Multifunctional Cu:ZnS quantum dots for degradation of Amoxicillin and Dye Sulphon Fast Black-F and efficient determination of urea for assessing environmental aspects.

This work is particularly aimed at the preparation of ZnS and Cu doped ZnS (Cu:ZnS) QDs by facile and easy technique, chemical precipitation method for the degradation of water pollutants and a simple scheme was proposed to prepare the urea-sensing system. The morphological and optical properties of the synthesized QDs was studied using high resolution transmission and scanning electron microscopes, X-ray diffraction, energy dispersive X-ray analysis, fluorescence and ultraviolet-visible spectroscopy, differential thermal and thermogravimetric analyses, Brunauer-Emmett-Teller analysis. The photocatalytic performance was systematically assessed by the photodegradation of an important pharmaceutical water pollutant, Amoxicillin (AMX) and a dye Fast Sulphon Black F (SFBF) in aqueous medium under UV light irradiation. Also, a very sensitive system was prepared by depositing the dots over an indium-tin-oxide (ITO) glass substrate for the sensing of biologically active molecule urea as it is an important monitor of public health in water and soil productivity. The results illustrated excellent photocatalytic efficiency (86.46% for AMX and 99.41% for SFBF) with stability up to four cycles of degradation reaction. The optimal photocatalyst dosage for achieving maximum removal of AMX was found to be 70 mg at a pH of 9.5, with a treatment time of 40 min. Similarly, for SFBF, the optimal photocatalyst dosage was determined to be 60 mg at pH 9, with a treatment time of 60 min. Further, the electrochemical analysis was done by fabricating Urease enzyme (UR)/Cu:ZnS QDs/ITO bioelectrode and then the fabricated bioelectrode, was utilized to determine the different concentrations of urea by cyclic voltammetry. Thus, the obtained limit of detection and sensitivity of the fabricated biosensing device for urea detection was obtained to be 0.0092 µM and 12 µA µM-1cm-2, respectively; under the optimized experimental conditions. Hence, it is anticipated that Cu:ZnS QDs can also successfully be applied as a promising material for fabrication of novel bioelectrode for urea determination and the biosensing platform is desirable and viable.

A Novel Decentralized Blockchain Architecture for the Preservation of Privacy and Data Security against Cyberattacks in Healthcare.

Nowadays, in a world full of uncertainties and the threat of digital and cyber-attacks, blockchain technology is one of the major critical developments playing a vital role in the creative professional world. Along with energy, finance, governance, etc., the healthcare sector is one of the most prominent areas where blockchain technology is being used. We all are aware that data constitute our wealth and our currency; vulnerability and security become even more significant and a vital point of concern for healthcare. Recent cyberattacks have raised the questions of planning, requirement, and implementation to develop more cyber-secure models. This paper is based on a blockchain that classifies network participants into clusters and preserves a single copy of the blockchain for every cluster. The paper introduces a novel blockchain mechanism for secure healthcare sector data management, which reduces the communicational and computational overhead costs compared to the existing bitcoin network and the lightweight blockchain architecture. The paper also discusses how the proposed design can be utilized to address the recognized threats. The experimental results show that, as the number of nodes rises, the suggested architecture speeds up ledger updates by 63% and reduces network traffic by 10 times.

Plant Secondary Metabolites as Defense Tools against Herbivores for Sustainable Crop Protection.

Plants have evolved several adaptive strategies through physiological changes in response to herbivore attacks. Plant secondary metabolites (PSMs) are synthesized to provide defensive functions and regulate defense signaling pathways to safeguard plants against herbivores. Herbivore injury initiates complex reactions which ultimately lead to synthesis and accumulation of PSMs. The biosynthesis of these metabolites is regulated by the interplay of signaling molecules comprising phytohormones. Plant volatile metabolites are released upon herbivore attack and are capable of directly inducing or priming hormonal defense signaling pathways. Secondary metabolites enable plants to quickly detect herbivore attacks and respond in a timely way in a rapidly changing scenario of pest and environment. Several studies have suggested that the potential for adaptation and/or resistance by insect herbivores to secondary metabolites is limited. These metabolites cause direct toxicity to insect pests, stimulate antixenosis mechanisms in plants to insect herbivores, and, by recruiting herbivore natural enemies, indirectly protect the plants. Herbivores adapt to secondary metabolites by the up/down regulation of sensory genes, and sequestration or detoxification of toxic metabolites. PSMs modulate multi-trophic interactions involving host plants, herbivores, natural enemies and pollinators. Although the role of secondary metabolites in plant-pollinator interplay has been little explored, several reports suggest that both plants and pollinators are mutually benefited. Molecular insights into the regulatory proteins and genes involved in the biosynthesis of secondary metabolites will pave the way for the metabolic engineering of biosynthetic pathway intermediates for improving plant tolerance to herbivores. This review throws light on the role of PSMs in modulating multi-trophic interactions, contributing to the knowledge of plant-herbivore interactions to enable their management in an eco-friendly and sustainable manner.

