Biogenic Polymer-Based Fluorescent Assemblies: Versatile Platforms for Ultrasensitive ATP Detection and Enzyme Assay.

Here, we investigated the optical properties of biocompatible supramolecular assemblies formed through electrostatic interactions between anionic fluorescent dyes and biogenic polymers. The dynamic equilibrium between the monomeric form (fluorescent) and aggregates (nonfluorescent) of dye molecules is responsible for the stimuli-responsive behavior of these polymer composites, which can respond to changes in pH, temperature, and ionic strength. Furthermore, we employed supramolecular assemblies for the purpose of turn-on fluorescence sensing of adenosine triphosphate (ATP) at physiological pH. Notably, no interference was observed even in the presence of well-known competing analytes such as pyrophosphate. In addition to its outstanding selectivity, the present system can detect ATP at concentrations as low as 4.8 nM. The superior detection capabilities are achieved through multiple interactions with biogenic polymers, involving the adenine ring, ribose unit (through hydrogen bonding), and phosphate groups (via charge pairing) of ATP. Given the remarkable sensitivity to ATP, we have applied the present system for the detection of a dephosphorylating enzyme, alkaline phosphatase.

Thiuram Disulfide Mediated Cu-Catalyzed Amidation of Terminal Alkynes: An Efficient Synthesis of Alkynyl Amides.

Terminal alkynes undergo a CO-free aminocarbonylation reaction mediated by thiuram disulfides. Thiuram disulfide acts as the source of the carbamoyl group in the amidation of terminal alkynes in the presence of copper-based reagent and catalyst. A series of alkynyl amides has been prepared with several structural variations following the current one-pot two-step protocol. The reaction proceeds through a mixed disulfide intermediate, which has been isolated and characterized by single-crystal XRD analysis.

Discerning toxic nerve gas agents via a distinguishable 'turn-on' fluorescence response: multi-stimuli responsive quinoline derivatives in action.

We have successfully synthesized quinoline derivatives that exhibit easy scalability and responsiveness to multiple stimuli. These derivatives are capable of forming self-assembled nanoscopic aggregates in an aqueous medium. Consequently, when placed in an aqueous environment, we observe dual fluorescence originating from both twisted intramolecular charge transfer and aggregation-induced emission. The introduction of nerve gas agents, such as diethyl chlorophosphate (DClP) or diethylcyanophosphate (DCNP), to the probe molecules facilitates the charge-transfer process, resulting in a red-shift in absorption maxima. Notably, when operating in fluorescence mode, both of these analytes produce distinct output signals, making them easily distinguishable. DCNP generates a blue fluorescence, while the addition of DClP yields cyan fluorescence. Our mechanistic investigation reveals that the initial step involves phosphorylation of the quinoline nitrogen end. However, in the case of DCNP, the released cyanide ion subsequently attacks the carbonyl carbon centre, forming a cyanohydrin derivative. The response to these target analytes appears to be influenced by the nucleophilicity of the quinoline nitrogen end and the electrophilic nature of the carbonyl unit.

Dynamics of caste and early childbearing in India: a perspective of three decades.

