Deuteration of heptamethine cyanine dyes enhances their emission efficacy.

The design of bright short-wave infrared fluorophores remains a grand challenge. Here we investigate the impact of deuteration on the properties in a series of heptamethine dyes, the absorption of which spans near-infrared and SWIR regions. We demonstrate that it is a generally applicable strategy that leads to enhanced quantum yields of fluorescence, longer-lived singlet excited states and suppressed rates of non-radiative deactivation processes.

Diversifying the dental curriculum: A review of the Bachelor of Dental Surgery degree reading lists in a UK dental school.

INTRODUCTION: Analysis of the diversity of reading lists on courses offered by universities is one way to assess what is being taught and how it shapes our understanding of the world. Very little work has been carried out so far within dentistry on decolonising the curriculum. Existing work looks at the representation of women or ethnic minorities but not at the dental curriculum per se. This article starts to address this. METHODS: The reading lists within the 5 year Bachelor of Dental Surgery curriculum in a large UK dental school were collected and assessed. A data extraction spreadsheet was developed and journal articles on every course reading list across the 5 year curriculum were read in detail. Information on authorship and author affiliations, alongside patient and population representation within the article itself, were collected and collated. RESULTS: We found that there are 2.5 times more male authors than female authors, and almost three times more male lead authors in the articles evaluated. The majority of journal articles included in the reading lists are written by academics and/or clinicians affiliated with institutions in the United Kingdom and most articles are from the global north. In addition, 65% of articles do not specify the focus patient or population group studied. DISCUSSION: It is unlikely that current reading lists within dentistry fully reflect the composition of the profession itself, the variety of knowledge needed to provide evidence-based practice in a globalised oral health arena or the heterogeneous nature of the patient population.

Role of the redox state of the Pirin-bound cofactor on interaction with the master regulators of inflammation and other pathways.

Persistent cellular stress induced perpetuation and uncontrolled amplification of inflammatory response results in a shift from tissue repair toward collateral damage, significant alterations of tissue functions, and derangements of homeostasis which in turn can lead to a large number of acute and chronic pathological conditions, such as chronic heart failure, atherosclerosis, myocardial infarction, neurodegenerative diseases, diabetes, rheumatoid arthritis, and cancer. Keeping the vital role of balanced inflammation in maintaining tissue integrity in mind, the way to combating inflammatory diseases may be through identification and characterization of mediators of inflammation that can be targeted without hampering normal body function. Pirin (PIR) is a non-heme iron containing protein having two different conformations depending on the oxidation state of the iron. Through exploration of the Pirin interactome and using molecular docking approaches, we identified that the Fe2+-bound Pirin directly interacts with BCL3, NFKBIA, NFIX and SMAD9 with more resemblance to the native binding pose and higher affinity than the Fe3+-bound form. In addition, Pirin appears to have a function in the regulation of inflammation, the transition between the canonical and non-canonical NF-κB pathways, and the remodeling of the actin cytoskeleton. Moreover, Pirin signaling appears to have a critical role in tumor invasion and metastasis, as well as metabolic and neuro-pathological complications. There are regulatory variants in PIR that can influence expression of not only PIR but also other genes, including VEGFD and ACE2. Disparity exists between South Asian and European populations in the frequencies of variant alleles at some of these regulatory loci that may lead to differential occurrence of Pirin-mediated pathogenic conditions.

Efficient 2D to 0D Energy Transfer in HgTe Nanoplatelet-Quantum Dot Heterostructures through High-Speed Exciton Diffusion.

