Using Iron L-Edge and Nitrogen K-Edge X-ray Absorption Spectroscopy to Improve the Understanding of the Electronic Structure of Iron Carbene Complexes.

Iron-centered N-heterocyclic carbene compounds have attracted much attention in recent years due to their long-lived excited states with charge transfer (CT) character. Understanding the orbital interactions between the metal and ligand orbitals is of great importance for the rational tuning of the transition metal compound properties, e.g., for future photovoltaic and photocatalytic applications. Here, we investigate a series of iron-centered N-heterocyclic carbene complexes with +2, + 3, and +4 oxidation states of the central iron ion using iron L-edge and nitrogen K-edge X-ray absorption spectroscopy (XAS). The experimental Fe L-edge XAS data were simulated and interpreted through restricted-active space (RAS) and multiplet calculations. The experimental N K-edge XAS is simulated and compared with time-dependent density functional theory (TDDFT) calculations. Through the combination of the complementary Fe L-edge and N K-edge XAS, direct probing of the complex interplay of the metal and ligand character orbitals was possible. The σ-donating and π-accepting capabilities of different ligands are compared, evaluated, and discussed. The results show how X-ray spectroscopy, together with advanced modeling, can be a powerful tool for understanding the complex interplay of metal and ligand.

Saliva Based Diagnostic Prediction of Oral Squamous Cell Carcinoma using FTIR Spectroscopy.

Oral cancer ranks as the sixth most prevalent form of cancer worldwide, presenting a significant public health concern. According to the World Health Organization (WHO), within a 5-year period following diagnosis, the mortality rate among oral cancer patients of all stages stands at 45%. In this study, a total of 60 patients divided into 2 groups were recruited. Group A included 30 histo-pathologically confirmed OSCC patients and Group B included 30 healthy controls. A standardized procedure was followed to collect saliva samples. FTIR spectroscopy was done for all the saliva samples collected from both Group A and B. An IR Prestige-21 (Shimadzu Corp, Japan) spectrometer was used to record IR spectra in the 40-4000 cm-1 range SVM classifier was applied in the classification of disease state from normal subjects using FTIR data. The peaks were identified at wave no 1180 cm-1, 1230 cm-1, 1340 cm-1, 1360 cm-1, 1420 cm-1, 1460 cm-1, 1500 cm-1, 1540 cm-1, 1560 cm-1, and 1637 cm-1. The observed results of SVM demonstrated the accuracy of 91.66% in the classification of Cancer tissues from the normal subjects with sensitivity of 83.33% while specificity and precision of 100.0%. The development of oral cancer leads to noticeable alterations in the secondary structure of proteins. These findings emphasize the promising use of ATR-FTIR platforms in conjunction with machine learning as a reliable, non-invasive, reagent-free, and highly sensitive method for screening and monitoring individuals with oral cancer.

Staphylococcal peroxidase inhibitor (SPIN): Investigation of the inhibitory N-terminal domain via a stabilizing disulfide insertion.

Staphylococcus aureus secretes an array of small proteins that inhibit key enzyme-catalyzed reactions necessary for proper function of the human innate immune system. Among these, the Staphylococcal Peroxidase Inhibitor, SPIN, blocks the activity of myeloperoxidase (MPO) and thereby disrupts the HOCl-generating system of neutrophils. Previous studies on S. aureus SPIN have shown that it relies on a C-terminal α-helical bundle domain to mediate initial binding to MPO, but requires a disordered N-terminal region to fold into a ß-hairpin conformation to inhibit MPO activity. To further investigate the structure/function relationship of SPIN, we introduced two cysteine residues into its N-terminal region to trap SPIN in its MPO-bound conformation and characterized the modified protein, which we refer to here as SPIN-CYS. Although control experiments confirmed the presence of the disulfide bond in SPIN-CYS, solution structure determination revealed that the N-terminal region of SPIN-CYS adopted a physically constrained series of lariat-like structures rather than a well-defined ß-hairpin. Nevertheless, SPIN-CYS exhibited a gain in inhibitory potency against human MPO when compared to wild-type SPIN. This gain of function persisted even in the presence of deleterious mutations within the C-terminal α-helical bundle domain. Surface plasmon resonance studies showed that the gain in potency arose through an increase in apparent affinity of SPIN-CYS for MPO, which was driven primarily by an increased association rate with MPO when compared to wild-type SPIN. Together, this work provides new information on the coupled binding and folding events required to manifest biological activity of this unusual MPO inhibitor.

