•Concentration limits imposed on legacy-BFRs to prevent further commercial use.•Notable variance in worldwide legislation regarding BFRs in consumer items & waste.•Limited effectiveness of ...concentration limits due to replacement/novel BFR use.•Lack of effective screening method may hinder plastic recycling processes.•Future legislation must be proactive in preventing cycle of hazardous chemical use.
Due to their toxicity and persistence, several families of brominated flame retardants (BFRs) have been listed as persistent organic pollutants (POPs) in the Stockholm Convention, a multilateral treaty overseen by the United Nations Environment Programme. This treaty mandates that parties who have signed must take administrative and legislative actions to prevent the environmental impacts that POPs pose, both within their jurisdictions and in the global environment. The specific BFRs listed in the Stockholm Convention are Polybrominated Diphenyl Ethers (PBDEs), Hexabromocyclododecane (HBCDD), and Hexabromobiphenyl (HBB), chemicals which must therefore be heavily restricted within the jurisdictions of the signatories. As an example, within the EU, hexabromobiphenyl (HBB), the PBDE commercial mixtures, and HBCDD are almost entirely prohibited in terms of both production and use in commercial goods. Waste articles containing excess concentrations of these BFRs are similarly restricted and must be disposed of in a manner that destroys or irreversible transforms the BFR in question. In some cases, specific exemptions for these limits are defined by the Convention for certain parties: for example, Penta- and Octa-BDE can be present in waste materials for recycling until 2030, while Deca-BDE can be applied to some aviation and automotive applications until 2036. However, in such cases, very specific criteria and guidelines apply for their use and/or production. Worldwide, China, Japan, India, and the United States of America have made significant advances in the regulation of POPs, in line with the provisions of the Stockholm Convention. China has established concentration limits for Penta- and Octa-BDEs in electronic goods. It is also currently availing of an exemption to allow for the use of HBCDD and has not yet ratified the Convention with regards to Deca-BDE. Japan meanwhile has classified HBB and Penta-/Octa-BDE compounds as Class I Specified Chemical Substances which virtually prohibits the manufacture, import, and use of these chemicals in all applications. India has banned the manufacture, trade, import, and use of HBB, HBCDD and some PBDEs, and has established concentration limits for all PBDEs in certain electrical goods. Finally, the United States has no federal mandate for the restriction of POPs and has not ratified the annexes to the Convention requiring them to do so. However, thirteen states have implemented their own state-wide concentration limits on a variety of flame retarding chemicals in various commercial applications. Though these limits worldwide are a very positive step for the removal of POP-BFRs from the environment, the increased use of replacement flame retardants renders such legislation only partially effective. The lack of effective screening mechanisms in waste management facilities means that BFR-treated plastics can be inadvertently recycled and remain in circulation. The rise in the use of novel BFRs (NBFRs) can furthermore hinder screening methods currently being developed and the additives themselves may pose similar issues to their predecessors owing to their similar chemical properties. Thus, restrictions on current BFRs will result in the use of new flame retardants, which may in turn be banned and replaced once again. Further research into and development of methods to screen for hazardous chemicals in end of life materials is therefore of the utmost importance. This must be coupled with pro-active legislation that eliminates the need for using such persistent and potentially harmful chemicals in the future.
Deep learning (DL) has the potential to transform medical diagnostics. However, the diagnostic accuracy of DL is uncertain. Our aim was to evaluate the diagnostic accuracy of DL algorithms to ...identify pathology in medical imaging. Searches were conducted in Medline and EMBASE up to January 2020. We identified 11,921 studies, of which 503 were included in the systematic review. Eighty-two studies in ophthalmology, 82 in breast disease and 115 in respiratory disease were included for meta-analysis. Two hundred twenty-four studies in other specialities were included for qualitative review. Peer-reviewed studies that reported on the diagnostic accuracy of DL algorithms to identify pathology using medical imaging were included. Primary outcomes were measures of diagnostic accuracy, study design and reporting standards in the literature. Estimates were pooled using random-effects meta-analysis. In ophthalmology, AUC's ranged between 0.933 and 1 for diagnosing diabetic retinopathy, age-related macular degeneration and glaucoma on retinal fundus photographs and optical coherence tomography. In respiratory imaging, AUC's ranged between 0.864 and 0.937 for diagnosing lung nodules or lung cancer on chest X-ray or CT scan. For breast imaging, AUC's ranged between 0.868 and 0.909 for diagnosing breast cancer on mammogram, ultrasound, MRI and digital breast tomosynthesis. Heterogeneity was high between studies and extensive variation in methodology, terminology and outcome measures was noted. This can lead to an overestimation of the diagnostic accuracy of DL algorithms on medical imaging. There is an immediate need for the development of artificial intelligence-specific EQUATOR guidelines, particularly STARD, in order to provide guidance around key issues in this field.