Large area absorbers with localized defect emission are of interest for energy concentration via the antenna effect. Transfer between 2D and 0D quantum-confined structures is advantageous as it affords maximal lateral area antennas with continuously tunable emission. We report the quantum efficiency of energy transfer in in situ grown HgTe nanoplatelet (NPL)/quantum dot (QD) heterostructures to be near unity (>85%), while energy transfer in separately synthesized and well separated solutions of HgTe NPLs to QDs only reaches 47 ± 11% at considerably higher QD concentrations. Using Kinetic Monte Carlo simulations, we estimate an exciton diffusion constant of 1-10 cm2/s in HgTe NPLs, the same magnitude as that of 2D semiconductors. We also simulate in-solution energy transfer between NPLs and QDs, recovering an R-4 dependence consistent with 2D-0D near-field energy transfer even in randomly distributed NPL/QD mixtures. This highlights the advantage of NPLs 2D morphology and the efficiency of NPL/QD heterostructures and mixtures for energy harvesting.

FracAtlas: A Dataset for Fracture Classification, Localization and Segmentation of Musculoskeletal Radiographs.

Digital radiography is one of the most common and cost-effective standards for the diagnosis of bone fractures. For such diagnoses expert intervention is required which is time-consuming and demands rigorous training. With the recent growth of computer vision algorithms, there is a surge of interest in computer-aided diagnosis. The development of algorithms demands large datasets with proper annotations. Existing X-Ray datasets are either small or lack proper annotation, which hinders the development of machine-learning algorithms and evaluation of the relative performance of algorithms for classification, localization, and segmentation. We present FracAtlas, a new dataset of X-Ray scans curated from the images collected from 3 major hospitals in Bangladesh. Our dataset includes 4,083 images that have been manually annotated for bone fracture classification, localization, and segmentation with the help of 2 expert radiologists and an orthopedist using the open-source labeling platform, makesense.ai. There are 717 images with 922 instances of fractures. Each of the fracture instances has its own mask and bounding box, whereas the scans also have global labels for classification tasks. We believe the dataset will be a valuable resource for researchers interested in developing and evaluating machine learning algorithms for bone fracture diagnosis.

Surface-modified graphene oxide-based composites for advanced sequestration of basic blue 41 from aqueous solution.

Advanced materials for the efficient treatment of textile wastewater need to be developed for the sustainable growth of the textile industry. In this study, graphene oxide (GO) was modified by the incorporation of natural clay (bentonite) and mixed metal oxide (copper-cobalt oxide) to produce GO-based binary and ternary composites. Two binary composites, GO/bentonite and GO/Cu-Co Ox (oxide), and one ternary composite, GO/bentonite/Cu-Co Ox, were characterized by Fourier transform-infrared spectroscopy (FTIR), scanning electron microscope (SEM), energy dispersive spectrometer (EDS) and Brunauer-Emmett-Teller (BET) analysis. The adsorption efficiency of these composites was evaluated against a cationic dye, Basic Blue 41 (BB41). The composites had several surface functional groups, and the ternary composite had tubular porous structures formed by the cross-linking of the bentonite and GO planes. The BET surface area of the ternary composite was 50% higher than that of the GO. The BB41 removals were 92, 89, 80, and 69% for GO/bentonite/Cu-Co oxide, GO/bentonite, GO and GO/Cu-Co oxide, respectively. The pseudo-2nd-order and intraparticle diffusion models best describe the kinetics results, indicating chemisorption and slow pore diffusion-controlled adsorption processes. The Langmuir isotherm-derived adsorption capacity of GO/bentonite/Cu-Co oxide was 351.1 mg/g, which was very close to the measured value. After five consecutive cycles, the ternary composite retained 90% BB41 removal efficiency compared to its 1st cycle. Electrostatic interaction and pore diffusion were predicted to be the controlling mechanisms for the adsorption of the BB41. The GO-based ternary composite can be a feasible and scalable adsorbent for BB41 in wastewater treatment.

Community health worker-led household screening and management of neonatal hyperbilirubinemia in rural Bangladesh: a cluster randomized control trial protocol.