Comparison of Buccal and Lingual-Based Triangular Flap During Mandibular Third Molar Extraction for Reducing Postoperative Complications: A Randomized Controlled Trial.

Background: Surgical removal of the mandibular third molar requires reflection of the mucoperiosteal flap. Several studies have suggested different varieties and innovative designs for flap reflection. We have designed a randomized controlled trial (RCT) to check the feasibility of two flap designs: lingual-based triangular flap (LBTF) and buccal-based triangular flap (BBTF) by calculating the duration of surgery and evaluating postoperative complications such as pain, swelling, and trismus. Materials and Method: It was a non-inferiority parallel-group RCT. The trial was registered in the Control Trial Register of India (CTRI/2021/10/037182) and was performed according to Consolidated Standards of Registered Trial (CONSORT) guidelines. Intraoperative surgery time and postoperative pain, swelling, and trismus were measured and analyzed by a two-sample t test. The Chi-square test was used to measure gender distribution in the study. Result: Of the total of 88 required subjects, gender distribution and performed surgical time were statistically insignificant with a p-value of 0.76 and 0.48, respectively. The pain was significantly higher in the LBTF group in the 5th and 7th postoperative days with a p-value of 0.02 and 0.028. The swelling was statistically higher during all the follow-ups except for the 28th day in the LBTF group with values of 0.006, 0.002 and 0.003, respectively. There was no significant difference in inter-incisional distance (IID) between the groups during postoperative check-ups. Conclusion: LBTF shows no edge over BBTF during mandibular third molar disimpaction.

Effect of COVID-19 pandemic on influenza; observation of a tertiary level virology laboratory.

The lockdown enforced amid the COVID-19 pandemic has affected the occurrence and trends of various respiratory virus infections, with a particular focus on influenza. Our study seeks to analyze the repercussions of the COVID-19 pandemic on the positivity of the influenza virus throughout a 4-year span, encompassing both the pre-COVID-19 era (2018 and 2019) and the COVID-19 period (2020 and 2021). Data collected from patients clinically diagnosed with Influenza-like Illness and Severe Acute Respiratory Illness (SARI) from January 2018 to December 2021 for influenza virus detection were acquired and analyzed through multiplex RT-qPCR. The statistical analysis was conducted using SPSS (Statistical Package for Social Sciences) Version 21.0 Software. A total of 4464 samples were tested over 4 years (2018-2021), with 3201 samples from the pre-COVID era and 1263 samples from the COVID era. Influenza A positivity dropped from 17.7 to 9.57% and Influenza B positivity decreased from 3.74 to 2.61%. Subtyping revealed changes in prevalence for both viruses. Seasonal variations showed more pronounced peaks in the pre-COVID-19 era with reduced activity during lockdown. Influenza A saw a resurgence in August 2021. Throughout the COVID-19 pandemic (2020-2021) SARI cases did not decrease. The positivity rate for Influenza A slightly rose to 7.79% from 4.23% in the COVID period (2020-2021). This increase correlates with heightened hospitalization rates during the pandemic, sparking concerns of potential coinfection with coronavirus and Influenza A. The notable drop in influenza cases in 2020-2021 is likely due to stringent precautions, lockdowns, drug repurposing, and prioritized testing, indicating no reduction in influenza transmission. Increased influenza positivity in SARI patients during COVID-19 highlights a heightened risk of coinfection. Emphasizing solely on COVID-19 may lead to underreporting of other respiratory pathogens, including influenza viruses.

Giant Cell Tumor of the Tendon Sheath of the Hand: Analysis of Factors Impacting Recurrence.

