Human Immunodeficiency Virus Preexposure Prophylaxis Awareness and Acceptability among Men Who Have Sex with Men and Transgender Persons in India: Systematic Review and Meta-analysis.

With increasing importance being given to preexposure prophylaxis (PrEP) for human immunodeficiency virus prevention among men who have sex with men (MSM) and transgender persons (TG), we undertook a systematic review and meta-analysis of PrEP awareness and acceptability among these key populations in India, and their sociodemographic and behavioral determinants. The systematic review was registered with PROSPERO (CRD42023390508). Studies were included if they provided quantitative data on PrEP awareness or acceptability among MSM or TG in India. MEDLINE, Scopus, Web of Science, and Embase were searched from inception to February 29, 2024, using keywords and database-specific terms. Relevant websites were also searched. Critical appraisal was done using the Joanna Briggs Institute Checklist for Prevalence Studies. Random-effects meta-analysis was done for common outcomes reported by the studies. Reporting was as per the Preferred Reporting Items for Systematic Reviews and Meta-analyses 2020 statement. Ten studies providing cross-sectional data, mostly from South West India, were included for qualitative synthesis. All were conducted in settings where PrEP was not available. The pooled prevalence among MSM and TG was 18.7% (95% confidence interval [CI] 8.7%, 28.7%) for awareness and 79.8% (95% CI 57.4%, 100.0%) for willingness to use daily oral PrEP. This review highlights the felt need for PrEP among MSM and TG in India. Further research is needed to understand user attitudes in different parts of the country.

Spectroscopy-based chemometrics combined machine learning modeling predicts cashew foliar macro- and micronutrients.

Precision nutrient management in orchard crops needs precise, accurate, and real-time information on the plant's nutritional status. This is limited by the fact that it requires extensive leaf sampling and chemical analysis when it is to be done over more extensive areas like field- or landscape scale. Thus, rapid, reliable, and repeatable means of nutrient estimations are needed. In this context, lab-based remote sensing or spectroscopy has been explored in the current study to predict the foliar nutritional status of the cashew crop. Novel spectral indices (normalized difference and simple ratio), chemometric modeling, and partial least square regression (PLSR) combined machine learning modeling of the visible near-infrared hyperspectral data were employed to predict macro- and micronutrients content of the cashew leaves. The full dataset was divided into calibration (70 % of the full dataset) and validation (30 % of the full dataset) datasets. An independent validation dataset was used for the validation of the algorithms tested. The approach of spectral indices yielded very poor and unreliable predictions for all eleven nutrients. Among the chemometric models tested, the performance of the PLSR was the best, but still, the predictions were not acceptable. The PLSR combined machine learning modeling approach yielded acceptable to excellent predictions for all the nutrients except sulphur and copper. The best predictions were observed when PLSR was combined with Cubist for nitrogen, phosphorus, potassium, manganese, and zinc; support vector machine regression for calcium, magnesium, iron, copper, and boron; elastic net for sulphur. The current study showed hyperspectral remote sensing-based models could be employed for non-destructive and rapid estimation of cashew leaf macro- and micro-nutrients. The developed approach is suggested to employ within the operational workflows for site-specific and precision nutrient management of the cashew orchards.

Causal network perturbation analysis identifies known and novel type-2 diabetes driver genes.

The molecular pathogenesis of diabetes is multifactorial, involving genetic predisposition and environmental factors that are not yet fully understood. However, pancreatic ß-cell failure remains among the primary reasons underlying the progression of type-2 diabetes (T2D) making targeting ß-cell dysfunction an attractive pathway for diabetes treatment. To identify genetic contributors to ß-cell dysfunction, we investigated single-cell gene expression changes in ß-cells from healthy (C57BL/6J) and diabetic (NZO/HlLtJ) mice fed with normal or high-fat, high-sugar diet (HFHS). Our study presents an innovative integration of the causal network perturbation assessment (ssNPA) framework with meta-cell transcriptome analysis to explore the genetic underpinnings of type-2 diabetes (T2D). By generating a reference causal network and in silico perturbation, we identified novel genes implicated in T2D and validated our candidates using the Knockout Mouse Phenotyping (KOMP) Project database.

Estimation of rice yield using multivariate analysis techniques based on meteorological parameters.