BACKGROUND: Early childbearing disrupts girls' otherwise healthy growth into adulthood and adversely affects their education, livelihood, and health. Individual, sociocultural, economic, environmental, and health service-related factors contribute to childbearing among young females. In India, caste affects health outcomes despite several affirmative policies aimed at improving the health and welfare of the backward castes/tribes. However, there is a dearth of empirical evidence about the impact of caste on early childbearing, more specifically, regarding the trajectory of inter-caste disparities in early childbearing. METHOD: This study used data from all five rounds of the National Family Health Survey (NFHS) in India to assess the association between caste and early childbearing over the last three decades. All women aged 20-24 [NFHS-1 (n = 17,218), NFHS-2 (n = 15,973), NFHS-3 (n = 22,807), NFHS-4 (n = 122,955) and NFHS-5 (n = 118,700)] were considered to create a pooled data set (n = 297,653) for analysis. Bivariate analysis and binary logistic regression were conducted using Stata (v17). ArcMap (v10.8) presented the caste-wise prevalence of early childbearing among the states and Union Territories (UTs). RESULTS: Many women continue to have early childbearing despite a considerable reduction over the last three decades from 47% in 1992-93 to 15% in 2019-21. Compared to NFHS-1, the odds of early childbearing increased by 15% in NFHS-2 and, after that, declined by 42% in NFHS-3 and 64% in NFHS-4 and NFHS-5. The inter-caste disparity in early childbearing persists, albeit with a narrowing gap, with the Scheduled castes (SC) remaining the most vulnerable group. Adjusting the effects of socio-demographic and economic characteristics, SC women had significantly higher odds of early childbearing (OR = 1.07, CI = 1.04-1.11) than those from the General caste. CONCLUSION: To decrease early childbirth, a focus on adolescent marriage prevention and increasing contraceptive use among young SC women is necessary. Strengthening ongoing programs and policies targeting educational and economic empowerment of the socially weaker castes/tribes will help in reducing early childbearing. Efforts to prevent early childbearing will accelerate the achievement of the Sustainable Development Goals (SDGs)-especially those related to health, poverty, nutrition, education, and general wellbeing, in addition to protecting women's reproductive rights.

Immuno-metabolic reprogramming of T cell: a new frontier for pharmacotherapy of Rheumatoid arthritis.

Rheumatoid arthritis (RA) is a persistent autoimmune condition characterized by ongoing inflammation primarily affecting the synovial joint. This inflammation typically arises from an increase in immune cells such as neutrophils, macrophages, and T cells (TC). TC is recognized as a major player in RA pathogenesis. The involvement of HLA-DRB1 and PTPN-2 among RA patients confirms the TC involvement in RA. Metabolism of TC is maintained by various other factors like cytokines, mitochondrial proteins & other metabolites. Different TC subtypes utilize different metabolic pathways like glycolysis, oxidative phosphorylation and fatty acid oxidation for their activation from naive TC (T0). Although all subsets of TC are not deleterious for synovium, some subsets of TC are involved in joint repair using their anti-inflammatory properties. Hence artificially reprogramming of TC subset by interfering with their metabolic status poised a hope in future to design new molecules against RA.

Liposome-Mediated Anti-Viral Drug Delivery Across Blood-Brain Barrier: Can Lipid Droplet Target Be Game Changers?

Lipid droplets (LDs) are subcellular organelles secreted from the endoplasmic reticulum (ER) that play a major role in lipid homeostasis. Recent research elucidates additional roles of LDs in cellular bioenergetics and innate immunity. LDs activate signaling cascades for interferon response and secretion of pro-inflammatory cytokines. Since balanced lipid homeostasis is critical for neuronal health, LDs play a crucial role in neurodegenerative diseases. RNA viruses enhance the secretion of LDs to support various phases of their life cycle in neurons which further leads to neurodegeneration. Targeting the excess LD formation in the brain could give us a new arsenal of antiviral therapeutics against neuroviruses. Liposomes are a suitable drug delivery system that could be used for drug delivery in the brain by crossing the Blood-Brain Barrier. Utilizing this, various pharmacological inhibitors and non-coding RNAs can be delivered that could inhibit the biogenesis of LDs or reduce their sizes, reversing the excess lipid-related imbalance in neurons. Liposome-Mediated Antiviral Drug Delivery Across Blood-Brain Barrier. Developing effective antiviral drug is challenging and it doubles against neuroviruses that needs delivery across the Blood-Brain Barrier (BBB). Lipid Droplets (LDs) are interesting targets for developing antivirals, hence targeting LD formation by drugs delivered using Liposomes can be game changers.

Factors affecting pregnancy registration in India: does the pregnancy intention matter?

