Dual functioning by the PhoR sensor is a key determinant to Mycobacterium tuberculosis virulence.

PhoP-PhoR, one of the 12 two-component systems (TCSs) that empower M. tuberculosis to sense and adapt to diverse environmental conditions, remains essential for virulence, and therefore, represents a major target to develop novel anti-TB therapies. Although both PhoP and PhoR have been structurally characterized, the signal(s) that this TCS responds to remains unknown. Here, we show that PhoR is a sensor of acidic pH/high salt conditions, which subsequently activate PhoP via phosphorylation. In keeping with this, transcriptomic data uncover that acidic pH- inducible expression of PhoP regulon is significantly inhibited in a PhoR-deleted M. tuberculosis. Strikingly, a set of PhoP regulon genes displayed a low pH-dependent activation even in the absence of PhoR, suggesting the presence of non-canonical mechanism(s) of PhoP activation. Using genome-wide interaction-based screening coupled with phosphorylation assays, we identify a non-canonical mechanism of PhoP phosphorylation by the sensor kinase PrrB. To investigate how level of P~PhoP is regulated, we discovered that in addition to its kinase activity PhoR functions as a phosphatase of P~PhoP. Our subsequent results identify the motif/residues responsible for kinase/phosphatase dual functioning of PhoR. Collectively, these results uncover that contrasting kinase and phosphatase functions of PhoR determine the homeostatic mechanism of regulation of intra-mycobacterial P~PhoP which controls the final output of the PhoP regulon. Together, these results connect PhoR to pH-dependent activation of PhoP with downstream functioning of the regulator. Thus, PhoR plays a central role in mycobacterial adaptation to low pH conditions within the host macrophage phagosome, and a PhoR-deleted M. tuberculosis remains significantly attenuated in macrophages and animal models.

Functional and transcriptional heterogeneity within the massively expanding HLADR+CD38+ CD8 T cell population in acute febrile dengue patients.

IMPORTANCE: CD8 T cells play a crucial role in protecting against intracellular pathogens such as viruses by eliminating infected cells and releasing anti-viral cytokines such as interferon gamma (IFNγ). Consequently, there is significant interest in comprehensively characterizing CD8 T cell responses in acute dengue febrile patients. Previous studies, including our own, have demonstrated that a discrete population of CD8 T cells with HLADR+ CD38+ phenotype undergoes massive expansion during the acute febrile phase of natural dengue virus infection. Although about a third of these massively expanding HLADR+ CD38+ CD8 T cells were also CD69high when examined ex vivo, only a small fraction of them produced IFNγ upon in vitro peptide stimulation. Therefore, to better understand such functional diversity of CD8 T cells responding to dengue virus infection, it is important to know the cytokines/chemokines expressed by these peptide-stimulated HLADR+CD38+ CD8 T cells and the transcriptional profiles that distinguish the CD69+IFNγ+, CD69+IFNγ-, and CD69-IFNγ- subsets.

Electrostatically Engineered Tetraphenylethylene-Based Fluorescence Sensor for Protamine and Trypsin: Leveraging Aggregation-Induced Emission for Enhanced Sensitivity and Selectivity.

The accurate detection of Protamine and Trypsin, two biomolecules with significant clinical and biological relevance, presents a substantial challenge because of their structural peculiarities, low abundance in physiological fluids, and potential interference from other substances. Protamine, a cationic protein, is crucial for counteracting heparin overdoses, whereas Trypsin, a serine protease, is integral to protein digestion and enzyme activation. This study introduces a novel fluorescence sensor based on a (4-(1,2,2-tris(4-phosphonophenyl)vinyl)phenyl)phosphonic acid octasodium salt (TPPE), leveraging aggregation-induced emission (AIE) characteristics and electrostatic interactions to achieve selective and sensitive detection of these biomolecules. Through comprehensive optical characterization, including ground-state absorption, steady-state, and time-resolved emission spectroscopy, the interaction mechanisms and aggregation dynamics of TPPE with Protamine and Trypsin were elucidated. The sensor exhibits very high sensitivity (LOD: 1.45 nM for Protamine and 32 pM for Trypsin), selectivity, and stability, successfully operating in complex biological matrices, such as human serum and urine. Importantly, this sensor design underscores the synergy between the AIE phenomena and biomolecular interactions, offering a promising alternative for analytical applications in biomedical research and clinical diagnostics. The principles outlined herein open new avenues for the development of other AIE-based sensors, expanding the toolkit available for detecting a wide range of biomolecules using similar design strategies.