This study aims to develop predictive models for rice yield by applying multivariate techniques. It utilizes stepwise multiple regression, discriminant function analysis and logistic regression techniques to forecast crop yield in specific districts of Haryana. The time series data on rice crop have been divided into two and three classes based on crop yield. The yearly time series data of rice yield from 1980-81 to 2020-21 have been taken from various issues of Statistical Abstracts of Haryana. The study also utilized fortnightly meteorological data sourced from the Agrometeorology Department of CCS HAU, India. For comparing various predictive models' performance, evaluation of measures like Root Mean Square Error, Predicted Error Sum of Squares, Mean Absolute Deviation and Mean Absolute Percentage Error have been used. Results of the study indicated that discriminant function analysis emerged as the most effective to predict the rice yield accurately as compared to logistic regression. Importantly, the research highlighted that the optimum time for forecasting the rice yield is 1 month prior to the crops harvesting, offering valuable insight for agricultural planning and decision-making. This approach demonstrates the fusion of weather data and advanced statistical techniques, showcasing the potential for more precise and informed agricultural practices.

Nonenzymatic dual glucose sensing on boronic acid modified zeolitic imidazolate framework-67 nanoparticles for diabetes management.

For early diabetes identification and management, the progression of an uncomplicated and exceedingly responsive glucose testing technology is crucial. In this study, we present a new sensor incorporating a composite of metal organic framework (MOF) based on cobalt, coated with boronic acid to facilitate selective glucose binding. Additionally, we successfully employed a highly sensitive electro-optical immunosensor for the detection of subtle changes in concentration of the diabetes biomarker glycated haemoglobin (HbA1c), using zeolitic imidazolate framework-67 (ZIF-67) coated with polydopamine which further modified with boronic acid. Utilizing the polymerization characteristics of dopamine and the NH2 groups, a bonding structure is formed between ZIF-67 and 4-carboxyphenylboronic acid. ZIF-67 composite served as an effective substrate for immobilising 4-carboxyphenylboronic acid binding agent, ensuring precise and highly selective glucose identification. The sensing response was evaluated through both electrochemical and optical methods, confirming its efficacy. Under optimized experimental condition, the ZIF-67 based sensor demonstrated a broad detection range of 50-500 mg dL-1, a low limit of detection (LOD) of 9.87 mg dL-1 and a high correlation coefficient of 0.98. Furthermore, the 4-carboxyphenylboronic acid-conjugated ZIF-67-based sensor platform exhibited remarkable sensitivity and selectivity in optical-based detection for glycated haemoglobin within the clinical range of 4.7-11.3%, achieving a LOD of 3.7%. These findings highlight the potential of the 4-carboxyphenylboronic acid-conjugated ZIF-67-based electro-optical sensor as a highly sensitive platform for diabetes detection.

The Effective Inhibitory Concentration of Interferon-ß Correlates with Infectivity and Replication Fitness of SARS-CoV-2 Variants.

India saw a spike in COVID-19 cases in early 2023, and this wave of infection was attributed to XBB sublineages of SARS-CoV-2 Omicron variant. The impact of XBB wave was significantly shorter with low burden of severe cases or hospitalization as compared with previous SARS-CoV-2 variants of concern. Although a combination of old and new mutations in the spike region of XBB.1.16 variant led to a drastic reduction in the ability of antibodies from prior immunity to neutralize this virus, additional nonspike mutations suggested a possible change in its ability to suppress innate immune responses. In this study, we tested the sensitivity of Delta, BA.2.75, and XBB.1.16 variants to interferon-ß (IFN-ß) treatment and found that XBB.1.16 variant was most sensitive to IFN-ß. We next tested the ability of serum antibodies from healthy individuals to neutralize XBB.1.16. We showed that most of the individuals with hybrid immunity maintained a low but significant level of neutralizing antibodies to XBB.1.16 variant. Therefore, our observations indicated that both hybrid immunity because of natural infection and enhanced sensitivity to IFNs may have contributed to the low impact of XBB.1.16 infections in India.

Rectourethral Fistula after Posterior Urethral Valves Ablation in an Infant: A Rare Complication.

Acquired rectourethral fistula (RUF) is a rare but major complication of posterior urethral valve ablation. We present a case of a 1-year-old boy managed in a staged manner by completion of posterior urethral valves ablation, colostomy, RUF division through anterior sagittal transanorectal approach, and stoma closure. The child is continent for urine and feces.