Isolated Oculomotor Nerve Palsy - A Rare Initial Manifestation of Tuberculous Meningitis.

Tuberculous meningitis (TBM) is a sub-acute / chronic meningitis known for its diverse manifestations which may lead to delayed diagnosis. An isolated oculomotor nerve palsy as an initial presentation of TB meningitis is quite rare. One such case has presented here; A 18 year female presented to us with ptosis of the left eye. Complete neurological examination revealed it to be a case of isolated 3rd cranial nerve palsy. Computed Tomography (CT) and Magnetic Resonance Imaging (MRI) brain revealed no significant abnormality. Cerebrospinal fluid (CSF) analysis was done and diagnosis of Tuberculous Meningitis was confirmed. This case report focuses on the fact that tuberculous meningitis should be included in the differential diagnosis of isolated oculomotor nerve palsy.

Exploitation of reverse vaccinology and immunoinformatics as promising platform for genome-wide screening of new effective vaccine candidates against Plasmodium falciparum.

BACKGROUND: In the current scenario, designing of world-wide effective malaria vaccine against Plasmodium falciparum remain challenging despite the significant progress has been made in last few decades. Conventional vaccinology (isolate, inactivate and inject) approaches are time consuming, laborious and expensive; therefore, the use of computational vaccinology tools are imperative, which can facilitate the design of new and promising vaccine candidates. RESULTS: In current investigation, initially 5548 proteins of P. falciparum genome were carefully chosen for the incidence of signal peptide/ anchor using SignalP4.0 tool that resulted into 640 surface linked proteins (SLP). Out of these SLP, only 17 were predicted to contain GPI-anchors using PredGPI tool in which further 5 proteins were considered as malarial antigenic adhesins by MAAP and VaxiJen programs, respectively. In the subsequent step, T cell epitopes of 5 genome derived predicted antigenic adhesins (GDPAA) and 5 randomly selected known malarial adhesins (RSKMA) were analysed employing MHC class I and II tools of IEDB analysis resource. Finally, VaxiJen scored T cell epitopes from each antigen were considered for prediction of population coverage (PPC) analysis in the world-wide population including malaria endemic regions. The validation of the present in silico strategy was carried out by comparing the PPC of combined (MHC class I and II) predicted epitope ensemble among GDPAA (99.97%), RSKMA (99.90%) and experimentally known epitopes (EKE) of P. falciparum (97.72%) pertaining to world-wide human population. CONCLUSIONS: The present study systematically screened 5 potential protective antigens from P. falciparum genome using bioinformatics tools. Interestingly, these GDPAA, RSKMA and EKE of P. falciparum epitope ensembles forecasted to contain highly promiscuous T cell epitopes, which are potentially effective for most of the world-wide human population with malaria endemic regions. Therefore, these epitope ensembles could be considered in near future for novel and significantly effective vaccine candidate against malaria.

Genome based screening of epitope ensemble vaccine candidates against dreadful visceral leishmaniasis using immunoinformatics approach.