Background Giant cell tumors of the tendon sheath (GCTTS) of the hand are considered the second most common benign tumors of the hand after ganglion cysts. Excision biopsy is considered the standard treatment at present. They are notorious for having a very high rate of recurrence as given in many studies. Many factors are said to be associated with recurrence of the tumors. The goal of this study is to evaluate the long-term results of a series of 48 patients operated on at a single institute and to find out if there is any correlation between the proposed risk factors with recurrence. Methods A retrospective analysis was done in cases of GCTTS operated on between 2015 and 2021. The patients were invited for follow-up for a minimum of 2 years, and the patient files were reviewed. Further data were collected at follow-up including recurrence, range of movement, sensation, skin necrosis, scarring, and digital neuropathy. A data analysis was done. The correlation between the proposed risk factors and recurrence was calculated with the Pearson correlation coefficient. A p -value of less than 0.05 was considered statistically significant. Results During the 6 years, 48 patients were operated on. Recurrence was observed in eight patients (16%) at an average of 38.7 months from the time of surgery. Of the risk factors, tumors with satellite nodules and tumor adjacency to joint correlated significantly with recurrence. No complications were observed during follow-up. Conclusion GCTTS of the hand has a high propensity to recur. The presence of satellite nodules and proximity to interphalangeal joints are two important risk factors for recurrence. Magnification during surgery ensures complete excision of the tumor and reduces the chance of recurrence.

Effectiveness of fluoride mouthrinse in prevention of demineralization during fixed orthodontic treatment: A systematic review and meta-analysis.

Enamel demineralization is a very common occurrence around bonded brackets in an orthodontic practice. Fluoride (FLR) applications have been used to prevent decalcification and further progression of white spot lesions. The purpose of this systematic review and meta-analysis was to systematically appraise available literature on the effectiveness of fluoride mouthrinse in the prevention of demineralization around fixed orthodontic appliances. A search was conducted for randomized controlled clinical trials among four electronic databases (MEDLINE, Google Scholar, PubMed, and Cochrane Review) through MeSH terms and keywords. Studies were excluded if random allocation was not conducted, or if they were animal or in vitro studies. About 146 articles were screened and 5 studies were selected for the present review. Only two studies were selected for MA due to variations in the measurement of outcomes among studies. This review concluded that rinsing with FLR in the course of the fixed orthodontic treatment lessens demineralization around the bracket. Using FLR mouthrinse to inhibit the formation of white spot lesions or dental caries in patients with multiple cavities or restoration can be considered in clinical practice.

Circulating serotypes and genotypes of dengue virus in North India: An observational study.

BACKGROUND OBJECTIVES: This study reports observation on circulating serotypes and genotypes of Dengue Virus in North India. METHODS: Serum samples were obtained from suspected cases of dengue referred to the virus diagnostic laboratory during 2014 to 2022. All samples were tested for anti-dengue virus IgM antibodies and NS1Ag by ELISA. NS1Ag positive samples were processed for serotyping and genotyping. RESULTS: Total 41,476 dengue suspected cases were referred to the laboratory of which 12,292 (29.6%) tested positive. Anti-Dengue Virus IgM antibodies, NS1Ag, both IgM and NS1Ag, were positive in 7007 (57.4%); 3200 (26.0%) and 2085 (16.0%) cases respectively. Total 762 strains were serotyped during 9-year period. DENV-1, DENV-2, DENV-3 and DENV-4 serotypes were found in 79 (10.37%), 506 (66.40%), 151 (19.82%) and 26 (3.41%) cases respectively. DENV-1, DENV-2 and DENV-3 were in circulation throughout. Total 105 strains were genotyped. Genotype IV of DENV-1 serotype was circulating till 2014 which was later replaced by genotype V. A distinct seasonality with increase in number of cases in post-monsoon period was seen. INTERPRETATION CONCLUSION: DENV-1, DENV-2 and DENV-3 were found to be in circulation in North India. Predominant serotype/genotype changed at times, but not at regular intervals.

Deep eutectic solvents: Preparation, properties, and food applications.

Deep Eutectic Solvents (DESs) emerge as innovative 21st-century solvents, supplanting traditional ones like ethanol and n-hexane. Renowned for their non-toxic, biodegradable, and water-miscible nature with reduced volatility, DESs are mostly synthesized through heating and stirring method. Physicochemical properties such as polarity, viscosity, density and surface tension of DESs influenced their application. This review paper gives the overview of application of eco-benign DESs in fruits, vegetables, cereals, pulses, spices, herbs, plantation crops, oil seed crops, medicinal and aromatic plants, seaweed, and milk for the extraction of bioactive compounds. Also, it gives insight of determination of pesticides, insecticides, hazardous and toxic compounds, removal of heavy metals, detection of illegal milk additive, purification of antibiotics and preparation of packaging film. Methodologies for separating bioactive compounds from DESs extracts are systematically examined. Further, safety regulations of DESs are briefly discussed and reviewed literature reveals prevalent utilization of DES-based bioactive compound rich extracts in cosmetics, indicating untapped potential of their application in the food industry.

