Understanding electrocatalytic mechanisms and ultra-trace uranyl detection with Pd nanoparticles electrodeposited in deep eutectic solvents.

This research paper investigates the electrocatalytic mechanisms and ultra-trace detection abilities of uranyl ions (UO22+) using palladium nanoparticles (PdNPs) electrodeposited in deep eutectic solvents (DESs). The unique properties of DESs, such as their adjustable viscosity and ionic conductivity, offer an advantageous and environmentally friendly medium for Pd nanoparticle electrodeposition, resulting in highly active and stable electrocatalysts. Various characterization techniques, including scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD), were used to examine the morphology, size distribution, and crystallographic structure of the Pd nanoparticles. Electrochemical tests revealed that the Pd-modified electrodes show exceptional electrocatalytic activity and current sensitivity towards uranyl ions, with detection limits as low as 3.4 nM. Density functional theory (DFT) calculations were conducted to elucidate the mechanism of the electrocatalytic reduction of UO22+ by the PdNPs, providing a plausible explanation for the high sensitivity of PdNPs in detecting uranyl ions based on the calculated structural parameters and reaction energetics. This study underscores the potential of Pd nanoparticles electrodeposited in DESs as a promising method for sensitive uranyl ion detection, contributing to advancements in environmental monitoring and nuclear safety.

Mechanistic Approach to Reveal Interaction of Uranyl Ions in Alkyltriphenylphosphonium Bromide-Based Deep Eutectic Solvent.

Speciation is known to control fundamental aspects of metal processing and electrochemical behavior such as solubility and redox potentials. Deep eutectic solvents (DESs) are an emerging class of green, low-cost and designer solvents and are being explored as alternatives for recycling nuclear fuel and critical materials. However, there is a lack of knowledge about the behavior of metals in them. Here, for the first time, we synthesized three new DESs based on alkyltriphenylphosphonium bromide (CnPPh3Br), with varied alkyl chain lengths (n), as the hydrogen-bond acceptor along with decanoic acid (DA) as the hydrogen-bond donor and explored the redox speciation of uranyl nitrate. The changes in the Fourier transform infrared and NMR spectra helped elucidate the formation of hydrogen bonds in DES. The absorption maxima of uranyl in DES was red-shifted by 10 nm compared to the free uranyl, with concomitant increase in intensity and luminescence lifetime, which suggested a strong interaction of uranyl nitrate with DES. Cyclic voltammetry was probed to understand the redox thermodynamics, transport properties, and heterogeneous electron transfer kinetics of the irreversible electron transfer of uranyl ions in the three DESs. Electrochemical and spectroscopic techniques together with density functional theory calculations unlocked microscopic insights into the solvation and speciation of UO22+ ions in three DESs and also the associated unusual trends observed in the physical properties of the DESs. The hydrogen-bonded structure of DES plays a crucial role in the redox behavior of the UO22+ ion due to its strong potent complexation with its components. The basic findings of the present work can have far-reaching consequences for the extraction, electrochemical separation, and future development of redox-based separation processes in the nuclear fuel cycle.

Quality of anticoagulation with warfarin in rural Chhattisgarh, India.

Background & objectives: In most of rural India, warfarin is the only oral anticoagulant available. Among patients taking warfarin, there is a strong association between poor control of the international normalized ratio (INR) and adverse events. This study was aimed to quantify INR control in a secondary healthcare system in rural Chhattisgarh, India. Methods: The INR data were retrospectively obtained from all patients taking warfarin during 2014-2016 at a secondary healthcare system in rural Chhattisgarh, India. Patients attending the clinic had their INR checked at the hospital laboratory and their warfarin dose adjusted by a physician on the same day. The time in therapeutic range (TTR) was calculated for patients who had at least two INR visits. Results: The 249 patients had 2839 INR visits. Their median age was 46 yr, and the median body mass index was 17.7 kg/m[2]. They lived a median distance of 78 km (2-3 h of travel) from the hospital. The median INR was 1.7 for a target INR of 2.0-3.0 (n=221) and 2.1 for a target of 2.5-3.5 (n=28). The median TTR was 13.0 per cent, and INR was subtherapeutic 66.0 per cent of the time. Distance from the hospital was not correlated with TTR. Interpretation & conclusions: INR values were subtherapeutic two-thirds of the time, and TTR values were poor regardless of distance from the health centre. Future studies should be done to identify interventions to improve INR control.