BACKGROUND: Pregnancy registration is one of the most critical components of women's reproductive health because it is the gateway to entering the continuum of care services such as antenatal care, institutional delivery, and postnatal care. There is a lack of studies exploring the relationship between pregnancy intention and pregnancy registration, especially in the Indian context. METHOD: This study used the National Family Health Survey-5 (2019-21) data to explore the relationship between birth intention and failure of pregnancy registration. The bivariate and multivariate (binary logistic regression) analysis was carried out. RESULTS: Adjusting the effects of socio-demographic and economic characteristics, compared with women with an intended pregnancy, the odds of failure of pregnancy registration were significantly high among women with a mistimed pregnancy (OR = 1.60, 95% CI = 1.47-1.73) and unwanted pregnancy (OR = 1.38, 95% CI = 1.26-1.52). The study found pregnancy intention as a significant predictor of pregnancy registration. CONCLUSIONS: Results suggest strengthening the interaction of grassroots-level health workers with women, especially those with possibly lower healthcare autonomy and unintended pregnancy. Higher and earlier pregnancy registration will enhance maternal healthcare utilization and reduce adverse health consequences to mothers and children, thus ensuring better maternal and child health.

Examining the influence of Mother-in-law on family planning use in South Asia: insights from Bangladesh, India, Nepal, and Pakistan.

BACKGROUND: Contraceptive use contributes to improved maternal and child health, education, empowerment of women, slow population growth, and economic development. The role of the family in influencing women's health and health-seeking behavior is undergoing significant changes, owing to higher education, media exposure, and numerous government initiatives, in addition to women's enhanced agency across South Asia. Against this backdrop, this study assesses the relationship between women's living arrangements and contraceptive methods used in selected south Asian countries (India, Pakistan, Nepal, and Bangladesh). METHODS: Data of currently married women aged 15-49 from the recent round of Demographic and Health Survey (DHS) of four South Asian countries, i.e., Nepal (2016), Pakistan (2017-18), Bangladesh (2017-18), and India (2019-21) had been used. Bivariate and multinomial logistic regression was performed using Stata with a 5% significance level. RESULTS: Living arrangement of women had a significant association with contraceptive use in South Asia. The Mother-in-law (MIL) influenced the contraceptive method used by the Daughter-in-law (DIL), albeit a country-specific method choice. Modern limiting methods were significantly higher among women living with MIL in India. The use of the modern spacing method was considerably high among women co-residing with husband and/or unmarried child(ren) and MIL in Nepal and India. In Bangladesh, women living with husband and other family member including MIL were more likely to use modern spacing methods.. Women co-residing with the MIL had a higher likelihood of using any traditional contraceptive method in India. CONCLUSIONS: The study suggests family planning program to cover MIL for enhancing their understanding on the benefits of contraceptive use and modifying norms around fertility. Strengthening the interaction between the grassroots level health workers and the MIL, enhancing social network of DIL may help informed choice and enhance the use of modern spacing methods. Women's family planning demands met with modern contraception, and informed contraceptive choices, must also be achieved to reach the 2030 Agenda for Sustainable Development.

Gynecological morbidity and treatment-seeking among older adult (aged 45-59) women in India.

BACKGROUND: Women's gynecological health needs are not limited to the reproductive years of their life. Women are at risk of hormonal changes, gynecological malignancies, and various genitourinary conditions as they move toward menopause and beyond. Concerns about older women's sexual and reproductive health and rights (SRHR) continue to be taboo in many countries, of little interest to researchers and professionals in the field of healthcare, and a "blind spot" in discussions about policy as a whole. Despite the widespread agreement, the life course approach to addressing SRHR concerns has received minimal attention. The study estimates the prevalence, assesses the correlates, and treatment-seeking of gynecological morbidity (GM) among older adult women aged 45-59 years (N = 18,547) in India. METHOD: The analysis was based on the nationally representative Longitudinal Ageing Study (2016-2017) data that adopted a multistage stratified area probability cluster sampling to select respondents. The outcome variables used in this analysis were 'had any GM' and 'sought treatment for any GM.' Women with any morbidity such as per vaginal bleeding, foul-smelling vaginal discharge, uterus prolapses, mood swings/irritability, fibroid/cyst, and dry vagina causing painful intercourse were considered to have any GM. Of the respondents with GM, who sought a doctor's consultation or treatment were considered 'sought treatment for any GM.' Binary logistic regression was conducted to examine the adjusted effect of socioeconomic and demographic predictors of GM and treatment-seeking. Stata (V 16) was used for statistical analyses with a 5% significance level. RESULTS: Fifteen percent of the women had any GM, and only 41% of them sought treatment. Age, marital status, education, number of pregnancies, hysterectomy, involvement in household decision-making, social group, religion, wealth status, and region were significantly associated with GM. The odds of treatment-seeking were higher among women with 10+ years of schooling (OR 1.66, CI 1.23, 2.23), with hysterectomy (OR 7.36, CI 5.92, 9.14), with five-plus pregnancies (OR 1.25, CI 0.96, 1.64), and those from the richest (OR 1.91, CI 1.40, 2.60) households than their respective counterparts. CONCLUSION: Many older adult women experience GM, and treatment-seeking is inadequate. The GM prevalence and treatment-seeking vary considerably by socioeconomic and demographic characteristics. Results suggest community-level awareness generation and the inclusion of this otherwise ignored group in programs targeting better health and wellbeing of women.