Visceral leishmaniasis (VL) is a dreadful protozoan disease caused by Leishmania donovani that severely affects huge populations in tropical and sub-tropical regions. The present study reports an unbiased genome based screening of 4 potent vaccine antigens against 8023 L. donovani proteins by following the criteria of presence of signal peptides, GPI-anchors and ≤1 transmembrane helix using advanced bioinformatics tools viz. SignalP4.0, PredGPI and TMHMM2.0, respectively. They are designated as genome based predicted signal peptide antigens (GBPSPA). The antigenicity/immunogenicity of chosen vaccine antigens (GBPSPA) with 4 randomly selected known leishmanial antigens (RSKLA) was compared by simulation study employing C-ImmSim software for human immune responses. This revealed better immunological responses. These antigens were further evaluated for the presence of B- and T-cell epitopes using immune epitope database (IEDB) based recommended consensus method of MHC class I and II tools. It was found to forecast CD4+ and CD8+ T-cell responses in genetically diverse human population worldwide as well as different endemic regions through IEDB based predicted population coverage (PPC) analysis tool. The worldwide percent PPC value of combined (HLA class I and II) epitope ensemble forecast was found to be 99.98, 99.96 and 50.04, respectively for GBPSPA, RSKLA and experimentally known epitopes (EKE) of L. donovani. Therefore, these potential antigens/epitope ensembles could favor the design of prospective and novel vaccine constructs like self-assembled epitopes as nano vaccine formulations against VL. Overall, the present study will serve as a model framework that might improve the effectiveness of designed vaccine against L. donovani and other related pathogens.

Biomedical applications of microbially engineered polyhydroxyalkanoates: an insight into recent advances, bottlenecks, and solutions.

Biopolymeric polyhydroxyalkanoates (PHAs) are fabricated and accumulated by microbes under unbalanced growth conditions, primarily by diverse genera of bacteria. Over the last two decades, microbially engineered PHAs gained substantial interest worldwide owing to their promising wide-range uses in biomedical field as biopolymeric biomaterials. Because of non-hazardous disintegration products, preferred surface alterations, inherent biocompatibility, modifiable mechanical properties, cultivation support for cells, adhesion devoid of carcinogenic impacts, and controllable biodegradability, the PHAs like poly-3-hydroxybutyrate, 3-hydroxybutyrate and 3-hydroxyvalerate co-polymers, 3-hydroxybutyrate and 4-hydroxybutyrate co-polymers, etc., are available for various medical applications. These PHAs have been exploited to design in vivo implants like sutures as well as valves for direct tissue repairing as well as in regeneration devices like bone graft substitutes, nerve guides as well as cardiovascular patches, etc. Furthermore, they are also emerged as attractive candidates for developing effective/novel drug delivery systems because of their biocompatibility and biodegradability with the ability to deliver and release the drugs at a specific site in a controllable manner and, therefore widen the therapeutic window with reduced side effects. However, there still remain some bottlenecks related to PHA purity, mechanical properties, biodegradability, etc., that are need to be addressed so as to make PHAs a realistic biomaterial. In addition, innovative approaches like PHAs co-production with other value-added products, etc., must be developed currently for economical PHA production. This review provides an insight toward the recent advances, bottlenecks, and potential solutions for prospective biomedical applications of PHAs with conclusion that relatively little research/study has been performed presently toward the viability of PHAs as realistic biopolymeric biomaterials.

Enhanced Quantum Cutting via Li+ Doping from a Bi3+/Yb3+-Codoped Gadolinium Tungstate Phosphor.

The Bi3+/Yb3+-codoped gadolinium tungstate phosphor has been synthesized through a solid-state reaction method. The structural characterization reveals the crystalline nature of the phosphor. The Bi3+-doped phosphor emits visible radiation from the blue to red regions upon excitation with 330 and 355 nm. The addition of Yb3+ to the Bi3+-doped phosphor reduces the emission intensity in the visible region and emits an intense near-infrared (NIR) photon centered at 976 nm through a quantum-cutting (QC) phenomenon. This is due to cooperative energy transfer (CET) from the 3P1 level of Bi3+ to the 2F5/2 level of Yb3+. The presence of Li+ ions in the Bi3+/Yb3+-codoped phosphor enhances the emission intensity in the NIR region up to by 3 times, whereas the emission intensity in the visible region is significantly reduced. The energy transfer (ET) from the Bi3+ ions to the Yb3+ ions is confirmed by lifetime measurements, and the lifetime for the 3P1 level of Bi3+ decreases continuously with increasing Yb3+ concentration. The ET efficiency (ηETE) and corresponding QC efficiency (ηQE) are calculated and found to be 29% and 129%, respectively. The presence of Li+ enhances the QC efficiency of the phosphor up to 43%. Thus, the Bi3+/Yb3+/Li+-codoped phosphor is a promising candidate to enhance the efficiency of a crystalline-silicon-based solar cell through spectral conversion.