Skin delivery of resveratrol encapsulated lipidic formulation for melanoma chemoprevention.

Objective: An unmet need for patient friendly products can be achieved with novel, biocompatible lipidic formulations which encapsulate and prolong release of medicaments. The aim of this study was to develop a commercially scalable resveratrol-loaded solid-lipid microparticulate (SLM) topical gel for melanoma chemoprevention. Methods: Preformulation studies were conducted and drug-excipient interactions examined using infra-red spectroscopy and differential scanning calorimetry (DSC). Resveratrol-loaded SLM topical gel was prepared and evaluated by in vitro and in vivo parameters. Results: Spherical microparticles of 2.98 µm average size were obtained and DSC thermograms provide evidence of trans-resveratrol encapsulation. In vitro and ex vivo drug diffusion studies revealed sustained release profiles. Optimised SLM gel provides optimum antioxidant, tyrosinase inhibition, cytotoxicity in B16F10 melanoma cell line and apoptosis efficacy. In vivo studies on C57BL mice exhibit significant tumour reduction. Conclusion: Promising role of trans-resveratrol-loaded SLM topical gel in melanoma chemoprevention is proven.

Burden & pattern of illnesses among the tribal communities in central India : A report from a community health programme.

Tribals are the most marginalised social category in the country and there is little and scattered information on the actual burden and pattern of illnesses they suffer from. This study provides information on burden and pattern of diseases among tribals, and whether these can be linked to their nutritional status, especially in particularly vulnerable tribal groups (PVTG) seen at a community health programme being run in the tribal areas of Chhattisgarh and Madhya Pradesh States of India. This community based programme, known as Jan Swasthya Sahyog (JSS) has been serving people in over 2500 villages in rural central India. It was found that the tribals had significantly higher proportion of all tuberculosis, sputum positive tuberculosis, severe hypertension, illnesses that require major surgery as a primary therapeutic intervention and cancers than non tribals. The proportions of people with rheumatic heart disease, sickle cell disease and epilepsy were not significantly different between different social groups. Nutritional levels of tribals were poor. Tribals in central India suffer a disproportionate burden of both communicable and non communicable diseases amidst worrisome levels of undernutrition. There is a need for universal health coverage with preferential care for the tribals, especially those belonging to the PVTG. Further, the high level of undernutrition demands a more augmented and universal Public Distribution System.

Deep Eutectic Solvent-Based Highly Sensitive Turn-On Fluorescent Probe for D2O.

Owing to the importance of heavy water in spectroscopy, nuclear energy generation, chemical characterization, and biological industry, a design of a robust, cheap, nontoxic, and sensitive D2O sensor is very important. In this work, taking advantage of the singular emission fluorescence of the deep eutectic solvent prepared in our laboratory, we propose a first of its kind highly sensitive turn-on fluorescent sensor to effectively sense D2O at an ultratrace level based on rapid exchange of the labile DES proton with deuterium. This method can be used as a full-range heavy water detection strategy with a limit of detection of 0.079% (v/v) or 870 ppm. The isotopic purity (IP) obtained from DES fluorescence measurements is also in close agreement with that of the conventional FT-IR method. The current DES-based sensor thus allows both sensing and isotopic purity of D2O and can serve as one of the most sensitive monitoring strategies for heavy water analysis.

Understanding the excited state dynamics and redox behavior of highly luminescent and electrochemically active Eu(III)-DES complex.