Noninvasive neuromodulatory effect on cognition in individuals with traumatic brain injury: A single-blinded, two-arm parallel randomized clinical trial.

Objectives: The study aimed to compare the effect of cranial electrical stimulation (CES) and transcranial direct current stimulation (tDCS) in improving cognition among individuals with mild traumatic brain injury. Patients and methods: The pretest-posttest randomized controlled study was conducted between November 2020 and March 2022. Seventy-two patients (64 males, 8 females; mean age: 40.5±9.5 years; range, 18 to 45 years) experiencing cognitive impairment within three months of traumatic brain injury were recruited. Participants were randomly assigned into two groups: Group 1 (CES with cognitive training, n=36) and Group 2 (tDCS with cognitive training, n=36). Participants were blinded in the study. Both groups received 30-min sessions of neuromodulation along with 30 min of cognitive training five days a week for four weeks. The patients were assessed at baseline and at the end of two and four weeks of intervention. The primary outcome measure was the Montreal Cognition Assessment (MoCA), and the secondary outcome measure was the Galveston Orientation Amnesia Test (GOAT). Results: Demographic and baseline characteristics depicted normal distribution for both groups (p>0.05). Within group analyses of both groups demonstrated significant differences for both outcome measures (MoCA: p=0.001; GOAT: p=0.001). Between group analyses of MoCA showed significant improvement with p-value of 0.001 while GOAT exhibited p-value of 0.002 showing significant difference between the two groups. Time group interaction effect and covariance analyses depicted significant improvement with p-value of 0.001 for both outcome measures with excellent effect size >0.80. Conclusion: Cranial electrical stimulation was a more effective noninvasive neuromodulatory device than tDCS in improving cognition among individuals with traumatic brain injury.

Coronary Artery Disease Assessment via On-Site CT Fractional Flow Reserve in Patients Undergoing Transcatheter Aortic Valve Replacement.

Purpose To examine the clinical feasibility of workstation-based CT fractional flow reserve (CT-FFR) for coronary artery disease (CAD) evaluation during preprocedural planning in patients undergoing transcatheter aortic valve replacement (TAVR). Materials and Methods In this retrospective single-center study, 434 patients scheduled for TAVR between 2018 and 2020 were screened for study inclusion; a relevant proportion of patients (35.0% [152 of 434]) was not suitable for evaluation due to insufficient imaging properties. A total of 112 patients (mean age, 82.1 years ± 6.7 [SD]; 58 [52%] men) were included in the study. Invasive angiography findings, coronary CT angiography results, and Agatston score were acquired and compared with on-site CT-FFR computation for evaluation of CAD and prediction of major adverse cardiovascular events (MACE) within a 24-month follow-up. Results Hemodynamic relevant CAD, as suggested by CT-FFR of 0.80 or less, was found in 41 of 70 (59%) patients with stenosis of 50% or more. MACE occurred in 23 of 112 (20.5%) patients, from which 14 of 23 had stenoses with CT-FFR of 0.80 or less (hazard ratio [HR], 3.33; 95% CI: 1.56, 7.10; P = .002). CT-FFR remained a significant predictor of MACE after inclusion in a multivariable model with relevant covariables (HR, 2.89; 95% CI: 1.22, 6.86; P = .02). An Agatston score of 1000 Agatston units or more (HR, 2.25; 95% CI: 0.98, 5.21; P = .06) and stenoses of 50% or more determined via invasive angiography (HR, 0.94; 95% CI: 0.41, 2.17; P = .88) were not significant predictors of MACE. Conclusion Compared with conventional CAD markers, CT-FFR better predicted adverse outcomes after TAVR. A relevant portion of the screened cohort, however, was not suitable for CT-based CAD evaluation. Keywords: CT, Transcatheter Aortic Valve Implantation/Replacement (TAVI/TAVR), Cardiac, Coronary Arteries, Outcomes Analysis © RSNA, 2024 See also the commentary by Weir-McCall and Pugliese in this issue.

Group tele-rehabilitation improves quality of life among subjects with Parkinson's disease: A two arm non-parallel non-randomized clinical trial.