Predictors of contraceptive use among young married women in India: Does pregnancy history matter?

AIM: Contraceptive use and its correlates among young women continue to draw research attention due to its implication for fertility reduction, improved maternal and child health, and sexual and reproductive rights. This study explores the association between pregnancy history and contraceptive use among currently married young women (aged 15-24 years at childbirth) in India. METHOD: Data from the National Family Health Survey (2019-2021) was analyzed through STATA with a significance level of 5%. The births in the last 5 years preceding the survey to the women aged 15-24 years at childbirth (n = 127 954) were considered for analysis. Multinomial logistic regression was used to check the unadjusted and adjusted effects of the pregnancy history on contraceptive use. RESULTS: Young women with a history of mistimed pregnancy had significantly lower odds of using modern limiting methods of contraception (odds ratio [OR] = 0.90, confidence interval [CI] = 0.82-0.98), and those with a prior unwanted pregnancy were more likely to use modern limiting methods of contraception (OR = 1.75, CI = 1.57-1.95). CONCLUSION: Pregnancy history influences young married women's current contraceptive use in India. Family planning programs may use the contacts with antenatal, delivery, and post-delivery care system as an opportunity to identify women with an unwanted pregnancy, especially those educationally and economically weaker, for targeted information and service delivery. Better counseling of potential young contraceptive acceptors will ensure informed decision-making and increased use of modern spacing methods.

Exploring the Relationship between Household Structure and Utilisation of Maternal Health Care Services in India.

The role of household structure, especially the mother-in-law (MIL) influencing daughter-in-law's maternal health care (MHC) seeking behaviour, has been a continuing debate due to the former's advantageous position in the household. This study assesses the association of household structure and particularly the presence of MIL with MHC utilisation in India using the National Family Health Survey-4 data (2015-16). The sample of women aged 15-49 years who have given birth during the last five years preceding the survey (n=184,641) was considered for analysis. The outcome variables were full-antenatal care, institutional delivery, and postnatal care. Binary logistic regression was used to check the adjusted effects of the household structure on MHC utilisation. The analyses were done with STATA (version 13) with a significance level of 5%. Adjusting the effects of socio-demographic and economic characteristics, women from non-nuclear households with MIL had higher odds of full-antenatal care (OR= 1.04, CI= 0.99-1.08) and institutional delivery (OR=1.05, CI=1.01- 1.10) than their counterparts from nuclear households. Women from non-nuclear households without MIL had lower chances of postnatal care (OR=0.98, CI=0.96-1.00) than those from nuclear households. The study unearths a very weak association between the presence of MIL in the household and MHC services utilisation of the daughter-in-law, a notable change from the earlier literature often portraying MIL as a barrier.

Degree-Based Graph Entropy in Structure-Property Modeling.

Graph entropy plays an essential role in interpreting the structural information and complexity measure of a network. Let G be a graph of order n. Suppose dG(vi) is degree of the vertex vi for each i=1,2,…,n. Now, the k-th degree-based graph entropy for G is defined as Id,k(G)=-∑i=1ndG(vi)k∑j=1ndG(vj)klogdG(vi)k∑j=1ndG(vj)k, where k is real number. The first-degree-based entropy is generated for k=1, which has been well nurtured in last few years. As ∑j=1ndG(vj)k yields the well-known graph invariant first Zagreb index, the Id,k for k=2 is worthy of investigation. We call this graph entropy as the second-degree-based entropy. The present work aims to investigate the role of Id,2 in structure property modeling of molecules.