Deep eutectic solvents (DES) are considered a novel class of environmentally benign molecular solvents that are considered as potential solvents for nuclear fuel reprocessing, material recycling, and many other technological applications in both research and industry. However, there is a complete dearth of understanding pertaining to the behavior of metal ions in DES. Herein, we have investigated the speciation, complexation behavior, photochemistry, and redox properties and tried to obtain insight into the chemical aspects of the europium ion in DES (synthesized from heptyltriphenylphosphonium bromide and decanoic acid). The same has been probed using time-resolved photoluminescence (TRPL), cyclic voltammetry (CV), synchrotron-based extended X-ray absorption fine structure (EXAFS) spectroscopy, and density functional theory (DFT) calculations. TRPL indicated the stabilization of europium in the +3 oxidation state, favoring the potential of the Eu(III)-DES complex to emit red light under near UV excitation and the existence of inefficient energy transfer between DES and Eu3+. EXAFS analysis revealed the presence of Eu-O and Eu-Br, which represent the local surroundings of Eu3+ in the Eu(III)-DES complex. TRPL measurement has also suggested two distinct local environments of europium ions in the complex. DFT calculations supported the EXAFS findings, confirming that the Eu(III)-DES structure involves not only the oxygen atom of decanoic acid but also the oxygen atoms from the nitrate ions, contributing to the local coordination of Eu(III). Electrochemical studies demonstrated that the redox reaction of Eu(III)/Eu(II) in DES displays quasi-reversible behavior. The reaction rate was observed to increase with higher temperatures. The findings of this study can contribute to the understanding of the fundamental properties and potential applications of this luminescent and electrochemically active complex and pave the way for further studies and the development of novel materials with enhanced luminescent and electrochemical properties.

Epidemiology of heart failure in rural Chhattisgarh, India.

Background Cardiovascular diseases, including heart failure (HF), are leading causes of death and disability in India. However, most studies in India only include urban populations or rural regions with improved access and may not represent the poorest patients or regions. We studied the epidemiology of HF patients admitted to a secondary care hospital in rural Chhattisgarh, India. Methods We did a retrospective chart review of patients hospitalized with HF in 2018 to obtain their demographic data and risk factors for developing HF. We reviewed echocardio-grams to assign patients to their most probable HF category. Results We studied 88 HF patients with a mean age of 42 years including 55 (62.5%) women. The most common categories of HF were cardiomyopathy (36.8%), rheumatic heart disease (RHD; 25.3%) and right heart failure (RHF; 18.4%). Prior tuberculosis was more prevalent in patients with RHF compared with other types of HF (43.8% v. 13.9%). Conclusions HF patients in this study from rural central India were young and predominantly women. Cardiomyopathy, RHD and RHF due to past tuberculosis were common causes of HF in this population. Further studies are needed to expand upon these single centre findings to better understand the risk factors and outcomes of HF among the rural poor.

Ethical qualms while treating diabetes in low-resource areas.

Diabetes care in low-resource rural areas is often compromised by access and finance barriers, leading to ethical dilemmas for physicians in diagnosis and treatment. Rural health workers should be educated on how poverty, disproportionate rural health infrastructure, and illiteracy impact diabetes care to facilitate a paradigm shift from blaming patients for poor adherence to improving health systems in order to address underlying structural care seeking barriers of cost, distance and social stigma. With these barriers urban, high resource protocols cannot be implemented and there is need for separate evidence-based protocols for rural, low resource populations. Having such set protocols coupled with continuous training and use of mobile/telemedicine technology could help shifting tasks to nurses and peripheral health workers. The National Programme For Prevention And Control Of Cancer, Diabetes, Cardiovascular Diseases & Stroke may benefit from this communitising care model by setting up PHC-level NCD clinics run by trained nurses and health workers with physician backup using technology as needed. This way of utilizing non-physician health workers to treat uncomplicated diabetes patients may not only allow physicians quality time and more resources to treat complicated diabetes patients but also provide good quality, accessible care within everyone's reach.

The ethics of compulsory notification of tuberculosis.

The Government of India has passed a notification making the non-reporting of tuberculosis (TB) by a clinical establishment a punishable offence. This article examines this move from an ethical standpoint. One of the main ethical concerns relates to the violation of patient confidentiality that may result from this. Also as regards improvement in patient care, there appears to be a poor cost-benefit ratio in terms of the actionable data obtained by this There may be possible adverse consequences by a limiting of access to care due to penalising of non-reporting. In terms of the bigger picture, the notification may lead to an increased tension between the private sector and Government. Moreover, it is the position of the authors that such a step distracts attention from the more important issues that plague TB care in India today.

A prospective study evaluating the impact of cartridge-based nucleic acid amplification test (CBNAAT) on the management of tuberculosis in a low-resource high-burden Indian rural setting.

