Electrochemically active porous carbon nanospheres prepared by inhibition of pyrolytic condensation of polymers.

Porous carbon is a pivotal material for electrochemical applications. The manufacture of porous carbon has relied on chemical treatments (etching or template) that require processing in all areas of the carbon/carbon precursor. We present a unique approach to preparing porous carbon nanospheres by inhibiting the pyrolytic condensation of polymers. Specifically, the porous carbon nanospheres are obtained by coating a thin film of ZnO on polystyrene spheres. The porosity of the porous carbon nanospheres is controlled by the thickness of the ZnO shell, achieving a BET-specific area of 1,124 m2/g with a specific volume of 1.09 cm3/g. We confirm that under the support force by the ZnO shell, a hierarchical pore structure in which small mesopores are connected by large mesopores is formed and that the pore-associated sp3 defects are enriched. These features allow full utilization of the surface area of the carbon pores. The electrochemical capacitive performance of porous carbon nanospheres was evaluated, achieving a high capacitance of 389 F/g at 1 A/g, capacitance retention of 71% at a 20-fold increase in current density, and stability up to 30,000 cycles. In particular, we achieve a specific area-normalized capacitance of 34.6 µF/cm2, which overcomes the limitations of conventional carbon materials.

Preparation of Well-Defined Double-Metal Cyanide Catalysts for Propylene Oxide Polymerization and CO2 Copolymerization.

Reevaluating the composition of the double metal cyanide catalyst (DMC) as a salt of (NC)6Co3- anions with 1:1 Zn2+/(X)Zn+ cations (X = Cl, RO, AcO), we prepared a series of well-defined DMCs, [ClZn+][Zn2+][(NC)6Co3-][ROH], [(RO)Zn+][Zn2+][(NC)6Co3-], [(AcO)Zn+][Zn2+][(NC)6Co3-], [(RO)Zn+]p[ClZn+](1-p)[Zn2+][(NC)6Co3-], [(AcO)Zn+]p[(tBuO)Zn+]q[Zn2+][(NC)6Co3-], and [(AcO)Zn+]p[(tBuO)Zn+]q[ClZn+]r[Zn2+][(NC)6Co3-]. The structure of [(MeOC3H6O)Zn+][Zn2+][(NC)6Co3-] was precisely determined at the atomic level through Rietveld refinement of the synchrotron X-ray powder diffraction data. By evaluating the catalyst's performance in both propylene oxide (PO) polymerization and PO/CO2 copolymerization, a correlation between structure and performance was established on various aspects including activity, dispersity, unsaturation level, and carbonate fraction in the resulting polyols. Ultimately, our study identified highly efficient catalysts that outperformed the state-of-the-art benchmark DMC not only in PO polymerization [DMC-(OAc/OtBu/Cl)(0.59/0.38/0.15)] but also in PO/CO2 copolymerization [DMC-(OAc/OtBu)(0.95/0.08)].

Plasma Surface Modification of 3Y-TZP at Low and Atmospheric Pressures with Different Treatment Times.

The efficiency of plasma surface modifications depends on the operating conditions. This study investigated the effect of chamber pressure and plasma exposure time on the surface properties of 3Y-TZP with N2/Ar gas. Plate-shaped zirconia specimens were randomly divided into two categories: vacuum plasma and atmospheric plasma. Each group was subdivided into five subgroups according to the treatment time: 1, 5, 10, 15, and 20 min. Following the plasma treatments, we characterized the surface properties, including wettability, chemical composition, crystal structure, surface morphology, and zeta potential. These were analyzed through various techniques, such as contact angle measurement, XPS, XRD, SEM, FIB, CLSM, and electrokinetic measurements. The atmospheric plasma treatments increased zirconia's electron donation (γ-) capacity, while the vacuum plasma treatments decreased γ- parameter with increasing times. The highest concentration of the basic hydroxyl OH(b) groups was identified after a 5 min exposure to atmospheric plasmas. With longer exposure times, the vacuum plasmas induce electrical damage. Both plasma systems increased the zeta potential of 3Y-TZP, showing positive values in a vacuum. In the atmosphere, the zeta potential rapidly increased after 1 min. Atmospheric plasma treatments would be beneficial for the adsorption of oxygen and nitrogen from ambient air and the generation of various active species on the zirconia surface.

