' insecure attachment. Future couple supportive care interventions can address survivors' attachment styles in close relationships in order to improve neuroendocrine functions for both breast cancer survivors and their spouses.

Efficacy of psychotherapy on diurnal cortisol patterns and suicidal ideation in adjustment disorder with depressed mood.

AIMS: The aims were to examine the effects of psychotherapy on depressive and anxiety symptoms, the occurrence of suicidal ideations and diurnal cortisol patterns in patients with adjustment disorder (AD) with depressed mood. METHODS: Participants recruited from an outpatient department of psychiatry at a general hospital were randomly assigned to one of two groups: 34 in psychotherapy group and 37 in control group. The control group consisted of one-session psychoeducation. Psychotherapy included the eight-weekly body-mind-spirit (BMS) group psychotherapy. Measures included Beck Depression Inventory-II and State Trait Anxiety Inventory. Salivary cortisol samples were collected from the patients at their homes on awakening; 30 and 45 min after awakening; and at 1200, 1700 and 2100 h. Measurements were taken at baseline and at months 2 (end of intervention), 5, 8 and 14. RESULTS: There was no differential change over time between the BMS and control groups in self-reported depression or anxiety symptoms. However, suicidal ideation appeared to be reduced in the psychotherapy group. Changes in diurnal cortisol patterns were also significantly different in group × time interactions, in favor of BMS group. CONCLUSIONS: Psychotherapy likely provides improvements in psychobiological stress responses and decreases the occurrence of suicidal ideation in patients with AD.

In situ repair of high-performance, flexible nanocrystal electronics for large-area fabrication and operation in air.

Colloidal semiconductor nanocrystal (NC) thin films have been integrated in light-emitting diodes, solar cells, field-effect transistors (FETs), and flexible, electronic circuits. However, NC devices are typically fabricated and operated in an inert environment since the reactive surface and high surface-to-volume ratio of NC materials render them sensitive to oxygen, water, and many solvents. This sensitivity has limited device scaling and large-scale device integration achievable by conventional fabrication technologies, which generally require ambient air and wet-chemical processing. Here, we present a simple, effective route to reverse the detrimental effects of chemical and environmental exposure, by incorporating, in situ, a chemical agent, namely, indium metal, which is thermally triggered to diffuse and repair the damage. Taking advantage of the recovery process, CdSe NC FETs are processed in air, patterned using the solvents of lithography, and packaged by atomic layer deposition to form large-area and flexible high-performance NC devices that operate stably in air.