Unraveling the Contributions to Spin-Lattice Relaxation in Kramers Single-Molecule Magnets.

The study of how spin interacts with lattice vibrations and relaxes to equilibrium provides unique insights into its chemical environment and the relation between electronic structure and molecular composition. Despite its importance for several disciplines, ranging from magnetic resonance to quantum technologies, a convincing interpretation of spin dynamics in crystals of magnetic molecules is still lacking due to the challenging experimental determination of the correct spin relaxation mechanism. We apply ab initio spin dynamics to a series of 12 coordination complexes of Co2+ and Dy3+ ions selected among ∼240 compounds that largely cover the literature on single-molecule magnets and well represent different regimes of spin relaxation. Simulations reveal that the Orbach spin relaxation rate of known compounds mostly depends on the ions' zero-field splitting and little on the details of molecular vibrations. Raman relaxation is instead found to be also significantly affected by the features of low-energy phonons. These results provide a complete understanding of the factors limiting spin lifetime in single-molecule magnets and revisit years of experimental investigations by making it possible to transparently distinguish Orbach and Raman relaxation mechanisms.

Lattice QCD Equation of State for Nonvanishing Chemical Potential by Resumming Taylor Expansions.

Taylor expansion in powers of baryon chemical potential (µ_{B}) is an oft-used method in lattice QCD to compute QCD thermodynamics for µ_{B}>0. Based only upon the few known lowest order Taylor coefficients, it is difficult to discern the range of µ_{B} where such an expansion around µ_{B}=0 can be trusted. We introduce a resummation scheme for the Taylor expansion of the QCD equation of state in µ_{B} that is based on the n-point correlation functions of the conserved current (D_{n}). The method resums the contributions of the first N correlation function D_{1},…,D_{N} to the Taylor expansion of the QCD partition function to all orders in µ_{B}. We show that the resummed partition function is an approximation to the reweighted partition function at µ_{B}≠0. We apply the proposed approach to high-statistics lattice QCD calculations using 2+1 flavors of Highly Improved Staggered Quarks with physical quark masses on 32^{3}×8 lattices and for temperatures T≈145-176 MeV. We demonstrate that, as opposed to the Taylor expansion, the resummed version not only leads to improved convergence but also reflects the zeros of the resummed partition function and severity of the sign problem, leading to its eventual breakdown. We also provide a generalization of scheme to include resummation of powers of temperature and quark masses in addition to µ_{B}, and show that the alternative expansion scheme of [S. Borsányi et al., Phys. Rev. Lett. 126, 232001 (2021).PRLTAO0031-900710.1103/PhysRevLett.126.232001] is a special case of this generalized resummation.

Impact of the process conditions on polymer pattern morphology during spin coating over topological surfaces.

Micro and nanofabrication techniques depend on the technology of polymer film casting. Spin coating is a relatively robust method to develop uniform polymer films over the substrate surface. However, polymer casting over a topographically prepatterned surface using the spin coating technique is challenging because of the complex transport phenomena involved in the process. Apart from the substrate wettability and the polymer composition, the geometry of the substrate prepatterns affects the polymer phase separation characteristics and thus the morphology of the polymer pattern. In this work the phase separation dynamics during the spinodal decomposition of a polymer-solvent system in a spin coating process is mathematically investigated. The effect of the prepattern topography, substrate wettability, spin-coating rotational speed, and polymer composition on the phase separation dynamics is investigated. The results reveal that the periodicity and phase difference of the polymer peaks with the topography are dependent on the geometric parameters and substrate wettability. The impact of the rotational motion, on the polymer film, is restricted by the surface roughness (due to the topological prepatterns). On reducing the polymer fraction in the solution, the transition from a uniform coating to film defects to isolated patches (wetting to dewetting) occurs. The surface wettability plays a crucial role in topology directed dewetting, which is not observed in flat substrates.

