Aqueous organic redox-flow-batteries: from electrolyte development to detailed stability studies

To reach the political aims of the Kyoto Protocol and the Paris Agreement, the energy production must change from fossil fuels to sustainable sources like water, sun, and wind. But the fluctuation output of these techniques must be compensated by a smart grid. Herein, the integration of large-scale energy storage systems is inevitable. The possibility to use cheap organic molecules in “green” and non-toxic electrolytes make the emerging technology of organic redox flow batteries a promising candidate for this mission. Nevertheless, this battery concept suffers from many problems. One of the major ones is the insufficient stability of the active materials. To overcome this technical teething trouble, a combination of material and sensor development to investigate and mitigate decomposition processes is required. But currently, the research is more focused on development of new redox-active molecules with intrinsically higher stabilities than on investigating, understanding, and improving the underlying processes. Beside some exceptions, most research groups concentrate on demonstrating stabilities by cycling the material as often as possible. In addition, the influence of the used SOC of the battery is mostly uninvestigated. A battery management system which might limit the used SOC could improve the device lifespan. Therefore, precise, fast, and cheap monitoring systems for SOC and SOH determination are needed. The commonly applied techniques suffer from major drawbacks, like expensive equipment, material limitations, temperature dependency, and the need for (re)calibrations to name only a few. A protocol that is capable of monitoring these parameters on the electrolyte level and not on the battery level could unlock a deeper understanding of the ongoing processes inside the device or electrolyte. Possible device lifespan improvements could then not only be addressed by the material itself but also by the cycling conditions or other external factors

State of charge and state of health assessment of viologens in aqueous-organic redox-flow electrolytes using in situ IR spectroscopy and multivariate curve resolution

Aqueous-organic redox flow batteries (RFBs) have gained considerable interest in recent years, given their potential for an economically viable energy storage at large scale. This, however, strongly depends on both the robustness of the underlying electrolyte chemistry against molecular decomposition reactions as well as the device's operation. With regard to this, the presented study focuses on the use of in situ IR spectroscopy in combination with a multivariate curve resolution approach to gain insight into both the molecular structures of the active materials present within the electrolyte as well as crucial electrolyte state parameters, represented by the electrolyte's state of charge (SOC) and state of health (SOH). To demonstrate the general applicability of the approach, methyl viologen (MV) and bis(3-trimethylammonium)propyl viologen (BTMAPV) are chosen, as viologens are frequently used as negolytes in aqueous-organic RFBs. The study's findings highlight the impact of in situ spectroscopy and spectral deconvolution tools on the precision of the obtainable SOC and SOH values. Furthermore, the study indicates the occurrence of multiple viologen dimers, which possibly influence the electrolyte lifetime and charging characteristics

Small Molecules as Long-Wavelength Fluorophores: Push-Pull Substituted 4-Alkoxy-1,3-thiazoles

A series of donor-pi-acceptor (D-pi-A) substituted 4-hydroxythiazoles have been synthesized. Electron-donating groups (4-methoxyphenyl and 4-dimethylaminophenyl) were installed in the 5-position of the thiazole; thiophene/pyridine-bridged acceptors (formyl groups and their Knoevenagel condensation products) were placed in the 2-position. The influence of D-pi-A character on the photophysical properties and electronic structure was investigated by means of UV/Vis and fluorescence spectroscopy

Kinship practices in Early Iron Age South-east Europe: genetic and isotopic analysis of burials from the Dolge njive barrow cemetery, Dolenjska, Slovenia

The burial of multiple individuals within a single funerary monument invites speculation about the relationships between the deceased: were they chosen on the basis of status, gender or relatedness, for example? Here, the authors present the results of aDNA and isotope analyses conducted on seven individuals from an Early Iron Age barrow at Dolge njive, south-eastern Slovenia. All seven individuals are close biological relatives. While the group composition suggests strict adherence to neither patrilineal nor matrilineal structures, the funerary tradition appears highly gendered, and family links through both the male and female lines seem important in structuring of the community. The results have implications for understanding of kinship and funerary practices in late prehistoric Europe