Discerning critical stressors and resources in the lives of cancer patients: A multivariate analysis of targets of intervention for enhancing cancer care and quality of life.

OBJECTIVE: This study examined the relationship between a broad variety of stressors, resources, and outcomes to identify targets of intervention to enhance the quality of life of cancer patients and contribute to a comprehensive model of cancer care. METHODS: Five hundred and sixty persons with a diagnosis of cancer completed measures of stressors (past negative life events, current problems, current symptoms, comorbidities), resources (coping self-efficacy, social support, satisfaction with care) and outcomes (emotional and functional well-being). RESULTS: Multivariate canonical correlations between pairs of canonical variates (stressors-outcomes, Rc  = 0.56; stressors-resources, Rc  = 0.42, resources-outcomes Rc  = 0.66) were significant (all ps < 0.0001), which confirmed the relationship between those components and supported proceeding to more granular levels of analysis. More refined analyses revealed that the most critical variables in relation to outcomes (i.e., emotional and functional well-being), were current problems and symptoms among the stressors and coping self-efficacy, social support and patient satisfaction among the resources. CONCLUSIONS: This study provided an approach to the discernment of the most critical aspects of interventions that may improve supportive care and quality of life outcomes. Thus, efforts to address current problems (e.g., financial, home life, work), as well as effective management of symptoms (e.g., pain, fatigue, sleep), using the coordinated integration of medical care, support services and psycho-social interventions would provide the greatest impact on quality-of-life outcomes. Interventions that focus on problem solving and reinforce patient agency and activation may be most effective in sustaining quality of life outcomes into survivorship.

Comparative genome analyses of four rice-infecting Rhizoctonia solani isolates reveal extensive enrichment of homogalacturonan modification genes.

BACKGROUND: Plant pathogenic isolates of Rhizoctonia solani anastomosis group 1-intraspecific group IA (AG1-IA) infect a wide range of crops causing diseases such as rice sheath blight (ShB). ShB has become a serious disease in rice production worldwide. Additional genome sequences of the rice-infecting R. solani isolates from different geographical regions will facilitate the identification of important pathogenicity-related genes in the fungus. RESULTS: Rice-infecting R. solani isolates B2 (USA), ADB (India), WGL (India), and YN-7 (China) were selected for whole-genome sequencing. Single-Molecule Real-Time (SMRT) and Illumina sequencing were used for de novo sequencing of the B2 genome. The genomes of the other three isolates were then sequenced with Illumina technology and assembled using the B2 genome as a reference. The four genomes ranged from 38.9 to 45.0 Mbp in size, contained 9715 to 11,505 protein-coding genes, and shared 5812 conserved orthogroups. The proportion of transposable elements (TEs) and average length of TE sequences in the B2 genome was nearly 3 times and 2 times greater, respectively, than those of ADB, WGL and YN-7. Although 818 to 888 putative secreted proteins were identified in the four isolates, only 30% of them were predicted to be small secreted proteins, which is a smaller proportion than what is usually found in the genomes of cereal necrotrophic fungi. Despite a lack of putative secondary metabolite biosynthesis gene clusters, the rice-infecting R. solani genomes were predicted to contain the most carbohydrate-active enzyme (CAZyme) genes among all 27 fungal genomes used in the comparative analysis. Specifically, extensive enrichment of pectin/homogalacturonan modification genes were found in all four rice-infecting R. solani genomes. CONCLUSION: Four R. solani genomes were sequenced, annotated, and compared to other fungal genomes to identify distinctive genomic features that may contribute to the pathogenicity of rice-infecting R. solani. Our analyses provided evidence that genomic conservation of R. solani genomes among neighboring AGs was more diversified than among AG1-IA isolates and the presence of numerous predicted pectin modification genes in the rice-infecting R. solani genomes that may contribute to the wide host range and virulence of this necrotrophic fungal pathogen.