New perspective in garnet phosphor: low temperature synthesis, nanostructures, and observation of multimodal luminescence.

Herein, we report a new concept for garnet materials in terms of the synthesis of nanocrystalline structure at low temperatures and its multimodal luminescence processes. Terbium- and ytterbium-ion-codoped yttrium gallium garnet nanophosphors have been synthesized via solution combustion technique; nearly pure phase nanophosphor samples were obtained. The synthesized nanophosphor shows efficient multimodal upconversion (UC), downshifting (DS), and quantum cutting (QC)/downconversion (DC) luminescence, which is a new paradigm in garnet material. The garnet nanophosphor shows strong green emission through DS and UC processes both. Furthermore, cooperative energy transfer (CET) has been described in detail, and a possible mechanism for the QC process is also proposed. A UV/blue photon absorbed by Tb(3+) ion splits into two near-infrared photons (wavelength range 900-1040 nm), emitted by a Yb(3+) ion pair, with an efficiency of more than 100%. The Yb(3+) concentration dependent ET from Tb(3+) to Yb(3+) has been verified using time domain analysis. An ET efficiency as high as 28% and a corresponding QC efficiency of about 128% (for 15 mol % of Yb(3+) concentration) have been attained. Such a multimode emitting nanophosphor could be very useful in display devices and for enhancing the conversion efficiency of next generation solar cells via spectral modification etc.

Evidence-based effectiveness of Ozone therapy in the treatment for oral lichen planus - A systematic review.

Oral lichen planus is a common, chronic mucocutaneous condition of uncertain origin. Early treatment of OLP can dramatically reduce the risk of further development, which in turn reduces the risk of developing cancer. Numerous methods can be used to treat OLP. Since the significance of ozone in treating this disease is still uncertain. This systematic review was conducted based on english databases, including PUBMED, SCOPUS, Embase, Ovid, and Journal of Web up to July 2022. We used the search phrases "ozone," "ozone in the treatment of oral lichen planus," "oral lichen planus," and "ozone therapy." Finally, five papers were selected for qualitative analysis. This review included a total of five papers, four of which were clinical trials and one was a longitudinal study. All studies included the erosive form of OLP, also ozone therapy was applied to patients who did not respond to conventional treatment. Ozone showed significant therapeutic effects in terms of reduction in pain and size of the lesion. The signs and symptoms associated with OLP such as burning sensation, lesion size, and scarring all considerably improved with ozone therapy.

Electromyographic Assessment of Masticatory Muscles & their Asymmetries in Adult Indian Population.

Objective: To study the surface electromyography (sEMG) and it is asymmetry under resting and dynamic conditions in masticatory muscles. Materials and Methods: sEMG of the masticatory muscles (bilateral masseter & temporalis) was done in 61 healthy subjects (mean age 28.5 ± 8.8 years) with bilateral functional molar occlusal relationship. Root mean square (RMS) values sEMG for each activity (rest, clenching, maximum mouth opening (MMO), left and right excursion) for a 10 s period were recorded and analyzed. Indices for asymmetry of muscles, relative activity and resultant torque were assessed and analyzed. Results: RMS values of sEMG during clenching were significantly higher for all masticatory muscles in males compared to females (p < 0.05). During excursive mandibular movement a statistically significant difference seen in ipsilateral temporalis muscle in males. sEMG of masticatory muscles during rest as well as functional activities of mandible was asymmetrical. A predominant masseteric activity was observed for all functional activities of mandible except during rest for which temporalis muscle activity was higher. Right sided torque was observed during rest, MMO and right lateral movements while a predominant left sided torque was present during left lateral movement and clenching. Conclusion: sEMG values of masticatory muscles obtained in our study can be used as reference for healthy Indian population. A perfect muscular symmetry might be illusive and a controlled asymmetry criterion appears to be more useful which corresponds to reality.

Persistent facial pain in post-stroke patients, a hospital-based cohort study; experience from North India.