Multi-Facet analysis of analytical and numerical models to resolve sustainable artificial recharge rates in unconfined aquifers.

Managed aquifer recharge (MAR) has emerged as a potential solution to resolve water insecurity, globally. However, integrated studies quantifying the surplus source water, suitable recharge sites and safe recharge capacity is limited. In this study, a novel methodology is presented to quantify transient injection rates in unconfined aquifers and generate MAR suitability maps based on estimated surplus water and permissible aquifer recharge capacity (PARC). Subbasin scale monthly surplus surface runoff was estimated at 75% dependability using a SWAT model. A linear regression model based on numerical solution was used to capture the aquifer response to injection and to calculate PARC values at subbasin level. The available surplus runoff and PARC values was then used to determine the suitable site and recharge rate during MAR operation. The developed methodology was applied in the semi-arid region of Lower Betwa River Basin (LBRB), India. The estimated surplus runoff was generally confined to the monsoon months of June to September and exhibited spatial heterogeneity with an average runoff rate of 5000 m3/d in 85% of the LBRB. Analysis of the PARC results revealed that thick alluvial aquifers had large permissible storage capacity and about 50% of the LBRB was capable of storing over 3500 m3/d of water. This study revealed that sufficient surplus runoff was generated in the LBRB, but it lacked the adequate safe aquifer storage capacity to conserve it. A total 65 subbasins was identified as the best suited sites for MAR which had enough surplus water and storage capacity to suffice 20% of the total water demand in the LBRB. The developed methodology was computationally efficient, could augment the field problem of determining scheduled recharge rates and could be used as a decision-making tool in artificial recharge projects.

Mitochondria-Directing Fluorogenic Probe: An Efficient Amyloid Marker for Imaging Lipid Metabolite-Induced Protein Aggregation in Live Cells and Caenorhabditis elegans.

The design and development of optical probes for sensing neurotoxic amyloid fibrils are active and important areas of research and are undergoing continuous advancements. In this paper, we have synthesized a red emissive styryl chromone-based fluorophore (SC1) for fluorescence-based detection of amyloid fibrils. SC1 records exceptional modulation in its photophysical properties in the presence of amyloid fibrils, which has been attributed to the extreme sensitivity of its photophysical properties toward the immediate microenvironment of the probe in the fibrillar matrix. SC1 also shows very high selectivity toward the amyloid-aggregated form of the protein as compared to its native form. The probe is also able to monitor the kinetic progression of the fibrillation process, with comparable efficiency as that of the most popular amyloid probe, Thioflavin-T. Moreover, the performance of SC1 is least sensitive to the ionic strength of the medium, which is an advantage over Thioflavin-T. In addition, the molecular level interaction forces between the probe and the fibrillar matrix have been interrogated by molecular docking calculations which suggest the binding of the probe to the exterior channel of the fibrils. The probe has also been demonstrated to sense protein aggregates from the Aß-40 protein, which is known to be responsible for Alzheimer's disease. Moreover, SC1 exhibited excellent biocompatibility and exclusive accumulation at mitochondria which allowed us to successfully demonstrate the applicability of this probe to detect mitochondrial-aggregated protein induced by an oxidative stress indicator molecule 4-hydroxy-2-nonenal (4-HNE) in A549 cell lines as well as in a simple animal model like Caenorhabditis elegans. Overall, the styryl chromone-based probe presents a potentially exciting alternative for the sensing of neurotoxic protein aggregation species both in vitro as well as in vivo.

Mannose-binding lectin gene 2 variant DD (rs 5030737) is associated with susceptibility to COVID-19 infection in the urban population of Patna City (India).