INTRODUCTION: Tele-rehabilitation has lately emerged as a promising medium for increasing patient adherence with significant positive results. One of the most prevalent neurological diseases affecting movement is Parkinson's disease (PD), which causes a variety of motor and non-motor symptoms among patients. Consequentially, the study was designed to compare the efficacy of group tele-rehabilitation with individual tele-rehabilitation in improving quality of life (QoL) among subjects with PD. METHOD: A two-group pretest-posttest, non-randomized clinical study recruited 68 subjects and classified them into two groups, i.e., Group A (group therapy, n = 36) and Group B (individual therapy, n = 32). Groups A and B received a supervised protocol consisting of a 40-min session on alternate days/week for twelve weeks via the WhatsApp Messenger application through group and individual therapy, respectively. The Parkinson's disease questionnaire (PDQ-39), mental and physical components of the Short Form Survey (SF-12) were used as primary outcome variables, while the Satisfaction questionnaire was used as a secondary outcome variable. RESULT: The p-values related to within-group analyses were <0.05 except SF-12 PCS >0.05 in Group A and <0.05 in Group B. While the p-values related to between-group analyses were <0.05 except for pre-scores of SF-12 (MCS and PCS). The effect sizes for PDQ-39, SF-12 (MCS), and SF-12 (PCS) were -2.37, 3.36, and 0.66 in Group A and 1.95, 2.69, and 2.03 in Group B, respectively. CONCLUSION: The study concluded that group tele-rehabilitation is more effective in improving QoL among subjects with PD as compared to individual tele-rehabilitation. Clinical trial Registration NoCTRI/2022/04/041818.

Advanced Functionalized Nanoclusters (Cu, Ag, and Au) as Effective Catalyst for Organic Transformation Reactions.

A considerable amount of research has been carried out in recent years on synthesizing metal nanoclusters (NCs), which have wide applications in the field of optical materials with non-linear properties, bio-sensing, and catalysis. Aside from being structurally accurate, the atomically precise NCs possess well-defined compositions due to significant tailoring, both at the surface and the core, for certain functionalities. To illustrate the importance of atomically precise metal NCs for catalytic processes, this review emphasizes 1) the recent work on Cu, Ag, and Au NCs with their synthesis, 2) the parameters affecting the activity and selectivity of NCs catalysis, and 3) the discussion on the catalytic potential of these metal NCs. Additionally, metal NCs will facilitate the design of extremely active and selective catalysts for significant reactions by elucidating catalytic mechanisms at the atomic and molecular levels. Future advancements in the science of catalysis are expected to come from the potential to design NCs catalysts at the atomic level.

Single-cell and bulk transcriptional profiling of mouse ovaries reveals novel genes and pathways associated with DNA damage response in oocytes.

Immature oocytes enclosed in primordial follicles stored in female ovaries are under constant threat of DNA damage induced by endogenous and exogenous factors. Checkpoint kinase 2 (CHEK2) is a key mediator of the DNA damage response in all cells. Genetic studies have shown that CHEK2 and its downstream targets, p53 and TAp63, regulate primordial follicle elimination in response to DNA damage, however the mechanism leading to their demise is still poorly characterized. Single-cell and bulk RNA sequencing were used to determine the DNA damage response in wildtype and Chek2-deficient ovaries. A low but oocyte-lethal dose of ionizing radiation induces a DNA damage response in ovarian cells that is solely dependent on CHEK2. DNA damage activates multiple ovarian response pathways related to apoptosis, p53, interferon signaling, inflammation, cell adhesion, and intercellular communication. These pathways are differentially employed by different ovarian cell types, with oocytes disproportionately affected by radiation. Novel genes and pathways are induced by radiation specifically in oocytes, shedding light on their sensitivity to DNA damage, and implicating a coordinated response between oocytes and pre-granulosa cells within the follicle. These findings provide a foundation for future studies on the specific mechanisms regulating oocyte survival in the context of aging, as well as therapeutic and environmental genotoxic exposures.

Bioenergetic profiles of peripheral mononuclear cells and systemic inflammation in women with Interstitial Cystitis/Bladder Pain Syndrome (IC/BPS).