Background: Post-stroke pain is common after a stroke and might be underreported. We describe Persistent Facial Pain (PFP) developed in post-stroke patients. Method: ology: This was a prospective hospital-based cohort study of stroke patients, and patients were followed up. Out of 415 stroke patients, 26 developed PFP. Result: Out of all PFP patients, six patients had an ischemic stroke, and 20 had a hemorrhagic stroke. 57.7% of patients had hypertension, while 34.6 patients had diabetes. The stroke location was left-sided in 12 patients and right-sided in 14 patients. 46.15% of patients responded to venlafaxine, 30.77% responded to amitriptyline, and 23.08% responded to pregabalin. Conclusion: Persistent facial pain is a pain syndrome that might be missed in patients post-stroke. It might be more common in hemorrhagic stroke patients than in ischemic stroke patients. It responds adequately to antidepressants. A high index of suspicion is required to diagnose and appropriately manage these patients.

Biotechnological innovations in nanocellulose production from waste biomass with a focus on pineapple waste.

New materials' synthesis and utilization have shown many critical challenges in healthcare and other industrial sectors as most of these materials are directly or indirectly developed from fossil fuel resources. Environmental regulations and sustainability concepts have promoted the use of natural compounds with unique structures and properties that can be biodegradable, biocompatible, and eco-friendly. In this context, nanocellulose (NC) utility in different sectors and industries is reported due to their unique properties including biocompatibility and antimicrobial characteristics. The bacterial nanocellulose (BNC)-based materials have been synthesized by bacterial cells and extracted from plant waste materials including pineapple plant waste biomass. These materials have been utilized in the form of nanofibers and nanocrystals. These materials are found to have excellent surface properties, low density, and good transparency, and are rich in hydroxyl groups for their modifications to other useful products. These materials are well utilized in different sectors including biomedical or health care centres, nanocomposite materials, supercapacitors, and polymer matrix production. This review explores different approaches for NC production from pineapple waste residues using biotechnological interventions, approaches for their modification, and wider applications in different sectors. Recent technological developments in NC production by enzymatic treatment are critically discussed. The utilization of pineapple waste-derived NC from a bioeconomic perspective is summarized in the paper. The chemical composition and properties of nanocellulose extracted from pineapple waste may have unique characteristics compared to other sources. Pineapple waste for nanocellulose production aligns with the principles of sustainability, waste reduction, and innovation, making it a promising and novel approach in the field of nanocellulose materials.

Unusual crystal structure evolution, multiple phase boundaries and phase coexistence in (1 - x)Ba(Cu1/3Nb2/3)O3-(x)PbTiO3 perovskite solid solution.

Exploring the functionalities of materials requires a profound understanding of the crystal structure. In this paper, room temperature crystal structures of a new solid solution (1 - x)Ba(Cu1/3Nb2/3)O3-(x)PbTiO3 have been investigated in the entire compositional span and different crystallographic phases and phase coexistence regions have been discovered. The confirmation of the symmetry of these crystal structures has been done with the help of Rietveld analysis of the high-resolution XRD data. Despite both the end components, Ba(Cu1/3Nb2/3)O3 and PbTiO3, having tetragonal (P4mm) symmetry, new cubic and monoclinic phases have been discovered for the intermediate compositions with multiple phase boundaries. The composition region 0.05 ≤ x ≤ 0.55 exhibits a cubic crystal structure and increasing PbTiO3 concentration to 0.62 results in a unique coexistence of two tetragonal phases with different tetragonalities. This transformation is mediated by coexisting cubic and tetragonal phases, for 0.59 and 0.60. The crystal structure of the solid solution later transforms into coexisting monoclinic and tetragonal phases for a wider compositional span i.e., 0.65 ≤ x ≤ 0.85. This composition region is very fascinating, as two phenomenologically different monoclinic structures have been observed in it. Finally, a tetragonal phase at x = 1 is achieved through the mediation of two coexisting tetragonal phases, for the region 0.85 < x ≤ 0.975. The evolution of different crystallographic structures and the coexisting phases are critically comprehended using the variations in the lattice parameters and unit cell volume. The presence of multiple phase boundaries spread across a wide range of compositions makes this solid solution very intriguing and a viable choice for exploring different properties with compositional tuning.