The study aimed to measure plasma levels of Mannose-Binding Lectin (MBL) and MBL-associated serine protease-2 (MASP-2) and their polymorphisms in COVID-19 patients and controls to detect association. As MBL is a protein of immunological importance, it may contribute to the first-line host defence against SARS-CoV-2. MBL initiates the lectin pathway of complement activation with help of MASP-1 and MASP-2. Hence, appropriate serum levels of MBL and MASPs are crucial in getting protection from the disease. The polymorphisms of MBL and MASP genes affect their plasma levels, impacting their protective function and thus may manifest susceptibility, extreme variability in the clinical symptoms and progression of COVID-19 disease. The present study was conducted to find plasma levels and genetic variations in MBL and MASP-2 in COVID-19 patients and controls using PCR-RFLP and ELISA, respectively.The present study was conducted to find plasma levels and genetic variations in MBL and MASP-2 in COVID-19 patients and controls using PCR-RFLP and ELISA, respectively. Our results indicate that median serum levels of MBL and MASP-2 were significantly low in diseased cases but attained normal levels on recovery. Only genotype DD was found to be associated with COVID-19 cases in the urban population of Patna city.

Guest Binding with Sulfated Cyclodextrins: Does the Size of Cavity Matter?

Sulfated cyclodextrins have recently emerged as potential candidates for producing host-induced guest aggregation with properties better than p-sulfonatocalixarenes that have previously shown numerous applications involving the phenomena of host-induced guest aggregation. In the class of sulfated cyclodextrins (SCD), sulfated ß-cyclodextrin (ß-SCD) remains the most extensively investigated host molecule. Although it is assumed that the host-induced guest aggregation is predominantly an outcome of interaction of the guest molecule with the charges on the exterior of SCD cavity, it has not been deciphered whether the variation in the cavity size will make a difference in the efficiency of host-induced guest-aggregation process. In this investigation, we present a systematic study of host-induced guest aggregation of a cationic molecular rotor dye, Thioflavin T (ThT) with three different sulfated cyclodextrin molecules, α-SCD, ß-SCD and γ-SCD, which differ in their cavity size, using steady-state emission, ground-state absorption and time-resolved emission measurements. The obtained photophysical properties of ThT, upon interaction with different SCD molecules, indicate that the binding strength of ThT with different SCD molecules correlate with the cavity size of the host molecule, giving rise to the strongest complexation of ThT with the largest host molecule (γ-SCD). The binding affinity of ThT towards different host molecules has been supported by molecular docking calculations. The results obtained are further supported with the temperature and ionic strength dependent studies performed on the host-guest complex. Our results indicate that for host-induced guest aggregation, involving oppositely charged molecules, the size of the cavity also plays a crucial role beside the charge density on the exterior of host cavity.

Thioflavin-T-Incorporated Cerium-ATP Coordination Polymer Nanoparticles: A Promising System for Detection of Uranyl Ion (UO22+) in Aqueous Medium.

Lanthanide-based coordination polymer nanoparticles (Ln-CPNs) are studied for analytical and biomedical sensing, mainly utilizing the luminescent properties of lanthanides. However, the inclusion of fluorescent guest molecules within the nanoparticles can lead to a stimuli-responsive system with modulated photo-physical properties that can be useful for detecting analytes. In this work, we have synthesized cerium(III) coordination polymer nanoparticles using adenosine triphosphate (ATP) molecules as the ligands. The porous polymeric structure enables CPNs for reversible inclusion and release of thioflavin-T (ThT), which is a weakly emissive dye in the free state but becomes highly emissive when incorporated into the Ce-ATP CPNs. Modulation of the photo-physical properties of ThT-incorporated CPNs in response to the radiotoxic and environmentally alarming uranyl ion (UO22+) has been used for its detection in aqueous medium in the range of 0-20 µM by fluorimetry with an LOD of 80 ng mL-1 (0.34 µM) in deionized water without interference from the most commonly occurring metal ions. Furthermore, the sensing platform has been successfully utilized for UO22+ determination in seawater sample without any pre-treatment and adjustment of pH.

Methods of Determining Irritable Bowel Syndrome and Efficiency of Probiotics in Treatment: A Review.