Inflammation is thought to contribute to the etiology of interstitial cystitis/bladder pain syndrome (IC/BPS). It is well-known that disruption in metabolism in immune cells contributes to inflammation in several inflammatory diseases. The purpose of this study was to investigate whether cellular bioenergetics is altered in monocytes and lymphocytes from women with IC/BPS, and if these alterations correlate with systemic inflammatory markers. Age and BMI matched adult healthy women (HS; n = 18) and women with IC/BPS (n = 18) were included in the study. Blood was collected to assess cellular bioenergetics in monocytes and lymphocytes using a Seahorse XF96 Analyzer and plasma cytokine levels were measured using Meso Scale Discovery immunoassays. The correlation between bioenergetic parameters, cytokines, and demographics was determined using Pearson correlation coefficients. Means of the two groups were compared using the two-group t-test. Patients with IC/BPS had reduced monocyte oxygen consumption rates and glycolytic rates compared to healthy subjects. In contrast, lymphocytes from these patients had increased oxygen consumption rates and glycolytic rates. Several cytokines and chemokines including Interferon-gamma (IFN-É£), tumor necrosis factor alpha (TNF-ɑ), Interleukin-6 (IL-6), Interleukin-8 (IL-8) and vascular endothelial growth factor (VEGF) levels were significantly elevated in the plasma of patients with IC/BPS. However, Transforming growth factor (TGF-ß) and Interleukin-10 (IL-10) levels were significantly decreased in IC/BPS patients compared to HS. In addition, Interferon gamma (IFN-É£), TNF-ɑ, IL-8, and TGF-ß levels correlated with several bioenergetic parameters in monocytes or lymphocytes from healthy subjects. In contrast, TNF-ɑ and IL-8 correlated with bioenergetic parameters in monocytes from IC/BPS patients. Monocyte and lymphocyte cellular bioenergetics and plasma cytokine levels are different in patients with IC/PBS compared to HS. It appears that systemic inflammation is greater in this cohort which may negatively impact immune cell function. The relationship between cellular bioenergetics and inflammation in monocytes and lymphocytes could be important in understanding the pathogenesis of IC/PBS and warrants further investigation.

Sesamol as a potent anticancer compound: from chemistry to cellular interactions.

Sesamol (SM), a well-known component isolated from sesame seeds (Sesamum indicum), used in traditional medicines in treating numerous ailments. However, numerous molecular investigations revealed the various mechanisms behind its activity, emphasizing its antiproliferative, anti-inflammatory, and apoptosis-inducing properties, preventing cancer cell spread to distant organs. In several cells derived from various malignant tissues, SM-regulated signal transduction pathways and cellular targets have been identified. This review paper comprehensively describes the anticancer properties of SM and SM-viable anticancer drugs. Additionally, the interactions of this natural substance with standard anticancer drugs are examined, and the benefits of using nanotechnology in SM applications are explored. This makes SM a prime example of how ethnopharmacological knowledge can be applied to the development of contemporary drugs.

The combined effect of neuro-modulation and neuro-stimulation on pain in patients with cervical radiculopathy - a double-blinded, two-arm parallel randomized controlled trial.

INTRODUCTION: Cervical radiculopathy is one of those disabling conditions which results in central and peripheral pain and thus affects the quality of life. Transcutaneous Electrical Nerve Stimulation (TENS) and exercises produce analgesic effect but their long-term effect has not been available to date. Transcranial Direct Current stimulation (tDCS) is known to produce promising effects on central pain by targeting cortical activity. PURPOSE: To determine the combined effect of tDCS and TENS with exercises on pain and quality of life in patients with cervical radiculopathy. METHOD: Forty four patients (male: female = 26:18) of the age group 18-50 years were recruited and randomly allocated into the experimental group and control group. The experimental group received active anodal tDCS for 20 min with an intensity of 2 mA, while the control group received sham anodal tDCS. TENS over the pain distribution area for 20 min with 5 Hz intensity and 80-150 ms pulse duration followed by neck-specific exercises were given in both groups. This protocol was given 5 days a week for 4 weeks. Pre and post-assessments were obtained through outcome measures that the Numeric Pain Rating Scale and Neck Disability Index for the measurement of pain, functional disability, and quality of life. RESULT: Paired t-test/Wilcoxon-Signed Rank test, and Index and Mann-Whitney U test were used to compare the demographic variables within and across the groups, respectively for Neck Disability for Numeric Pain Rating Scale, keeping the P-value < 0.05 as significant. One-way repeated-measures analysis of variance (ANOVA) was applied to determine the between-subject factor differences. Post hoc tests with Bonferroni correction for repeated analyses were performed. Results depicted a significant effect for NDI (P = 0.001 for both groups) and NPRS (P = 0.003 for the experimental group and 0.007 for the control group). Significant Interaction effect (time*group) was observed for NDI (F = 42, 5382.77) and NPRS (F = 42, 1844.57) with a P-value of 0.001 for both outcome measures. Clinical significance was observed for both outcome measures having a mean difference in 50.21 and 4.57 for NDI and NPRS, respectively compared with the established MCID of 13.2 and 2.2 scores for respective outcome measures. CONCLUSION: It was concluded that active tDCS along with TENS and exercise intervention was effective on pain, disability, and quality of life in patients with cervical radiculopathy.