On neighborhood Zagreb index of product graphs.

The properties and activities of chemicals are strongly related to their molecular structures. Topological indices defined on these molecular structures are capable to predict those properties and activities. In this article, a new topological index named as neighborhood Zagreb index (MN ) is presented. Here the chemical importance of the MN index is investigated and it is shown that the newly introduced index is useful in predicting physico-chemical properties with high accuracy compared to some well-established and often used indices. The isomer-discrimination ability of MN is also examined. To demonstrate how the computational formula of the novel index for chemical compounds is simple and convenient, the chemical structures of favipiravir and hydroxychloroquine are used. In addition, some explicit results for this index of different product graphs such as Cartesian, tensor and wreath product are derived. Some of these results are applied to obtain the MN index of some special structures.

Direct Observation of the Reduction of a Molecule on Nitrogen Pairs in Doped Graphene.

Incorporating functional atomic sites in graphene is essential for realizing advanced two-dimensional materials. Doping graphene with nitrogen offers the opportunity to tune its chemical activity with significant charge redistribution occurring between molecules and substrate. The necessary atomic scale understanding of how this depends on the spatial distribution of dopants, as well as their positions relative to the molecule, can be provided by scanning tunneling microscopy. Here we show that a noncovalently bonded molecule such as CoPc undergoes a variable charge transfer when placed on N-doped graphene; on a nitrogen pair, it undergoes a redox reaction with an integral charge transfer whereas a lower fractional charge transfer occurs over a single nitrogen. Thus, the charge state of molecules can be tuned by suitably tailoring the conformation of dopant atoms.

Rotation in an Enantiospecific Self-Assembled Array of Molecular Raffle Wheels.

Tailored nano-spaces can control enantioselective adsorption and molecular motion. We report on the spontaneous assembly of a dynamic system-a rigid kagome network with each pore occupied by a guest molecule-employing solely 2,6-bis(1H-pyrazol-1-yl)pyridine-4-carboxylic acid on Ag(111). The network cavity snugly hosts the chemically modified guest, bestows enantiomorphic adsorption and allows selective rotational motions. Temperature-dependent scanning tunnelling microscopy studies revealed distinct anchoring orientations of the guest unit switching with a 0.95 eV thermal barrier. H-bonding between the guest and the host transiently stabilises the rotating guest, as the flapper on a raffle wheel. Density functional theory investigations unravel the detailed molecular pirouette of the guest and how the energy landscape is determined by H-bond formation and breakage. The origin of the guest's enantiodirected, dynamic anchoring lies in the specific interplay of the kagome network and the silver surface.

Precise Predictions of Charmed-Bottom Hadrons from Lattice QCD.

We report the ground state masses of hadrons containing at least one charm and one bottom quark using lattice quantum chromodynamics. These include mesons with spin (J) and parity (P), (J^{P}): 0^{-}, 1^{-}, 1^{+}, and 0^{+} and the spin 1/2 and 3/2 baryons. Among these hadrons, only the ground state of 0^{-} is known experimentally, and therefore our predictions provide important information for the experimental discovery of all other hadrons with these quark contents.

Mass transfer of a neutral solute in porous microchannel under streaming potential.

The mass transport of a neutral solute in a porous wall, under the influence of streaming field, has been analyzed in this study. The effect of the induced streaming field on the electroviscous effect of the fluid for different flow geometries has been suitably quantified. The overall electroosmotic velocity profile and expression for streaming field have been obtained analytically using the Debye-Huckel approximation, and subsequently used in the analysis for the mass transport. The analysis shows that as the solution Debye length increases, the strength of the streaming field and, consequently, the electroviscous effect diminishes. The species transport equation has been coupled with Darcy's law for quantification of the permeation rate across the porous wall. The concentration profile inside the mass transfer boundary layer has been solved using the similarity transformation, and the Sherwood number has been calculated from the definition. In this study, the variation of the permeation rate and solute permeate concentration has been with the surface potential, wall retention factor and osmotic pressure coefficient has been demonstrated for both the circular as well as rectangular channel cross-section.