Background: Irritable bowel syndrome (IBS) is a prevalent lifestyle-associated ailment linked to the gut microbiota that significantly influences patients' quality of life. A notable correlation exists between Blastocystis infections and susceptibility to IBS, with infected individuals exhibiting an increased likelihood of developing the condition. Despite promising results from using probiotics to modulate the gut microbiota and manage IBS, the precise mechanisms and potential risks remain unclear. Objective: This review aims to explore the therapeutic potential of probiotics, particularly Saccharomyces boulardii, in the management of IBS, highlighting the role of the gut microbiota and the gut-brain axis in IBS pathophysiology. Methods: A comprehensive literature survey was conducted to examine the association between gut microbiota and IBS, the role of probiotics in managing IBS, the mechanisms of their action, and the potential risks associated with their long-term use. Additionally, this study addresses the influence of Blastocystis infections on IBS susceptibility and evaluates various ongoing clinical trials investigating probiotic use for IBS. Results: S boulardii, a yeast species with probiotic properties, has demonstrated effectiveness in both the treatment and prophylaxis of IBS. Its administration is associated with a decrease in the proinflammatory cytokine interleukin 8 and an increase in the anti-inflammatory cytokine interleukin 10. Probiotics appear to function by inhibiting the growth of pathogenic microorganisms and regulating neurotransmitter activity, influencing the gut-brain axis. However, selecting appropriate probiotic strains and dosing regimens is crucial because of potential adverse effects, such as infections and allergic reactions. Conclusions: Probiotics, specifically S boulardii, offer a promising avenue for IBS management by modulating gut microbiota. However, further research is necessary to delineate the precise mechanisms of action, optimal strains, dosing regimens for IBS treatment, and potential risks associated with long-term use. A comprehensive approach incorporating probiotics, a low-FODMAP diet, and cognitive-behavioral therapy may provide effective management of IBS symptoms.

Evaluation of C4b as an adjunct marker in symptomatic RT-PCR negative Covid-19 cases.

Introduction: Detecting low viral load has been a challenge in this pandemic, which has led to its escalated transmission. Complement activation has been implicated in pathogenesis of Covid-19 infection. Thus, evaluation of complement activation in suspected Covid-19 infection may help to detect infection and limit false negative cases thus limiting transmission of infection. We speculate that measuring C4b, produced from an activated complement system due to the presence of Covid-19 may help in its detection, even when the viral titers are low. Methods: Plasma C4b levels of symptomatic RT-PCR positive patients (cases, n = 40); symptomatic RT-PCR negative patients (n = 35) and asymptomatic RT-PCR negative controls (n = 40) were evaluated. Plasma C5b-9, IL-6, D-dimer and C1-Inhibitor (C1-INH) were also measured in cases and controls. ELISA kits were used for all measurements. Statistical analyses were carried out using Stata, version 12 (Stata Corp., Texas, USA). Results: C4b levels were found to be significantly increased in RT-PCR positive patients as compared to asymptomatic RT-PCR negative controls. RT-PCR negative but symptomatic patients still showed increased C4b levels. The significantly higher levels of C4b in cases with a cut-off value of ≥ 116 ng/ml with optimum sensitivity and specificity of 80% and 52% respectively is indicative of its possible use as an adjunct marker. Increased levels of D-dimer, IL6, along with decreased levels of C1-INH were found in cases compared to controls. Whereas, C5b-9 levels were not significantly raised in cases. Conclusions: The results of our study suggests that plasma C4b may help to detect infection in false negative cases of RT-PCR that escape detection owing to low viral load. However, to confirm it a large-scale study is needed. Supplementary Information: The online version contains supplementary material available at 10.1007/s12291-022-01033-z.

Immunophenotyping and Transcriptional Profiling of Human Plasmablasts in Dengue.

Plasmablasts represent a specialized class of antibody-secreting effector B cells that transiently appear in blood circulation following infection or vaccination. The expansion of these cells generally tends to be massive in patients with systemic infections such as dengue or Ebola that cause hemorrhagic fever. To gain a detailed understanding of human plasmablast responses beyond antibody expression, here, we performed immunophenotyping and RNA sequencing (RNA-seq) analysis of the plasmablasts from dengue febrile children in India. We found that plasmablasts expressed several adhesion molecules and chemokines or chemokine receptors that are involved in endothelial interactions or homing to inflamed tissues, including skin, mucosa, and intestine, and upregulated the expression of several cytokine genes that are involved in leukocyte extravasation and angiogenesis. These plasmablasts also upregulated the expression of receptors for several B-cell prosurvival cytokines that are known to be induced robustly in systemic viral infections such as dengue, some of which generally tend to be relatively higher in patients manifesting hemorrhage and/or shock than in patients with mild febrile infection. These findings improve our understanding of human plasmablast responses during the acute febrile phase of systemic dengue infection. IMPORTANCE Dengue is globally spreading, with over 100 million clinical cases annually, with symptoms ranging from mild self-limiting febrile illness to more severe and sometimes life-threatening dengue hemorrhagic fever or shock, especially among children. The pathophysiology of dengue is complex and remains poorly understood despite many advances indicating a key role for antibody-dependent enhancement of infection. While serum antibodies have been extensively studied, the characteristics of the early cellular factories responsible for antibody production, i.e., plasmablasts, are only beginning to emerge. This study provides a comprehensive understanding of the transcriptional profiles of human plasmablasts from dengue patients.