Background: Extreme hyperbilirubinemia leading to neurologic disability and death is disproportionately higher in low- and middle-income countries (LMIC) such as Bangladesh, and is largely preventable through timely treatment. In LMICs, an estimated half of all newborns are born at home and few receive screening or treatment for hyperbilirubinemia, leading to 6 million newborns per year who need phototherapy treatment for hyperbilirubinemia but are untreated. Household screening and treatment for neonatal hyperbilirubinemia with phototherapy administered by a trained community health worker (CHW) may increase indicated treatment for neonatal hyperbilirubinemia in comparison to the existing care system in Bangladesh. Methods: 530 Bangladeshi women in their second or third trimester of pregnancy from the rural community of Sakhipur, Bangladesh will be recruited for a cluster randomized trial and randomized to the intervention arm - home screening and treatment for neonatal hyperbilirubinemia - or the comparison arm to receive usual care. In the intervention arm, CHWs will provide mothers with two prenatal visits, visit newborns by 2 days of age and then daily for 3 days to measure transcutaneous bilirubin (TcB) and monitor for clinical danger signs. Newborns without danger signs but with a TcB above the treatment threshold, but >15 mg/dL will be treated with light-emitting diode (LED) phototherapy at home. Newborns with danger signs or TcB ≥15 mg/dL will be referred to a hospital for treatment. Treatment rates for neonatal hyperbilirubinemia in each arm will be compared. Conclusion: This study will evaluate the effectiveness of CHW-led home phototherapy to increase neonatal hyperbilirubinemia treatment rates in rural Bangladesh. LMICs are expanding access to postnatal care by using CHWs, and our work will give CHWs a curative treatment option for neonatal hyperbilirubinemia. Similar projects in other LMICs can be pursued to dramatically extend healthcare access to vulnerable newborns with hyperbilirubinemia.

Dental management of patients with sensory impairments.

This article discusses the different types of sensory impairments and their aetiology. It considers how the oral health status in patients with sensory impairments is impacted by their disability and the barriers these patients face in dental care. It also discusses legislation relevant to dental care professionals when caring for patients with disabilities, including the Mental Capacity Act (2005), the Equality Act (2010) and the Accessible Information Standard (2016). Finally, it provides recommendations to dental care professionals on how they can best manage patients with sensory impairments and communicate with them effectively in order to provide them with quality dental care.

Deciphering the role of predicted miRNAs of polyomaviruses in carcinogenesis.

Human polyomaviruses are relatively common in the general population. Polyomaviruses maintain a persistent infection after initial infection in childhood, acting as an opportunistic pathogen in immunocompromised populations and their association has been linked to carcinogenesis. A comprehensive understanding of the underlying molecular mechanisms of carcinogenesis in consequence of polyomavirus infection remains elusive. However, the critical role of viral miRNAs and their potential targets in modifying the transcriptome profile of the host remains largely unknown. Polyomavirus-derived miRNAs have the potential to play a substantial role in carcinogenesis. Employing computational approaches, putative viral miRNAs along with their target genes have been predicted and possible roles of the targeted genes in many significant biological processes have been obtained. Polyomaviruses have been observed to target intracellular signal transduction pathways through miRNA-mediated epigenetic regulation, which may contribute to cancer development. In addition, BKPyV-infected human renal cell microarray data was coupled with predicted target genes and analysis of the downregulated genes indicated that viruses target multiple signaling pathways (e.g. MAPK signaling pathway, PI3K-Akt signaling pathway, PPAR signaling pathway) in the host as well as turning off several tumor suppression genes (e.g. FGGY, EPHX2, CACNA2D3, CDH16) through miRNA-induced mechanisms, assuring cell transformation. This study provides a conceptual framework for the underlying molecular mechanisms involved in the course of carcinogenesis upon polyomavirus infection.

Understanding the Behavior of Monocationic and Dicationic Room-Temperature Ionic Liquids through Resonance Energy-Transfer Studies.

