Fieldwaters8420
Eumelanin is responsible for photoprotection in living organisms. It is made of 5,6-dihydroxyindole (DHI) oligomers. However, lack of detailed structural knowledge limits understanding its function and exploiting its potential in material science. To uncover the relationship between structural stability and optical properties, we have studied a virtual library of 830 DHI dimers. We find a preference for oxidized, polycyclic structures which speaks in favor of graphite-like structures for the larger oligomers, and propose an electrocyclic formation mechanism. Besides widely considered quinone oxidation patterns, also structures with interfragment double bonds and zwitterionic resonance structures are stable. Future theoretical melanine models will have to cover this diversity, and we introduce a new representative set of 49 stable dimers. Some stable oxidized dimers have absorption energies as low as 1.3 eV. They may be present as substructures in the naturally found oligomers and contribute to the absorption spectrum of the biopolymer.Similarities in sizes, shapes, and physical properties between carbon dioxide (CO2 ) and acetylene (C2 H2 ) make it a great challenge to separate the major impurity CO2 from products in C2 H2 production. The use of porous materials is an appealing path to replace current very costly and energy-consuming technologies, such as solvent extraction and cryogenic distillation; however, high CO2 /C2 H2 uptake ratio with minor adsorption of C2 H2 at standard pressure was only unexpectedly observed in scarce examples in recent years although the related research started early at 1950s, and general design strategies to realize this aim are still absent. This work has successfully developed an efficient PIET strategy and obtained the second highest CO2 /C2 H2 adsorption ratio for porous materials in a proof-of-concept MOF with a photochromism-active bipyridinium zwitterion. An unprecedented photocontrollable gate effect, owing to change of interannular dihedral after photoinduced generation of radical species, was also observed for the first time. These findings will inspire design and synthesis of porous materials for high efficient gas adsorption and separation.trans,trans-Muconic acid has been widely used as a biomarker in biological monitoring of benzene-exposed workers during routine occupational health services. In the present study, a novel microextraction technique, in-syringe ionic liquid-dispersive liquid-liquid microextraction, was implemented for preconcentration of trans,trans-muconic acid followed by analytical determination by high-performance liquid chromatography with ultraviolet detection. Moreover, the important variables affecting the performance of applied microextraction technique including needle diameter, volume of the spiked sample, volume of the ionic liquid, salt addition, rotation speed of centrifugation, centrifuge time, and ultrasonic time were optimized by experimental design. A good linear relationship was observed at the range of 0.032-10 μg/mL between the peak area and the concentration levels (R2 = 0.9997). The limit of detection and extraction recovery for trans,trans-muconic acid were 0.011 μg/mL and >96.2%, respectively. This method provided easy and rapid analysis of low amounts of trans,trans-muconic acid in human urine with simple equipment.
Child abuse is an important independent risk factor for suicide. The purpose of the project was to evaluate the implementation of a universal suicide risk screening and assessment tool in an outpatient child abuse evaluation clinic.
Participants consisted of all patients between the ages of 10 and 18 years who received services at the study site within a 3-month period (n = 162). The study site implemented a tool created for the sole purpose of detecting suicide risk, the Ask Suicide-Screening Questions (ASQ) tool. Data was retrospectively collected using electronic health records; rates of compliance with screening and screen positive rates were calculated.
Suicide risk screening with the ASQ was conducted on 90.7% (147) of the patients. Forty-three (29.2%) patients screened positive for suicide risk. This is a significant increase in detection rates compared to baseline preimplementation data. Of the 67 preteens, 10-12 years of age, that were screened, 14.9% (10/67) screened positive for suicide risk, making up 23% of the positive screens.
Implementing a universal suicide risk screening tool was a successful strategy for detecting suicide risk. A quarter of the youth who screened positive on the ASQ were preteens, highlighting the importance of screening the 10- to 12-year olds for suicide risk.
Implementing a universal suicide risk screening tool was a successful strategy for detecting suicide risk. A quarter of the youth who screened positive on the ASQ were preteens, highlighting the importance of screening the 10- to 12-year olds for suicide risk.
The 'Toronto consensus principles and guidelines' (TG) provided paediatric-specific staging system affordable by population-based cancer registries (CRs). Within the European Rare Cancers Joint Action, a pilot study of the application of TG for childhood cancer (CC) was conducted to test the ability of CRs to reconstruct stage, describe stage across countries and assess survival by stage.
Twenty-five CRs representing 15 countries contributed data on a representative sample of patients with neuroblastoma (NB) and Wilms tumour (WT) <15years, diagnosed between 2000 and 2016. Outcome was calculated by Kaplan-Meier method and by Cox regression model.
Stage was reconstructed for 95% of cases. Around half of the children had localised or locoregional disease at diagnosis. The proportion of metastatic cases was 38% for NB and 13% for WT. Three-year survival was >90% for locoregional cases both of NB and WT, 58% for NB M-stage and 77% for WT stage-IV. Older age was associated with more advanced stage.