A cationic AIEgen and hexametaphosphate based simple and convenient fluorometric assay for alkaline phosphatase and its inhibitor.

Alkaline phosphatase (ALP) is an important biomarker to diagnose a number of diseases, such as anaemia, hepatobiliary diseases, chronic nephritis, and hypothyroidism. Therefore, the development of simple and convenient assays to monitor levels of ALP is highly desirable. In the present study, an aggregation-induced emission based simple, real-time, and direct fluorescence detection platform has been developed, by using a tetracationic pyridinium derivative of tetraphenylethylene (TPy-TPE) and anionic sodium hexametaphosphate (HMP) as component units. The sensing system, based on the TPy-TPE-HMP assembly, is highly responsive to the ALP dependent disintegration of the TPy-TPE-HMP aggregation complex, owing to HMP digestion by ALP. The sensing platform has an ALP detection limit of 16 mU mL-1 and linear range of 0-742 mU mL-1, respectively. The enzyme kinetic parameters, Km and Vmax, have been evaluated. In addition, the potential applicability of the TPy-TPE-HMP sensing system has also been shown with diluted human serum samples. Moreover, the TPy-TPE-HMP probe system is also useful for screening inhibitors of ALP.

Pharmaceuticals in water as emerging pollutants for river health: A critical review under Indian conditions.

The wastewaters from pharmaceutical manufacturing units, hospitals, and domestic sewage contaminated with excretal matters of medicine users are the prime sources of pharmaceutical pollutants (PPs) in natural water bodies. In the present study, PPs have been considered one of the emerging pollutants (EPs) and a cause of concern in river health assessment. Beyond the reported increase in antibiotic-resistant bacteria (ABRB), PPs have been found adversely affecting the biotic diversity in such water environments. Considering Algae, Macroinvertebrates, and Fishes as three distinct trophic level indicators, the present study puts forward a framework for showing River Health Condition (RHC) based on the calculation of a River Health Index (RHI). The RHI is calculated using six Indicator Group Scores (IGS) which individually reflect river health in a defined category of water quality characteristics. While Dissolved Oxygen Related Parameters (DORP), Nutrients (NT), and PPs are taken as causative agents affecting RHCs, scores of Algal-Bacterial (AB) symbiosis, Macroinvertebrates (MI), and Fishes (F) are considered as an effect of such environmental conditions. Current wastewater treatment technologies are also not very effective in the removal of PPs. The objective of the present study is to review the harmful effects of PPs on the aquatic environment, particularly on the chemical and biotic indicators of river health. Based on predicted no-effect concentrations (PNEC) for algae, macroinvertebrates, and fishes in the aquatic environment and measured environmental concentration (MEC) in the river, the estimated risk quotient (RQ) for norfloxacin in the Isakavagu-Nakkavagu stream of river Godavari, Hyderabad is found 293 for algae, 39 for MI, and 335 for fish. Among PPs, in Indian rivers, the presence of caffeine is the most frequent, with algae at the highest level of risk (RQmax= 24.5). Broadly six PPs, including azithromycin, caffeine, diclofenac, naproxen, norfloxacin, and sulfamethoxazole are found above PNEC values in Indian rivers. The application of IGS and RHI in understanding and presenting the river health condition (RHC) through colored hexagons has been demonstrated for the river Ganga near Varanasi (India) as an example. Identification of critical indicator groups, based on IGS provides a scientific basis for planned intervention for river health restoration to achieve an acceptable category.