The present work has been undertaken with an objective to understand the differences in the local structural organization of imidazolium-based monocationic ionic liquids (MILs) and dicationic ionic liquids (DILs) through resonance energy-transfer (RET) studies. In this study, a neat IL is used as a donor and a charged species rhodamine 6G (R6G) is used as an acceptor unit because of the fact that they satisfy the spectroscopic criteria that are needed for an RET event to take place. Additionally, R6G, being a charged species, is expected to facilitate the electrostatic interactions with the ILs which are also charged. Specifically, two imidazolium-based germinal DILs and their monocationic counterparts are used for the present investigations. Additionally, the studies are carried out in some selected MILs where the lengths of the alkyl side chains are kept unchanged for MILs and DILs. Interestingly, the present data reveal that the RET interaction is more favorable for DILs than for MILs, even though the DILs are relatively bulkier than their monocationic counterparts. More interestingly, the RET interaction is also found to be more favorable for DILs than for MILs, where the length of the alkyl group is kept fixed for MILs and DILs. The result of the present study delineates that the alkyl chain length on the cation is not the sole factor contributing to the RET outcomes for DILs and MILs but the local structure of DILs also contributes significantly to the same. The current investigation clearly indicates that DILs have a more compact local structure than that of MILs. Essentially, the current study highlights that a cost-effective, noninvasive technique such as RET is quite effective in capturing the differences in the nanostructural organization of MILs and DILs.

Mechanistic Investigation of the Defect Activity Contributing to the Photoluminescence Blinking of CsPbBr3 Perovskite Nanocrystals.

Exploration of the full potential of the perovskite nanocrystals (NCs) for different applications requires a thorough understanding of the pathways of recombination of the photogenerated charge carriers and associated dynamics. In this work, we have tracked the recombination routes of the charge carriers by probing photoluminescence (PL) intermittency of the immobilized and freely diffusing single CsPbBr3 NCs employing a time-tagged-time-resolved method. The immobilized single CsPbBr3 NCs show a complex PL time-trace, a careful analysis of which reveals that nonradiative band-edge recombination through trap states, trion recombination, and trapping of the hot carriers contribute to the blinking behavior of any given NC. A drastically suppressed PL blinking observed for the NCs treated with a tetrafluoroborate salt indicates elimination of most of the undesired recombination processes. A fluorescence correlation spectroscopy (FCS) study on the freely diffusing single NCs shows that enhanced PL and suppressed blinking of the treated particles are the outcome of an increase in per-particle brightness, not due to any increase in the number of particles undergoing "off"-"on" transition in the observation volume. The mechanistic details obtained from this study on the origin of blinking in CsPbBr3 NCs provide deep insight into the radiative and nonradiative charge carrier recombination pathways in these important materials, and this knowledge is expected to be useful for better design and development of bright photoluminescent samples of this class for optoelectronic applications.

Photoluminescence Flickering and Blinking of Single CsPbBr3 Perovskite Nanocrystals: Revealing Explicit Carrier Recombination Dynamics.

To obtain an in-depth understanding of the dynamics and mechanism of carrier recombination in CsPbBr3 nanocrystals (NCs), we have investigated the photoluminescence (PL) of this material at the single-particle level using the time-tagged-time-resolved method. The study reveals two distinct types of PL fluctuations of the NCs, which are assigned to flickering and blinking. The flickering is found to be due to excess surface trap on the NCs, and the flickering single particles are transformed into blinking ones with significant enhancement of PL intensity and stability on postsynthetic surface treatment. Intensity-correlated lifetime analysis of the PL time trace reveals both trap-mediated nonradiative band-edge carrier recombination and positive trion recombination in single NCs. Dynamical and statistical analysis suggests a diffusive nature of the trap states to be responsible for the PL intermittency of the system. These findings throw light on the nature of the trap states, reveal the manifestation of these trap states in PL fluctuation, and provide an effective way to control the dynamics of CsPbBr3 NCs.

Understanding the Microscopic Behavior of Binary Mixtures of Ionic Liquids through Various Spectroscopic Techniques.