The utility of extended outpatient civil commitment

Objective: This study considers three hypotheses regarding the impact of extended involuntary outpatient commitment orders on services utilization. Method: Service utilization of Victorian Psychiatric Case Register (VPCR) patients with extended ( >= 180 day) outpatient commitment orders was compared to that of a diagnostically-matched treatment compliant group with similarly extended (>= 180 day) periods of outpatient care (N = 1182)-the former receiving care during their extended episode on an involuntary basis while the latter participated in care voluntarily. Pre/post first extended episode mental health service utilization was compared via paired t tests with individuals as their own controls. Logistic and OLS regression as well as repeated measures ANOVA via the GLM SPSS program and post hoc t tests were used to evaluate between group and across time differences. Results: Extended episodes of care for both groups were associated with subsequent reduced use of hospitalization and increases in community treatment days. Extended orders did not promote voluntary participation in the period following their termination. Community treatment days during the extended episode for those on orders were raised to the level experienced by the treatment compliant comparison group during their extended episode and maintained at that level via subsequent renewal of orders throughout the patients' careers. Approximately six community treatment days were required for those on orders to achieve a one-day reduction in hospital utilization following the extended episode. Conclusion: Outpatient commitment for those on extended orders in the Victorian context enabled a level of community-based treatment provision unexpected in the absence of this delivery system and provided an alternative to hospitalization. (c) 2006 Elsevier Inc. All rights reserved

Preventing psychiatric hospitalization and involuntary outpatient commitment

Over the course of a decade in Victoria, Australia, this study considered how, for whom, under what circumstances, and with what consequences for a patient's treatment career involuntary outpatient commitment was used to prevent psychiatric hospitalization. Records were obtained from the Victorian Psychiatric Case Register for patients with career hospitalizations, 8,879 exposed to outpatient orders. Descriptive statistics and logistic regression were used to determine the characteristics of patients solely selected for placement on orders directly from the community, in lieu of re-hospitalization, versus patients selected for placement on orders only from the hospital or for those who experienced both hospital and community-initiated orders. Ordinary least squares regression was used to evaluate the relationship of sole reliance on community-initiated orders and experienced changes in future hospital utilization. Outpatient orders were infrequently issued directly from the community by comparison with orders issued at termination of inpatient episodes. Patients whose placements on orders were carried out only through direct community placement differed from those whose placement was primarily initiated from hospital or from both hospital and community. The former group, while largely comprised of people with schizophrenia, was less likely to include such patients than the comparison samples. It also included fewer males and never married individuals as well as more individuals with major affective disorders. Those served solely with community-initiated orders showed significantly less use of subsequent inpatient care than individuals in the comparison samples, all other diagnostic and pre-morbid adjustment characteristics taken into account. For patients at risk of beginning a career of long-term psychiatric hospitalization, sole reliance on community-initiated orders appeared to prevent additional hospital involvement. The issuance of orders from hospital and the combined-order strategy were associated with protective oversight throughout extended inpatient careers. Sole reliance on community-initiated outpatient orders provided a least restrictive alternative to hospitalization

Biological Sexing of a 4000-Year-Old Egyptian Mummy Head to Assess the Potential of Nuclear DNA Recovery from the Most Damaged and Limited Forensic Specimens

High throughput sequencing (HTS) has been used for a number of years in the field of paleogenomics to facilitate the recovery of small DNA fragments from ancient specimens. Recently, these techniques have also been applied in forensics, where they have been used for the recovery of mitochondrial DNA sequences from samples where traditional PCR-based assays fail because of the very short length of endogenous DNA molecules. Here, we describe the biological sexing of a ~4000-year-old Egyptian mummy using shotgun sequencing and two established methods of biological sex determination (RX and RY), by way of mitochondrial genome analysis as a means of sequence data authentication. This particular case of historical interest increases the potential utility of HTS techniques for forensic purposes by demonstrating that data from the more discriminatory nuclear genome can be recovered from the most damaged specimens, even in cases where mitochondrial DNA cannot be recovered with current PCR-based forensic technologies. Although additional work remains to be done before nuclear DNA recovered via these methods can be used routinely in operational casework for individual identification purposes, these results indicate substantial promise for the retrieval of probative individually identifying DNA data from the most limited and degraded forensic specimens