BACKGROUND: The cartridge-based nucleic acid amplification test (CBNAAT) Xpert MTB/RIF is more sensitive than smear microscopy for the diagnosis of tuberculosis (TB). It is also more expensive, costing 1450 INR as compared to 10 INR per smear. OBJECTIVES: We conducted a prospective study to evaluate the impact of CBNAAT results on patient management in our low-resource, high-burden Indian rural setting. MATERIALS AND METHOD: Between February and July 2017, clinicians were asked to complete one questionnaire at the time of CBNAAT request and another when reviewing the result. The first questionnaire, "Form 1," concerned pretest treatment status and asked clinicians to rate their confidence in the diagnosis. "Form 2" concerned postresult treatment and investigation plan. RESULTS: Over the study period, 206 CBNAATs were requested. Form 1 was not completed for 85 patients and 21 were excluded leaving 100 in the main analysis. MTB was detected (MTB-D) in 60 of 100 (60%) of samples tested. At the time of CBNAAT request, 56 of 100 (56%) of patients were already on treatment, this being empirical in 34 of 100 (34%). Despite this, 17 of 60 (28.3%) of MTB-D results occurred in patients not yet started on treatment. Postresult treatment status was available for 94 of 100 CBNAATs (55 MTB-D and 39 MTB-ND). Following an MTB-D result, all 17 patients not on treatment started and all 38 on so already continued. Following an MTB Not Detected (MTB-ND) result, 26 of 27 (96.3%) of patients not yet on treatment remained so, but only 2 of 12 (16.7%) already on treatment stopped. Even where the clinician's pretest confidence in TB was low, 9of 30 (30%) of CBNAAT results were MTB-D. CONCLUSION: In a low-resource high-burden setting, CBNAAT may have greatest impact where the clinician's pretest confidence in TB is low and empirical treatment has not been started. This is because MTB-D results will lead to appropriate initiation of treatment and MTB-ND results may enable clinicians to hold-off treatment.

Predictors of tuberculosis treatment outcomes among a retrospective cohort in rural, Central India.

INTRODUCTION: Programmatic design affects access to healthcare and can influence tuberculosis treatment outcomes. Potential predictors of tuberculosis treatment outcomes in one rural Indian setting were examined to improve outcomes with a focus on access to care. METHODS: Routinely collected tuberculosis treatment data from Jan Swasthya Sahyog, a community based healthcare system in rural Chhattisgarh, India were examined from 2003-2015. Predictors were analyzed for associations with death, loss to follow-up or failure in multivariable logistic regression models. The effect of distance from treatment on outcomes was graphed and Pearson's correlation coefficients (r2) calculated. Descriptive time to event analyses were performed for all deaths and loss to follow-up from January 2010 to September 2015. RESULTS: 4979 patients with active TB were treated during the study period. Patients were mostly male, malnourished, diagnosed with pulmonary disease and many travelled lengthy distances. Positive treatment outcomes improved from 55% to 80% from 2003 to 2015 for all patients though positive treatment outcomes have been above 80% in the primary care setting since 2012. The annual case fatality rate was 4.4% with small yearly variation.Gender and site of treatment (primary versus secondary care facility) and also season of treatment initiation and travel time to care best predicted outcomes in both the complete model and model which included only patients with initial BMI data. No differences were found between primary and secondary care patients for initial BMI, percentage of sputum positivity among those with pulmonary disease and grade of sputum positivity among the sputum positive. Those who traveled the furthest to access care achieved the worst outcomes during the summer and, to a lesser degree, the monsoon. Distance from care was associated with treatment outcomes in a dose-response manner out to substantial distances. From 2010 to 2015, most patients who died or were lost to follow-up did so in the first week of treatment. CONCLUSIONS: The provision of care through local facilities improves the treatment of tuberculosis in rural India. Interventions addressing death or loss to follow-up should focus on the newly diagnosed. Rural Indian physicians should be aware of how access issues affect TB treatment outcomes.

Sustaining for-profit emergency healthcare services in low resource areas.

The Bawaskars in their Comment "Emergency care in rural settings: Can doctors be ethical and survive?" raise a context-specific question about the sustainability of emergency care in rural, low resource areas. This could be broadened to "What efforts are needed to sustain emergency care systems run by the private sector in rural, low resource areas without catastrophically affecting patients or healthcare providers?" There are enough constitutional, legal and ethical imperatives to state that all emergency care should be available to everyone irrespective of paying capacity. The State should be responsible for providing emergency care via the public sector or for strategically purchasing it from private providers. Even if that arrangement is not viable, private sector providers cannot expect the community to underwrite the sustainability of such services and the return on investment in their training. Finally, we suggest that the principles of ethics cannot be invoked for justifying the financial viability and sustainability of the private sector in an unequal world.