In recent times, it has been shown that certain binary mixtures of pure ionic liquids having appropriate chemical composition can behave like a new chemical entity. However, current knowledge about the microscopic behavior of these interesting systems is rather limited. The present study is undertaken with an objective to understand the microscopic behavior in terms of intermolecular interaction, structure, and dynamics of these systems. In the present study, few (IL + IL) mixtures are chosen with a common cation and a variation of anion. The investigations are also carried out by taking individual pure ILs so that the difference in the behavior of pure IL and (IL + IL) mixtures is understood. Initially, the systems have been investigated by studying the thermophysical properties of the concerned mixtures. The synergistic effect between combining pure ILs through photochromism has also been studied. These mixtures have been investigated further through steady-state and time-resolved fluorescence spectroscopy, electron paramagnetic resonance (EPR), nuclear magnetic resonance (NMR), and fluorescence correlation spectroscopy (FCS). Interestingly, time-resolved fluorescence data also pointed out that (IL + IL) mixtures are not only spatially heterogeneous but also dynamically heterogeneous. EPR measurements have suggested that the micropolarity ( ET(30)) of the (IL + IL) mixture is close to that of aliphatic polyalcohols. Measurements of translational diffusion coefficients of the diffusing species through NMR and FCS studies have provided an idea about the nanostructural organization within (IL + IL) binary mixtures. The analysis of data essentially reveals that the mixtures of ILs that are used in the current study do not behave like a nonideal solution. The behavior of the IL mixtures is observed to be more like quasi-ideal type.

A Leap to Hybrid Governance for European Union Healthcare on Organ Donations.

This article evaluates two proposals that the Organs Directive along with the commission's Action Plan 2009-2015 can be viewed as a form of hybrid governance. The Organs Directive is the first legally-binding supranational risk regulation devised in the field of organ donation and transplantation. The Directive is modelled on the earlier Directive dealing with blood, tissue, and cells. The Action Plan, which is soft law, will complement the Directive. The Directive and Action Plan requires additional administration procedures from the Member States with the EU Commission regularly monitoring the implementation of the work programme to ensure it is manageable for them. Before probing the Directive, the Impact Assessment (IA) undertaken by the EU Commission on organ donations, which is used to determine the rationale behind the adoption of the stringent Directive with the Action Plan, will be examined. The social, economic, and health impacts of the four regulatory options available to the Commission will be considered. The Directive and the Action Plan, which are finally adopted, will be discussed in detail, before the arguments are placed highlighting the fact that the Directive and Action Plan display a mode of hybrid governance. Next, the advantages and disadvantages of hybrid governance are laid out and conclusions are drawn as to whether the hybrid model was the best form of action in EU healthcare. In the conclusion, the article proposes the emergence of an "integrated model" within the Organs Directive, which is based on the fusion of the three governance structures: the OMC, comitology, and agencies.

Influence of Divalent Counterions on the Dynamics in DNA as Probed by Using a Minor-Groove Binder.

DNA dynamics, to which water, counterions, and DNA motions contribute, is a topic of considerable interest because it is closely related to the efficiency of biological functions performed by it. Simulation studies and experiments suggest that the counterion dynamics in DNA probed by a minor-groove binder are similar for various monovalent counterions. To date, the influence on DNA dynamics of higher-valence counterions, which are also present around DNA and are known to bind more strongly to it than monovalent ions, has not been studied. Herein we investigated DNA dynamics in the presence of Mg2+ and Ca2+ , chosen for their relative abundance in cells, by using minor-groove binder 4',6-diamidino-2-phenylindole (DAPI) as a fluorescence probe. The dynamics, as measured from the time-resolved fluorescence Stokes shifts of DAPI bound to calf thymus DNA on a subpicosecond-to-nanosecond timescale, were found to be very similar in the presence of both the divalent ions and Na+ ions. The observation is explained by considering the screening of the electric field of the divalent ion by its hydration shell, preferential binding of the ions to the phosphate groups, and displacement of ions from the minor groove by DAPI due to the stronger binding interaction of the latter. Furthermore, the similarity of our results in the presence of Na+ to those reported for smaller oligonucleotides suggests that the chain length of DNA does not influence the DNA dynamics.