Biochar Adsorbents for Arsenic Removal from Water Environment: A Review.

Arsenic intake can cause human health disorders to the lungs, urinary tract, kidney, liver, hyper-pigmentation, muscles, neurological and even cancer. Biochar is potent, economical and ecologically sound adsorbents for water purification. After surface modifications, adsorption capacity of biochar significantly increased due to high porosity and reactivity. Adsorption capacities of the biochar derived from the municipal solid waste and KOH mixed municipal solid waste were increased from 24.49 and 30.98 mg/g for arsenic adsorption. Complex formation, electrostatic behavior and ion exchange are important mechanisms for arsenic adsorption. Organic arsenic removal using biochar is a major challenge. Hence, more innovative research should be conducted to achieve one of the 17 sustainable development goals of the United Nations i.e. "providing safe drinking water for all". This review is focused on the arsenic removal from water using pristine and modified biochar adsorbents. Recent advances in production methods of biochar adsorbents and mechanisms of arsenic removal from water are also illustrated.

Does Long-term Oxygen Therapy and Noninvasive Ventilation Predispose Rhino-orbital-cerebral Mucormycosis in COVID-19 Patients?

How to cite this article: Kumar A, Kumar A, Kumar N, Kumar A, Sinha C, Singh PK. Does Long-term Oxygen Therapy and Noninvasive Ventilation Predispose Rhino-orbital-cerebral Mucormycosis in COVID-19 Patients? Indian J Crit Care Med 2022;26(9):1063-1064.

Supramolecular Control on the Optical Properties of a Dye-Polyelectrolyte Assembly.

Control of fluorescent molecular assemblies is an exciting area of research with large potential for various important applications, such as, fluorescence sensing/probing, cell imaging and monitoring drug-delivery. In the present contribution, we have demonstrated control on the extent of aggregation of a dye-polyelectrolyte assembly using a macrocyclic host molecule, sulfobutylether-ß-cyclodextrin (SBE-ß-CD). Initially, a cationic molecular rotor based organic dye, Auramine-O (AuO), undergoes aggregation in the presence of an anionic polyelectrolyte, polystyrene sulfonate (PSS), and displays a broad intense new emission band along with large variation in its absorption features and excited-state lifetime. A manipulation of the monomer-aggregate equilibrium of the dye-polyelectrolyte assembly has been achieved by introducing a cyclodextrin based supramolecular host, SBE-ß-CD, which leads to relocation of AuO molecules from polyelectrolyte (PSS) to supramolecular host cavity, owing to the formation of a host-guest complex between AuO and SBE-ß-CD. A reversible control on this manipulation of monomer-aggregate equilibrium is further achieved by introducing a competitive guest for the host cavity i. e., 1-Adamantanol. Thus, we have demonstrated an interesting control on the dye-polyelectrolyte aggregate assembly using a supramolecular host molecule which open up exciting possibilities to construct responsive materials using a repertoire of various host-specific guest molecules.

Effectiveness of COVID-19 vaccine in preventing infection and disease severity: a case-control study from an Eastern State of India.

Effectiveness of corona virus disease-19 (COVID-19) vaccines used in India is unexplored and need to be substantiated. The present case-control study was planned to elicit the effectiveness of COVID-19 vaccines in preventing infection and disease severity in the general population of Bihar, India. This case-control study was conducted among people aged ≥45 years during April to June 2021. The cases were the COVID-19 patients admitted or visited All India Institute of Medical Sciences (AIIMS), Patna, Bihar, India, and were contacted directly. The controls were the individuals tested negative for severe acute respiratory syndrome coronavirus-2 (SARS CoV-2) at the Virology laboratory, AIIMS-Patna and contacted telephonically for collection of relevant information. The vaccine effectiveness (VE) was calculated by using the formula (VE = 1 - odds ratio). The adjusted VE for partial and full vaccination were estimated to be 52.0% (95% confidence interval (CI) 39.0-63.0%) and 83.0% (95% CI 73.0-89.0%) respectively for preventing SARS CoV-2 infection. The sub-group analyses of the cases have shown that the length of hospital stays (LOS) (partially vaccinated: 9 days vs. unvaccinated: 12 days; P = 0.028) and the severity of the disease (fully vaccinated: 30.3% vs. partially vaccinated: 51.3% and unvaccinated: 54.1%; P = 0.035) were significantly low among vaccinated compared to unvaccinated individuals. To conclude, four out of every five fully vaccinated individuals are estimated to be protected from contracting SARS CoV-2 infection. Vaccination lowered LOS and chances of development of severe disease.