European CRs were able to reconstruct stage according to the TG. Stage should be included in the routine collection of variables. Stage information had clear prognostic value and should be used to investigate survival variations between countries or over time.
European CRs were able to reconstruct stage according to the TG. Stage should be included in the routine collection of variables. Stage information had clear prognostic value and should be used to investigate survival variations between countries or over time.
Starting from 2014, the Indonesian government has implemented Universal Health Coverage (UHC) with the aim to make healthcare services accessible and affordable to all Indonesian citizens. A major reason for childhood cancer treatment failure in low- and middle-income countries, particularly among families with low socioeconomic status (SES), is abandonment of expensive cancer treatment. Our study compared childhood cancer treatment outcomes of the overall, low, and high SES population before and after introduction of UHC at a large Indonesian academic hospital.
Medical records of 1040 patients diagnosed with childhood cancer before (2011-2013, n=506) and after (2014-2016, n=534) introduction of UHC were abstracted retrospectively. Data on treatment outcome, SES, and health-insurance status at diagnosis were obtained.
After introduction of UHC, the number of insured patients increased from 38% to 82% (P<0.001). Among low SES population, insurance coverage increased from 40% to 85% (P<0.001), and among high SES population from 33% to 77% (P<0.001). In the overall population, treatment abandonment decreased from 36% to 22% (P<0.001). Event-free survival estimates at four years after diagnosis of overall population improved from 16% to 22% (P<0.001). Hazard ratio for treatment failure was 1.26 (CI 1.07-1.48, P=0.006) for uninsured versus insured patients. In the low SES population, treatment abandonment decreased from 36% to 19% (P<0.001). Event-free survival estimates at four years after diagnosis of low SES population improved from 14% to 22% (P<0.001).
Introduction of UHC in Indonesia contributed significantly to better treatment outcome and event-free survival of children with cancer from low SES families.
Introduction of UHC in Indonesia contributed significantly to better treatment outcome and event-free survival of children with cancer from low SES families.Effective control on chemoselectivity in the catalytic hydrogenation of C=O over C=C bonds is uncommon with Pd-based catalysts because of the favored adsorption of C=C bonds on Pd surface. Here we report a unique orthorhombic PdSn intermetallic phase with unprecedented chemoselectivity toward C=O hydrogenation. We observed the formation and metastability of this PdSn phase in situ. During a natural cooling process, the PdSn nanoparticles readily revert to the favored Pd3 Sn2 phase. Instead, using a thermal quenching method, we prepared a pure-phase PdSn nanocatalyst. PdSn shows an >96 % selectivity toward hydrogenating C=O bonds of various α,β-unsaturated aldehydes, highest in reported Pd-based catalysts. Further study suggests that efficient quenching prevents the reversion from PdSn- to Pd3 Sn2 -structured surface, the key to the desired catalytic performance. Density functional theory calculations and analysis of reaction kinetics provide an explanation for the observed high selectivity.
The consistent prevalence and occasionally severe consequences of bullying and victimization suggest the need to include a more accurate assessment of these episodes within the Emergency Departments (ED). However, the literature on mental health related symptoms of bullying/victimization treated in the ED is still scarce. The aim of this study is to assess the prevalence of peer victimization amongst children and adolescents referred to an Italian Pediatric Emergency Department. Differences between Hospital Departments, type of victimization and ages are tested.
A retrospective observational study was conducted with 705 subjects. The age range was from 6 to 18 years old (M = 13.09; SD = 3.048).
15.3% of the sample reported to be victimized (8.2% occasionally; 7.1% systematically). For the Child and Adolescent Psychiatry Unit, we found a significant association between peer victimization and being adolescent (Fisher's p = 0.003). In addition, a significant association was found between verbal victimization and Child and Adolescent Psychiatry Unit (Fisher's p = 0.02) and physical victimization and Child Abuse Department (Fisher's p < 0.001).
Findings suggest the importance of an accurate assessment of victimization experiences of children and adolescents with access to ED, to prevent future re-victimization and crystallization of symptoms across time.
Findings suggest the importance of an accurate assessment of victimization experiences of children and adolescents with access to ED, to prevent future re-victimization and crystallization of symptoms across time.Site-selective incorporation of deuterium into biologically active compounds is of high interest in pharmaceutical industry. We present a mild and environmentally benign metal-free method for the remote selective radical C-H monodeuteration of aliphatic C-H bonds in various amides with inexpensive heavy water (D2 O) as the deuterium source. The method uses the easily installed N-allylsulfonyl moiety as an N-radical precursor that generates the remote C-radical via site-selective 1,5- or 1,6-hydrogen atom transfer (HAT). Methyl thioglycolate, that readily exchanges its proton with D2 O, serves as the radical deuteration reagent and as a chain-carrier. The highly site-selective monodeuteration has been applied to different types of unactivated sp3 -C-H bonds and also to the deuteration of C-H bonds next to heteroatoms. The potential utility of this method is further demonstrated by the site-selective incorporation of deuterium into natural product derivatives and drugs.