An energy decomposition analysis (EDA) for single chemical bonds is presented within the framework of Kohn–Sham density functional theory based on spin projection equations that are exact within wave ...function theory. Chemical bond energies can then be understood in terms of stabilization caused by spin-coupling augmented by dispersion, polarization, and charge transfer in competition with destabilizing Pauli repulsions. The EDA reveals distinguishing features of chemical bonds ranging across nonpolar, polar, ionic, and charge-shift bonds. The effect of electron correlation is assessed by comparison with Hartree–Fock results. Substituent effects are illustrated by comparing the C–C bond in ethane against that in bis(diamantane), and dispersion stabilization in the latter is quantified. Finally, three metal–metal bonds in experimentally characterized compounds are examined: a MgI–MgI dimer, the ZnI–ZnI bond in dizincocene, and the Mn–Mn bond in dimanganese decacarbonyl.
Abstract
Lowering of the electron kinetic energy (KE) upon initial encounter of radical fragments has long been cited as the primary origin of the covalent chemical bond based on Ruedenberg’s ...pioneering analysis of H
$_{2}^{+}$$
2
+
and H
2
and presumed generalization to other bonds. This work reports KE changes during the initial encounter corresponding to bond formation for a range of different bonds; the results demand a re-evaluation of the role of the KE. Bonds between heavier elements, such as H
3
C–CH
3
, F–F, H
3
C–OH, H
3
C–SiH
3
, and F–SiF
3
behave in the opposite way to H
$_{2}^{+}$$
2
+
and H
2
, with KE often increasing on bringing radical fragments together (though the total energy change is substantially stabilizing). The origin of this difference is Pauli repulsion between the electrons forming the bond and core electrons. These results highlight the fundamental role of constructive quantum interference (or resonance) as the origin of chemical bonding. Differences between the interfering states distinguish one type of bond from another.
Online customer reviews (OCRs) have become a major source of information for customers in the Internet. Understanding the impact of OCRs on customers' decisions is an important challenge for ...academics and practitioners. We apply a choice-based conjoint experiment that combines all relevant levels of the OCR dimensions (valence, volume, and variance) and that estimates the effect of OCRs on choice. The experimental setting allows us to estimate the direct effects but also the interaction effects of the OCR dimensions, which have been largely neglected in previous research. The impact of the OCR dimensions is evaluated against the results from a control group that did not face OCRs when making their choices. Therefore, our experiment enables us to investigate the extent to which the presence of OCRs affects customers' consideration of brand, price, and technical product attributes. By contrast to previous findings, our results show that volume and variance do not affect customers' choices directly but that they moderate the impact of valence on customers' choices. Moreover, we find that OCRs decrease the importance of brand for customer purchase decisions, indicating that managing OCRs have become a challenge for brand management.
Reactive oxygen species (ROS) are essential for cellular signaling and physiological function. An imbalance between ROS production and antioxidant protection results in a state of oxidative stress ...(OS), which is associated with perturbations in reduction/oxidation (redox) regulation, cellular dysfunction, organ failure, and disease. The pathophysiology of OS is closely interlinked with inflammation, mitochondrial dysfunction, and, in the case of surgery, ischemia/reperfusion injury (IRI). Perioperative OS is a complex response that involves patient, surgical, and anesthetic factors. The magnitude of tissue injury inflicted by the surgery affects the degree of OS, and both duration and nature of the anesthetic procedure applied can modify this. Moreover, the interindividual susceptibility to the impact of OS is likely to be highly variable and potentially linked to underlying comorbidities. The pathological link between OS and postoperative complications remains unclear, in part due to the complexities of measuring ROS- and OS-mediated damage. Exogenous antioxidant use and exercise have been shown to modulate OS and may have potential as countermeasures to improve postoperative recovery. A better understanding of the underlying mechanisms of OS, redox signaling, and regulation can provide an opportunity for patient-specific phenotyping and development of targeted interventions to reduce the disruption that surgery can cause to our physiology. Anesthesiologists are in a unique position to deliver countermeasures to OS and improve physiological resilience. To shy away from a process so fundamental to the welfare of these patients would be foolhardy and negligent, thus calling for an improved understanding of this complex facet of human biology.