Early outcomes of radiofrequency ablation in unresectable metastatic colorectal cancer from a tertiary cancer hospital in India.

AIMS: The study was carried out to evaluate the early outcomes using Radiofrequency Ablation (RFA) for unresectable liver metastases in the management of metastatic colorectal cancer (mCRC) from an area of low endemicity. MATERIAL AND METHODS: 60 Patients with unresectable colorectal liver metastases had undergone 88 sessions of RFA from January 2007 till December 2013. The results were retrospectively analysed to evaluate the outcomes in terms of efficacy and survival rates. RESULTS: The median follow up of patients in our series was 24.8months. 35/52 (67.3%) patients had complete response at 3 months while 8 patients were lost to follow up. Of the 17 patients who had recurrence, 4 (23.5%) were at the ablated site while 13 patients (76.4%) progressed elsewhere. Abdominal pain was commonest post procedural symptom (20%). There was no procedure related mortality or any major complications. Mean disease free interval and Progression free survival was 6.7 and 13.1 months. Estimated median survival in patients with liver limited disease and those with small lesion (<3cm) was 3.79 years and 3.45 years respectively. Median survival in patients with lesion size 3-5 cms was 1.5 years. Annual survival rates would be 94.5%, 55.2% and 26.2% for 1, 3 and 5 years. CONCLUSION: Radiofrequency ablation of unresectable liver metastases is effective in treatment of mCRC. Estimated survival rates and Annual survival rates at our institute from the low endemic region also follow the global trend. Size of the lesion was an important predictor of efficacy of RFA. Presence of extrahepatic disease and lesion size >3 cm was associated with decreased survival.

Approaches and Recent Trends in Gene Delivery for Treatment of Atherosclerosis.

BACKGROUND: The development and progression of atherosclerosis is known to occur at a sluggish pace and the lesions remain concealed for a long duration before the factual situation of the complex atherosclerotic etiology affecting various organ gets apprehended. The root cause mainly involves an imbalance or malfunction of the cholesterol metabolizing pathway. The till date therapeutic alternatives include oral hypo-lipidemic agents along with advances made in biotechnology/tissue engineering and surgical procedures for management purpose. However, with the advent and upsurge of nanotech delivery systems, along with meticulous indulgence and identification of the causative genes in the etiology of disease have opened a new therapeutic area that has far reaching application potential for effective management of such chronic disease requiring lifelong therapy. METHODS: Various genes that have implication in atherosclerosis were reviewed along with research in delivery vectors that have been employed for gene therapeutics and hurdles in successful delivery were elaborated. Relevant patents are discussed systematically to clearly support and highlight the developments made. RESULTS: Patenting activity in the delivery of genes for atherosclerosis so far primarily covers use of viral vectors. With the identification of new targets, a list of candidate genes are available that can be potentially exploited for therapeutic purpose. Though the delivery of candidate genes using viral vectors has been well explored, the limitation of viral vectors have seized the much needed clinical success. Non-viral vectors can prove to be the key for conquering this limitations and offer a vast area for exploration for achieving an effective control and remission to the disease and increasing the assortment of patents as reviewed in this article. CONCLUSION: In view of the many limitations in employing viral vectors for delivery, designing non-viral vectors for successful delivery of therapeutic gene in atherosclerosis should be realized and focused for effective management of the disease.

Design of novel assessment techniques for opioid dependent patients.

Assessment of opioid dependent patients in a replacement program has traditionally relied on conventional methods such as urine testing or face to face examination with a physician. We are introducing new assessment techniques based on pupillometry, reaction time and slurring of speech. The pupillometry test uses a webcam, controlled lighting and customized software to measure pupil parameters. The reaction time test uses a push-button to detect time to respond to a visual stimulus. The slurred speech test involves detection of slurring of a set of individual test words. These three tests will be combined to provide the physician with an objective "sedation index" for patients. These techniques will be used with remote dispensing technology currently under development.