Synthesis, in vitro cytotoxic activity and molecular docking study of androstene and estrone derivatives.

The development and discovery of steroidal drugs to cure cervical cancer is of the most important. The Claisen condensation of androstene and estrone with aromatic aldehydes was catalyzed by potassium tert. butoxide in tert. butanol to give the corresponding 2-arylidene and 16-arylidene estrone. Subsequently, the 16-arylidene estrone reacted with acid chloride in presence of quaternary amine in halogenated solvent resulting in the steroidal arylidene derivatives. Synthesis, Characterization and in vitro cytotoxic activity of arylidenes are rationalized. Fifteen compounds are synthesized and six of them were evaluated for cytotoxic activity against cervical cancer cell line. HT-3 cell line examination revealed a considerable growth inhibition. Compounds 4a, 4b, 6b, 8c, and 8d, which are estrone-based arylidenes, are the most potent of the series, with IC50 value of 7.15, 10.76, 6.37, 3.56, and 1.55 µM/ml against HT-3 cell line. In addition, molecular docking studies were performed for the steroidal arylidenes to elucidate the binding interactions. Compound 4a, 4b, 6b, 8c and 8d showed excellent binding energy. Docking studies agreed well with in vitro studies. The end result offers an alternative approach to develop steroidal arylidenes that are more effective and are based on estrone, leading to the development of novel anticancer agents.

Study of paraCEST response on six-coordinated Co(II) and Ni(II) complexes of a pyridine-tetraamide-based ligand.

This study highlights the successful synthesis of a potential ligand, 2,2',2'',2'''-((pyridine-2,6-diylbis(methylene))bis(azanetriyl))tetraacetamide (PATA), along with its corresponding Co(II) and Ni(II) complexes for paraCEST-based agents. X-ray diffraction data confirmed that both the complexes are six coordinated with distorted octahedral geometries, but only the [Co(PATA)]2+ complex has a good structural feature to show paraCEST activity. After a thorough characterization of the ligand and both of its complexes, various studies, including solution-state magnetic properties, redox properties, temperature, and pH variation studies, were carried out. [Co(PATA)]2+ remained inert in the presence of competing ions, under acidic conditions, at high temperatures, and in the physiological pH range. The paraCEST response of [Co(PATA)]2+ has been measured in the presence of HEPES buffer medium, and a high paraCEST feature was discovered at both 37 and 25 °C. The pH variation paraCEST studies were carried out and the exchange rate constant of the probe at 37 and 25 °C was also determined. However, due to the fast exchange of water protons, the [Ni(PATA)(OH2)]2+ complex remained inactive in the CEST process.

Assessment of knowledge and awareness among North Indian populations about oral precancerous lesions (OPL): A cross-sectional survey study.

Background: A precancerous lesion is a morphologically altered tissue in which oral cancer is more likely to occur than its apparently normal counterpart. They are quite common in the Indian population due to the habitual habit of chewing tobacco. The aim of this study was to evaluate the awareness of oral precancerous lesions by a questionnaire-based survey among the study subjects having been diagnosed with it. Methods: In this descriptive study, a structured questionnaire having 11 survey questions has been used to record the response from study subjects who have been diagnosed and reported for treatment for oral premalignant lesions in the Department of Oral Medicine and Radiology. A total of 1013 study subjects were assessed for awareness about OPL and its consequences. Results: 44.3% of the study population was addicted to smoking tobacco (cigarettes) while 57.9% of study subjects were addicted to non-smoking tobacco (Pan masala). The reason behind their addiction was reported to be stress (54.9%) and workload (25.3%). Most of the study subjects were diagnosed with oral sub-mucous fibrosis (53.4%). 78.6% of study subjects diagnosed with OPL were not aware of it and 94% were willing to quit the addiction. Conclusion: The awareness about OPL among patients was found to be low. Although many wanted to quit their addiction to smoking and chewing tobacco but were unable to do so. So it is a need for time to develop a national policy on tobacco use and related diseases. This policy will definitely reduce the burden of oral premalignant lesions and oral cancer in Indian population.

Easily synthesizable molecular probe for the nanomolar level detection of Cd2+ in near aqueous media: Theoretical investigations and live cell imaging.