Isolated Myocysticercosis of Pectoralis Major: A Rare Case.

Isolated myocysticercosis is a neglected tropical disease and a rare diagnosis, with only a handful of cases being reported in the literature. It is highlighted that recently, it has not only been limited to endemic regions but also persists globally due to widespread migration from endemic regions. We present a case of isolated myocysticercosis of the right pectoralis major without neurological involvement in a non-pork-eater. High-resolution ultrasonography is an effective method of diagnosis. Anti-helmintic drugs are effective treatment options; if not responding, surgical excision is the management of choice. Ultrasound-guided excision is a better treatment modality to prevent complications.

Reconsidering the discontinuation of M.Phil. programs in clinical psychology and psychiatric social work: An imperative for India's mental health future.

This viewpoint critically examines the New Education Policy (NEP) 2020's decision to discontinue M.Phil. programs in Clinical Psychology and Psychiatric Social Work in India. It explores the crucial roles these programs play in addressing the country's shortage of mental health professionals and evaluates the potential impact of this decision on mental healthcare. The article advocates for the necessity of these programs in maintaining the quality and accessibility of mental health services and calls for a reconsidered policy approach that balances educational reforms with the specialized needs of the mental health sector.

Development and techno-economic analysis of Grewia biopolymer-based dual coagulant system for wastewater treatment at pilot scale.

Use of Grewia biopolymer as a natural coagulant aid was explored in a dual-coagulant system (conventional coagulant + biopolymer) for wastewater treatment. Such use not only improved turbidity removal efficiency over a wide pH range (5-9) but also helped reducing the concentration demand of inorganic coagulants by 25-50 %. Response surface methodology was employed for investigating the interaction between factors (initial pH, coagulant, and biopolymer concentration) affecting coagulation/flocculation of aqueous laterite suspension, and process optimization for more than 80 % turbidity removal in the desired final pH range (6-7). Mechanisms potentially involved in coagulation/flocculation using biopolymer was elucidated. Techno-economic assessment indicated the feasibility of pilot-scale production of the biopolymer and its use in wastewater treatment. This study demonstrates that Grewia biopolymer has the potential to be used as a coagulant aid and will help researchers select appropriate markets for further cost reduction and successful implementation of biopolymer-based wastewater treatment.

Exploring the diversity of vaginal microbiota between healthy women and cervical cancer patients in India.

Introduction. Cervicovaginal diversity has been reported as a predictive biomarker for cervical cancer risk. We recently reported the bio-therapeutic potential of vaginal probiotics from healthy Indian women against vaginal pathogens, isolated from the invasive cervical cancer (ICC) patients.Gap Statement. The cervicovaginal microflora from cervical cancer patients has not yet been reported from Indian population.Aim. The present study aimed at comparing the cervicovaginal microbiome between healthy controls (HC) and ICC patients from the Indian population.Methodology. In total, 30 vaginal swabs (15 from HC and 15 from ICC) were subjected to 16S rRNA gene sequencing. Alpha diversity was evaluated by Shannon and Chao1 index; and beta diversity by principle coordinate analysis (PCoA) of weighted and unweighted UniFrac distances. The relative abundance of the microbial taxa was done according to linear discriminant analysis effect size (LEfSe).Results. Predominance of Staphylococcus spp. in ICC and Lactobacillus gasseri in HC groups was observed. Alpha-diversity was found to be higher in ICC as compared to HC but was statistically non-significant. LEfSe analysis revealed Bacteroides fragilis and Escherichia coli as the marker genera in ICC with a marked decrease in Lactobacillus sp. Contrarily, in HC, L. gasseri, L. iners and L. fermentum were found to be abundant.Conclusion. Differences in the vaginal microbiome between healthy and ICC women could help in the early prediction of cervical cancer risk and thus in designing prevention strategies.