The complex cellular interactions that underlie pathologies related to reduced oxygen delivery after surgery are poorly defined and difficult to measure. Heywood and colleagues explored the patterns ...of protein expression in skin biopsies taken from a subgroup of patients enrolled in a randomised trial designed to evaluate perioperative goal-directed therapy. One of their key findings was that a failure of participants to maintain preoperative systemic oxygen delivery was associated with an upregulation of intracellular proteins involved in counteracting oxidative stress. Their study highlights the importance of oxidative stress in the perioperative setting and suggests that maintenance of baseline oxygen delivery might be an important regulator of redox balance.
Increasing human population interacts with local and global environments to deplete biodiversity and resources humans depend on, thus challenging societal values centered on growth and relying on ...technology to mitigate environmental stress. Although the need to address the environmental crisis, central to conservation science, generated greener versions of the growth paradigm, we need fundamental shifts in values that ensure transition from a growth-centered society to one acknowledging biophysical limits and centered on human well-being and biodiversity conservation. We discuss the role conservation science can play in this transformation, which poses ethical challenges and obstacles. We analyze how conservation and economics can achieve better consonance, the extent to which technology should be part of the solution, and difficulties the “new conservation science” has generated. An expanded ambition for conservation science should reconcile day-today action within the current context with uncompromising, explicit advocacy for radical transitions in core attitudes and processes that govern our interactions with the biosphere. A widening of its focus to understand better the interconnectedness between human well-being and acknowledgment of the limits of an ecologically functional and diverse planet will need to integrate ecological and social sciences better. Although ecology can highlight limits to growth and consequences of ignoring them, social sciences are necessary to diagnose societal mechanisms at work, how to correct them, and potential drivers of social change.
Graded index (GRIN) lenses are commonly used for compact imaging systems. It is not widely appreciated that the ion-exchange process that creates the rotationally symmetric GRIN lens index profile ...also causes a symmetric birefringence variation. This property is usually considered a nuisance, such that manufacturing processes are optimized to keep it to a minimum. Here, rather than avoiding this birefringence, we understand and harness it by using GRIN lenses in cascade with other optical components to enable extra functionality in commonplace GRIN lens systems. We show how birefringence in the GRIN cascades can generate vector vortex beams and foci, and how it can be used advantageously to improve axial resolution. Through using the birefringence for analysis, we show that the GRIN cascades form the basis of a new single-shot Müller matrix polarimeter with potential for endoscopic label-free cancer diagnostics. The versatility of these cascades opens up new technological directions.
Recent advances in selected configuration interaction methods have made them competitive with the most accurate techniques available and, hence, creating an increasingly powerful tool for solving ...quantum Hamiltonians. In this work, we build on recent advances from the adaptive sampling configuration interaction (ASCI) algorithm. We show that a useful paradigm for generating efficient selected CI/exact diagonalization algorithms is driven by fast sorting algorithms, much in the same way iterative diagonalization is based on the paradigm of matrix vector multiplication. We present several new algorithms for all parts of performing a selected CI, which includes new ASCI search, dynamic bit masking, fast orbital rotations, fast diagonal matrix elements, and residue arrays. The ASCI search algorithm can be used in several different modes, which includes an integral driven search and a coefficient driven search. The algorithms presented here are fast and scalable, and we find that because they are built on fast sorting algorithms they are more efficient than all other approaches we considered. After introducing these techniques, we present ASCI results applied to a large range of systems and basis sets to demonstrate the types of simulations that can be practically treated at the full-CI level with modern methods and hardware, presenting double- and triple-ζ benchmark data for the G1 data set. The largest of these calculations is Si2H6 which is a simulation of 34 electrons in 152 orbitals. We also present some preliminary results for fast deterministic perturbation theory simulations that use hash functions to maintain high efficiency for treating large basis sets.
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