The present investigation highlights a quinoline-based small molecule probe (DEQ) for the detection of Cd2+ among other metal ions in near-aqueous media. The probe DEQ and its Cd2+ complex (DEQ-Cd) have been synthesized and characterized by all possible spectroscopic methods. The weakly emissive DEQ showed its strong emission in the presence of Cd2+, which is attributed to the photoinduced electron transfer (PET) along with the chelation-enhanced fluorescence (CHEF) mechanism. The 1:1 binding mode between ligand and Cd2+ is confirmed by single crystal XRD analysis, which is further supported by Job's plot and HRMS. The detection limit of the probe to recognize Cd2+ was found to be as low as 89 nM. Furthermore, DEQ can act as a reversible fluorescence probe with the off-on-off mechanism by the alternative addition of Cd2+ and EDTA. DFT and TD-DFT studies exposed the proposed mechanism after Cd2+ insertion and the obtained results for electronic spectra are in line with the experimental results. The response towards pH was quite interesting and allowed us to study its application in live cell imaging. With all the positive results, the proposed ligand DEQ can be used as a potential probe for the detection of Cd2+ in real-life applications.

Comparative paraCEST effect of amide and hydroxy groups in divalent cobalt and nickel complexes of tripyridine-based ligands.

Co(II) and Ni(II) complexes of two tri-pyridine-based ligands with two hydroxy and two amide exchangeable protons (TDTA) and with six amide exchangeable protons (TMTP) were investigated for application as paraCEST-based magnetic resonance imaging (MRI) contrast agents. The two hydroxy groups present in the TDTA ligand were found to be passive while the amide group was active towards the CEST process. In the case of the Co(II) and Ni(II) complexes of the TMTP ligand, all three coordinated amide groups participated in the exchange process, and excellent CEST signals were observed. The X-ray structure of the four complexes revealed the seven-coordinate geometry of Co(II) complexes and the six-coordinate geometry of Ni(II) complexes. The presence of amide protons and hydroxy protons in the complexes was detected by the NMR method. The stability of the complexes in solution at high temperatures, in different pH ranges and acidic conditions, in the presence of competing cations, and biologically relevant anions was investigated. Potentiometric titrations were carried out to determine the ligand's protonation constants and the complexes' thermodynamic stability constant at 25.0 °C and I = 0.15 mol L-1 NaClO4. ParaCEST studies of [Co(TMTP)]2+ and [Ni(TMTP)]2+ at variable pH and variable pulse power are highlighted.

Robust Optical Detection of Ga3+ by a Rhodamine- and Coumarin-Based Proficient Probe: Theoretical Investigations and Biological Applications.

The present investigation highlights a rhodamine-B- and coumarin-based efficient probe that selectively detects Ga3+ over other metal ions. The active pocket of the ligand for trapping the metal ions and the binding stoichiometry of its Ga3+ complex were discovered by single-crystal X-ray diffraction (SC-XRD) analysis. This binding stoichiometry was further confirmed in the solution state by mass spectrometry and Job's plot. The detection limit was found to be at the nanomolar level. Pyrophosphate being a well-known quencher could easily quench the fluorescence intensity of the RC in the presence of Ga3+ and reversibly recognize Ga3+ in the solution. The spiro ring opening of the ligand after Ga3+ insertion is proposed to be the principal mechanism for the turn-on fluorescence response. This ring opening was confirmed by SC-XRD data and nuclear magnetic resonance (NMR) titration experiments. Both ground- and excited-state calculations of the ligand and complex have been carried out to obtain information about their energy levels and to obtain the theoretical electronic spectra. Furthermore, the live-cell imaging of the probe only and the probe after the addition of Ga3+ have been carried out in HaCaT cells and satisfactory responses were observed. Interestingly, with the help of this probe, Ga3+ can be tracked inside the intracellular organelle such as lysosomes along with other regions of the cell. The article highlights a rhodamine-coumarin-based probe for the detection of Ga3+ over other metal ions with a nanomolar level detection limit. Structural characterization of the ligand and its Ga3+ complex was investigated by SC-XRD. Density functional theory (DFT) and time-dependent DFT (TD-DFT) studies were carried out to explore the excited-state energies and electronic spectra. The application of the probe for the detection of Ga3+ in live cells has been explored, and positive responses were observed.