1,1'-Bis-(diphenylphosphino)ferrocene appended d8- and d10-configuration based thiosquarates: the molecular and electronic configurational insights into their sensitization and co-sensitization properties for dye sensitized solar cells.

Three new d8- and d10-configuration based 1,1'-bis-(diphenylphosphino)ferrocene (dppf) appended thiosquarates complexes with general composition [M(mtsq)2dppf] (M = Ni2+ (NiL2); Zn2+ (ZnL2) and Cd2+ (CdL2)) (mtsq = 3-ethoxycyclobutenedione-4-thiolate) have been synthesized and characterized spectroscopically as well as in case of NiL2 by single crystal X-ray diffraction technique. The single crystal X-ray analysis reveals square planar geometry around Ni(II) in NiL2, where Ni(II) coordinates with two sulfur centres of two mtsq ligands in monodentate fashion and two phosphorus of a dppf ligand in chelating mode. The supramolecular architecture of NiL2 is sustained by intermolecular C-H⋯O interactions to form one-dimensional chain. Further, the application of these newly synthesized complexes as sensitizers and co-sensitizers/co-absorbents with ruthenium based N719 sensitizer in dye-sensitized solar cells (DSSCs) have been explored. The DSSC set-up based on NiL2 offers best photovoltaic performance with photovoltaic efficiency (η) 5.12%, short-circuit current (Jsc) 11.60 mA cm-2, open circuit potential (Voc) 0.690 V and incident photon to current conversion efficiency (IPCE) 63%. In co-sensitized DSSC set-up, ZnL2 along with state-of-the-art N719 dye displays best photovoltaic performance with η 6.65%, Jsc 14.47 mA cm-2, Voc 0.729 V and IPCE 69%, thereby showing an improvement by 15.25% in photovoltaic efficiency in comparison to the photovoltaic efficiency of N719 sensitized DSSC set-up. Variation in co-sensitization behaviour have been ascribed to the differences in the excited state energy level of co-sensitizers. The ZnL2 and CdL2 have a higher energy level position than N719 dye, allowing efficient electron transfer to N719 during light irradiation, while excited state of NiL2 is lower than N719 dye, preventing photoexcited electron transfer to N719, resulting in its lowest overall efficiency among the three co-sensitized DSSC setups.

Tailoring the Photophysical Properties of a Homoleptic Iron(II) Tetra N-Heterocyclic Carbene Complex by Attaching an Imidazolium Group to the (C∧N∧C) Pincer Ligand─A Comparative Study.

We here report the synthesis of the homoleptic iron(II) N-heterocyclic carbene (NHC) complex [Fe(miHpbmi)2](PF6)4 (miHpbmi = 4-((3-methyl-1H-imidazolium-1-yl)pyridine-2,6-diyl)bis(3-methylimidazol-2-ylidene)) and its electrochemical and photophysical properties. The introduction of the π-electron-withdrawing 3-methyl-1H-imidazol-3-ium-1-yl group into the NHC ligand framework resulted in stabilization of the metal-to-ligand charge transfer (MLCT) state and destabilization of the metal-centered (MC) states. This resulted in an improved excited-state lifetime of 16 ps compared to the 9 ps for the unsubstituted parent compound [Fe(pbmi)2](PF6)2 (pbmi = (pyridine-2,6-diyl)bis(3-methylimidazol-2-ylidene)) as well as a stronger MLCT absorption band extending more toward the red spectral region. However, compared to the carboxylic acid derivative [Fe(cpbmi)2](PF6)2 (cpbmi = 1,1'-(4-carboxypyridine-2,6-diyl)bis(3-methylimidazol-2-ylidene)), the excited-state lifetime of [Fe(miHpbmi)2](PF6)4 is the same, but both the extinction and the red shift are more pronounced for the former. Hence, this makes [Fe(miHpbmi)2](PF6)4 a promising pH-insensitive analogue of [Fe(cpbmi)2](PF6)2. Finally, the excited-state dynamics of the title compound [Fe(miHpbmi)2](PF6)4 was investigated in solvents with different viscosities, however, showing very little dependency of the depopulation of the excited states on the properties of the solvent used.