Fluorescence Probe for Imaging N-Methyl-d-aspartate Receptors and Monitoring GSH Selectively Using Two-Photon Microscopy.

N-Methyl-d-aspartate (NMDA) is an excitotoxic amino acid used to identify a specific subset of glutamate receptors. The activity of NMDA receptors is closely related to the redox level of the biological system. Glutathione (GSH) as an antioxidant plays a key role with regard to modulation of the redox environment. In this work we designed and developed a GSH-specific fluorescent probe with the capability of targeting NMDA receptors, which was composed of a two-photon naphthalimide fluorophore, a GSH-reactive group sulfonamide, and an ifenprodil targeting group for the NMDA receptor. This probe exhibited high selectivity toward GSH in comparison to other similar amino acids. Two-photon fluorescence microscopy allowed this probe to successfully monitor GSH in neuronal cells and hippocampal tissues with an excitation at 750 nm. It could serve as a potential practical imaging tool to explore the function of GSH and related biological processes in the brain.

Concise syntheses and anti-inflammatory effects of isocorniculatolide B and corniculatolide B and C.

The first total syntheses of isocorniculatolide B, corniculatolide B, and corniculatolide C, consisting of isomeric corniculatolide skeletons, have been accomplished in a divergent manner. The key features of the synthesis involve the construction of diaryl ether linkages by nucleophilic aromatic substitution, installation of a C14-substituted alkyl side chain via a sequence of Baeyer-Villiger reaction and Claisen rearrangement, and efficient construction of corniculatolide and isocorniculatolide frameworks, including 17-membered (exterior) macrolactone skeletons from a versatile diaryl ether intermediate by Mitsunobu macrolactonization. Moreover, we prepared the structural congeners of isomeric corniculatolides via diverted total synthesis approach including desmethyl analogues and related dimeric macrolides. The anti-inflammatory activities of the synthesized natural products, analogues and synthetic intermediates were also investigated. In particular, corniculatolide B significantly inhibited the protein expression of COX-2 and the mRNA expressions of TNF-α, IL-1ß and IL-6 by inhibiting of NF-κB signaling in intestinal epithelial cells induced by lipopolysaccharide treatment. It also significantly inhibited the promoter activity and the phosphorylation of subunits p50 and p65 of NF-κB to the same extent as Bay 11-7082, a potent IκB kinase inhibitor. These results suggest that corniculatolide B might have therapeutic potential in inflammatory bowel disease via NF-κB signaling pathway.

The Role of NRF2/KEAP1 Signaling Pathway in Cancer Metabolism.

The nuclear factor-erythroid 2 p45-related factor 2 (NRF2, also called Nfe2l2) and its cytoplasmic repressor, Kelch-like ECH-associated protein 1 (KEAP1), are major regulators of redox homeostasis controlling a multiple of genes for detoxification and cytoprotective enzymes. The NRF2/KEAP1 pathway is a fundamental signaling cascade responsible for the resistance of metabolic, oxidative stress, inflammation, and anticancer effects. Interestingly, a recent accumulation of evidence has indicated that NRF2 exhibits an aberrant activation in cancer. Evidence has shown that the NRF2/KEAP1 signaling pathway is associated with the proliferation of cancer cells and tumerigenesis through metabolic reprogramming. In this review, we provide an overview of the regulatory molecular mechanism of the NRF2/KEAP1 pathway against metabolic reprogramming in cancer, suggesting that the regulation of NRF2/KEAP1 axis might approach as a novel therapeutic strategy for cancers.

Transcriptome Profiling of the Rice Blast Fungus Magnaporthe oryzae and Its Host Oryza sativa During Infection.