Effect of counter-anions on the aggregation of Thioflavin-T.

The aggregation of small molecules in aqueous solution is known to be influenced by the ionic strength of the medium; however, the role played by the identity of salt in the phenomenon of small molecule aggregation is rarely investigated. In the present contribution, we have investigated the effect of counter-anions on the aggregation of a popular cationic amyloid sensing probe, Thioflavin-T (ThT), by taking six different anions, viz. chloride, bromide, acetate, iodide, tetrafluoroborate, and perchlorate. Our results clearly indicate that it is not the ionic strength of the medium which solely controls aggregation of small molecules but distinct ions behave distinctly with regard to the organization. In fact, distinct ion effects play a major role in the salt induced organization of fluorophores. Using detailed steady-state emission, time-resolved emission, and ground-state absorption measurements, the optical properties of salt induced aggregates of ThT have been characterized. We have rationalized our observations on the basis of the theory of matching water affinity, which suggests that the matching free hydration energy is a critical aspect for the formation of contact ion pairs, which eventually results in aggregation. In brief, a larger sized anion, perchlorate, has a lower free energy of hydration and forms a suitable contact ion pair, with a larger organic cation, ThT, having weaker hydration. This contact ion-pair formation subsequently leads to the formation of an aggregate assembly which is found to be emissive in nature. Therefore, it is possible to induce aggregation of ThT by selecting the right counterion with the appropriate size, which may help us to evaluate the false positive signals when high ionic strength and specific counterions are present in the sensing matrix.

Supramolecular tuning of thioflavin-T aggregation hosted by polystyrene sulfonate.

Tunable and controllable emission is an extremely desirable feature for advanced functional materials that finds usage in optoelectronic utilization, fluorescence probing/sensing, drug-delivery monitoring, etc. In the present contribution, we have employed a macrocyclic host molecule, sulfobutyl ether-ß-cyclodextrin (SBE-ß-CD), as a tuning agent for an intensely emissive aggregate assembly of a molecular rotor dye, thioflavin-T (ThT), in the presence of an anionic polyelectrolyte, polystyrene sulfonate (PSS). The macrocyclic host breaks the PSS templated ThT aggregates and leads to encapsulation of released ThT molecules, tailoring the emission response of the system in terms of intensity and wavelength. Utilizing the established selectivity of the cyclodextrin-adamantane system, reverse control of this tunable emission has been further achieved. The controllable fluorescence system has been extensively investigated using ground-state absorption, steady-state and time-resolved emission spectroscopy. This kind of supramolecular tailoring of self-assembled aggregate emission has enormous potential in the field of fluorescence sensors and probes, and imaging and tracking in biological systems.

Metallic contamination of global river sediments and latest developments for their remediation.

This review article represents the comparative study of heavy metal concentration in water and sediments of 43 important global rivers. The review is a solitary effort in the area of heavy metal contamination of river-sediments during last ten years. The interpretation of heavy metal contamination in sediments has been verified with different indices, factors, codes and reference guidelines, which is based on geochemical data linked to background value of metals. It is observed that health hazards arise due to dynamics of movement of metals between water and sediments, which is primarily influenced by several factors such as physical, chemical, biological, hydrological and environmental. Also, the reason behind accumulation and assimilation of heavy metals on river water system is explained with appropriate mechanisms. Several factors e.g. pH, ORP, organic matter etc. are mainly involved in the distribution, accumulation and assimilation of metals in the sediment phase to water phase. Remediation technologies such as in-situ and ex-situ have been discussed for the removal of heavy metals from contaminated sediments. We have also compared the performance efficiencies of the technologies adopted by different researchers during the period 2003 to 2019 for the removal of metal bound sediments. Many researchers have preferred in-situ over ex-situ remediation due to low cost and time saving remediation effects. In this work we have also incorporated the safety measures and strategies which can prevent the metal accumulation in sediments of river system.