The rice blast (fungal pathogen: Magnaporthe oryzae and host: Oryza sativa) is one of the most important model pathosystems for understanding plant-microbe interactions. Although both genome sequences were published as the first cases of pathogen and host, only a few in planta transcriptome data during infection are available. Due to technical difficulties, previously reported fungal transcriptome data are not highly qualified to comprehensively profile the expression of fungal genes during infection. Here, we report the high-quality transcriptomes of M. oryzae and rice during infection using a sheath infection-based RNA sequencing approach. This comprehensive expression profiling of the fungal pathogen and its host will provide a better platform for understanding the plant-microbe interactions at the genomic level and serve as a valuable resource for the research community.

Text mining analysis of teachers' reports on student suicide in South Korea.

A teacher as a suicide prevention gatekeeper has an important role in identifying suicide risks and warning signs in students. After a student's suicide, teachers in Korea have to write a student suicide case report based on their direct and indirect observations. In particular, the section 'characteristic of student suicide' of this report contains valuable information about the suicide; however, it is unstructured, and thus cannot be analyzed using conventional statistical methods. We aimed to identify the characteristics of observed Korean students, who have committed suicide, using text mining techniques as well as to improve our understanding of suicidal behaviors in the school contexts. Therefore, a series of text mining techniques: topic analysis, word correlation, and word frequency analysis, in three problem categories: health, school, and family problems, were used to analyze the characteristics of student suicides. Topic analysis showed that only 30% of the student suicide case reports identified problematic student characteristics related to suicide. Correlations between words showed that words in one problem category were often correlated with words in other problem categories. Frequency word analysis showed that the three problem categories varied across gender and school levels. These results provide interesting insights into the characteristics of suicides among Korean students and important implications for suicide intervention in the education field.

In Vivo Albumin Traps Photosensitizer Monomers from Self-Assembled Phthalocyanine Nanovesicles: A Facile and Switchable Theranostic Approach.

Albumin is a promising candidate as a biomarker for potential disease diagnostics and has been extensively used as a drug delivery carrier for decades. In these two directions, many albumin-detecting probes and exogenous albumin-based nanocomposite delivery systems have been developed. However, there are only a few cases demonstrating the specific interactions of exogenous probes with albumin in vivo, and nanocomposite delivery systems usually suffer from tedious fabrication processes and potential toxicity of the complexes. Herein, we demonstrate a facile "one-for-all" switchable nanotheranostic (NanoPcS) for both albumin detection and cancer treatment. In particular, the in vivo specific binding between albumin and PcS, arising from the disassembly of injected NanoPcS, is confirmed using an inducible transgenic mouse system. Fluorescence imaging and antitumor tests on different tumor models suggest that NanoPcS has superior tumor-targeting ability and the potential for time-modulated, activatable photodynamic therapy.

Subtypes of suicidal ideation in Korean adolescents: A multilevel latent profile analysis.

OBJECTIVE: This study intended to classify subtypes of Korean adolescents with suicidal ideation based on mental health problems and to explore the relationship between such subtypes and individual-, school- and community-level factors. METHOD: Data from high school freshmen who participated in the 2013 school-based mental health screening test and data about school and community variables obtained from public sources were combined and analyzed. A multilevel latent profile analysis using mental health issues as class indicators that included several predictors was conducted. RESULTS: Three latent profiles were identified: Group 1 (6.5%) had high scores for both the internalizing and externalizing problems; Group 2 (40.2%) had high scores for internalizing problems, such as depression and mood related symptoms; and Group 3 (53.3%) had lower scores for all mental health problems compared to Groups 1 and 2. Gender, peer conflict, family conflict and academic problems were significant predictors at the individual level; school dropout rate was a significant school-level variable; and percent of youth in the total population, availability of mental health services, number of social welfare facilities and percentage of the total budget devoted to education/welfare were significant community-level variables. CONCLUSION: The present findings suggest that adolescents with suicidal ideation can be classified into several distinct subtypes based on mental health problems. These profiles and their associated covariates will aid in the establishment of youth suicide prevention policies.

A Two-Photon Fluorescent Probe for Imaging Endogenous ONOO- near NMDA Receptors in Neuronal Cells and Hippocampal Tissues.

In this study, we developed a two-photon fluorescent probe for detection of peroxynitrite (ONOO-) near the N-methyl-d-aspartate (NMDA) receptor. This naphthalimide-based probe contains a boronic acid reactive group and an ifenprodil-like tail, which serves as an NMDA receptor targeting unit. The probe displays high sensitivity and selectivity, along with a fast response time in aqueous solution. More importantly, the probe can be employed along with two-photon fluorescence microscopy to detect endogenous ONOO- near NMDA receptors in neuronal cells as well as in hippocampal tissues. The results suggest that the probe has the potential of serving as a useful imaging tool for studying ONOO- related diseases in the nervous system.

The impact of psychological problems and adverse life events on suicidal ideation among adolescents using nationwide data of a school-based mental health screening test in Korea.

The aim of this study was to investigate the risk factors for suicidal ideation in adolescents by gender and age. This study used 2013 nationwide school-based mental health screening test data from 591,303 seventh grade students and 618,271 tenth grade students in Korea. Suicidal ideation, four psychological problems, and three adverse life events were evaluated using the Adolescents Mental Health and Problem Behavior Screening Questionnaire-II. Of all students, 12.9-14.7% of the boys and 17.1-23.2% of the girls had suicidal ideation. Mood had the greatest impact on the risk for suicidal ideation and other factors also significantly increased the risk of suicidal ideation. Distractibility was positively related to suicidal ideation only in seventh grade students and behavioral problems increased suicidal ideation more in girls than in boys. Violence constituted the most powerful factor for suicidal ideation among the events; however, bullying constituted the most important event that increased suicidal ideation in seventh grade girls. All factors except 'Distractibility' increased the risk of severe suicidal ideation. The risk factors for suicidal ideation in adolescents differed by gender and age. Interventions should be made according to these characteristics to reduce suicidal ideation in adolescents.

Phthalocyanine-Assembled Nanodots as Photosensitizers for Highly Efficient Type†I Photoreactions in Photodynamic Therapy.

Owing to their unique, nanoscale related optical properties, nanostructures assembled from molecular photosensitizers (PSs) have interesting applications in phototheranostics. However, most nanostructured PS assemblies are super-quenched, thus, preventing their use in photodynamic therapy (PDT). Although some of these materials undergo stimuli-responsive disassembly, which leads to partial recovery of PDT activity, their therapeutic potentials are unsatisfactory owing to a limited ability to promote generation reactive oxygen species (ROS), especially via type I photoreactions (i.e., not by 1 O2 generation). Herein we demonstrate that a new, nanostructured phthalocyanine assembly, NanoPcA, has the ability to promote highly efficient ROS generation via the type I mechanism. The results of antibacterial studies demonstrate that NanoPcA has potential PDT applications.

Nanostructured Phthalocyanine Assemblies with Protein-Driven Switchable Photoactivities for Biophotonic Imaging and Therapy.

Switchable phototheranostic nanomaterials are of particular interest for specific biosensing, high-quality imaging, and targeted therapy in the field of precision nanomedicine. Here, we develop a "one-for-all" nanomaterial that self-assembles from flexible and versatile phthalocyanine building blocks. The nanostructured phthalocyanine assemblies (NanoPcTBs) display intrinsically unique photothermal and photoacoustic properties. Fluorescence and reactive oxygen species generation can be triggered depending on a targeted, protein-induced, partial disassembly mechanism, which creates opportunities for low-background fluorescence imaging and activatable photodynamic therapy. In vitro evaluations indicate that NanoPcTB has a high selectivity for biotin receptor-positive cancer cells (e.g., A549) compared to biotin receptor-negative cells (e.g., WI38-VA13) and permits a combined photodynamic and photothermal therapeutic effect. Following systemic administration, the NanoPcTBs accumulate in A549 tumors of xenograft-bearing mice, and laser irradiation clearly induces the inhibition of tumor growth.

A Far-Red-Emitting Fluorescence Probe for Sensitive and Selective Detection of Peroxynitrite in Live Cells and Tissues.

In this study, the far-red-emitting fluorescence probe 1, containing a rhodamine derivative and a hydrazide reactive group, was developed for peroxynitrite detection and imaging. This probe, which is cell permeable and shows high sensitivity and selectivity in fluorometric detection of peroxynitrite over other ROS/RNS, was successfully utilized to detect exogenous and endogenous peroxynitrite in HeLa and RAW 264.7 cells, respectively. More importantly, 1 can also be used to detect endogenous peroxynitrite generated in Pseudomonas aeruginosa (PAO1)-infected mouse bone marrow-derived neutrophils. We anticipate that the new probe will serve as a powerful molecular imaging tool in investigations of the role(s) played by peroxynitrite in a variety of physiological and pathological contexts.

Duty-Related Trauma Exposure and Posttraumatic Stress Symptoms in Professional Firefighters.

Firefighters commonly encounter traumatic events during duty hours. The purpose of this study was to investigate the characteristics of duty-related trauma as risk factors for posttraumatic stress disorder in professional firefighters. A sample of 212 firefighters participated in the study and completed self-reported questionnaires. Potentially traumatic events (PTE) were assessed using a list of 17 traumatic event types. The posttraumatic stress symptoms (PTSS) were measured by the Impact of Event Scale-Revised (Lim et al., 2009; Weiss, 2007). A higher score for the composite index, which reflects both multiple PTE and peritraumatic suffering, increased the odds for significant PTSS after adjusting for age, sex, marital status, education, numbers of years worked, childhood trauma, and depressive symptoms (adjusted odds ratio [AOR] = 2.26, p = .001, Cohen's d = 0.20). Furthermore, indirect (AOR = 1.93, p = .009, Cohen's d = .16) and colleague-related PTE (AOR = 1.97, p = .037, Cohen's d = .16) showed significant associations with PTSS. It is noteworthy that the combination of multiple PTE and peritraumatic suffering was more predictive of PTSS than either factor alone. Our findings also suggest that daily work exposure to indirect PTE may contribute to the occurrence of PTSS among professional firefighters.

Alkoxide Migration at a Nickel(II) Center Induced by a π-Acidic Ligand: Migratory Insertion versus Metal-Ligand Cooperation.

Two pathways of alkoxide migration occurring at a nickel(II) center supported by a PPP ligand (PPP- = P[2-PiPr2-C6H4]2-) are presented in this Article. In the first route, the addition of a π-acidic ligand to a (PPP)Ni alkoxide species reveals the formation of a P-O bond. This reaction occurs via metal-ligand cooperation (MLC) involving a 2-electron reduction at nickel. To demonstrate a P-O bond formation, a nickel(II) isopropoxide species (PPP)Ni(OiPr) (4) was prepared. Upon addition of a π-acidic isocyanide ligand CNtBu, a nickel(0) isocyanide species (PPOiPrP)Ni(CNtBu) (6b) was generated; P-O bond formation occurred via reductive elimination (RE). When CO is present, migratory insertion (MI) occurs instead. The reaction of 4 with CO(g) results in the formation of (PPP)Ni(COOiPr) (5), representing an alternative pathway. The corresponding RE product (PPOiPrP)Ni(CO) (6a) can be independently produced from the substitution reaction of {(PPOiPrP)Ni}2(µ-N2) (3) with CO(g). While two different carbonylation pathways in 4 seem feasible, C-O bond forming migratory insertion singly occurs. Regeneration of a (PPP)Ni moiety via a P-O bond cleavage was demonstrated by treating 3 with CO2(g). The formation of (PPP)Ni(OCOOiPr) (7) clearly shows that an isopropoxide group migrates onto the bound CO2 ligand, and a P-Ni moiety is regenerated.