Pyridine Iodine(I) Cations: Kinetic Trapping as a Sulfonate Complexes.

Seven pyridine iodine(I) sulfonate complexes were prepared and isolated at low temperatures and characterized by X-ray diffraction analysis. The inherently instable pyridine iodine(I) cations are stabilized by an oxygen of sulfonate anions via the I⋅⋅⋅O halogen bond. In these complexes, the iodine atom of the pyridine iodine(I) cation acts as an electron acceptor and the sulfonate oxygen as the electron donor. These complexes are stable enough in the crystalline state, yet decompose rapidly under ambient conditions, also being unstable in solution. The (pyridine)N-I bond lengths [2.140(3)-2.197(2) Å] and the I⋅⋅⋅O halogen bonds [2.345(6)-2.227(3) Å] are analogous to (imide)N-I⋅⋅⋅O-N-pyridine uncharged halogen-bonded complexes formed from N-haloimides and pyridine N-oxides, thus confirming the existence of elusive pyridine iodine(I) cation.

Lipid Nanocapsule: A Novel Approach to Drug Delivery System Formulation Development.

Nanocapsules are polymeric nanoparticles encased in a polymeric coating composed of a predominantly non-ionic surfactant, macromolecules, phospholipids, and an oil core. Lipophilic drugs have been entrapped using various nanocarriers, including lipid cores, likely lipid nanocapsules, solid lipid nanoparticles, and others. A phase inversion temperature approach is used to create lipid nanocapsules. The PEG (polyethyleneglycol) is primarily utilised to produce nanocapsules and is a critical parameter influencing capsule residence time. With their broad drug-loading features, lipid nanocapsules have a distinct advantage in drug delivery systems, such as the capacity to encapsulate hydrophilic or lipophilic pharmaceuticals. Lipid nanocapsules, as detailed in this review, are surface modified, contain target-specific patterns, and have stable physical and chemical properties. Furthermore, lipid nanocapsules have target-specific delivery and are commonly employed as a marker in the diagnosis of numerous illnesses. This review focuses on nanocapsule synthesis, characterisation, and application, which will help understand the unique features of nanocapsules and their application in drug delivery systems.

Ortho-Substituent Effects on Halogen Bond Geometry for N-Haloimide⋯2-Substituted Pyridine Complexes.

The nature of (imide)N-X⋯N(pyridine) halogen-bonded complexes formed by six N-haloimides and sixteen 2-substituted pyridines are studied using X-ray crystallography (68 crystal structures), Density Functional Theory (DFT) (86 complexation energies), and NMR spectroscopy (90 association constants). Strong halogen bond (XB) donors such as N-iodosuccinimide form only 1:1 haloimide:pyridine crystalline complexes, but even stronger N-iodosaccharin forms 1:1 haloimide:pyridine and three other distinct complexes. In 1:1 haloimide:pyridine crystalline complexes, the haloimide's N─X bond exhibits an unusual bond bending feature that is larger for stronger N-haloimides. DFT complexation energies (ΔEXB ) for iodoimide-pyridine complexes range from -44 to -99 kJ mol-1 , while for N-bromoimide-pyridine, they are between -31 and -77 kJ mol-1 . The ΔEXB of I⋯N XBs in 1:1 iodosaccharin:pyridine complexes are the largest of their kind, but they are substantially smaller than those in [bis(saccharinato)iodine(I)]pyridinium salts (-576 kJ mol-1 ), formed by N-iodosaccharin and pyridines. The NMR association constants and ΔEXB energies of 1:1 haloimide:pyridine complexes do not correlate as these complexes in solution are heavily influenced by secondary interactions, which DFT studies do not account for. Association constants follow the σ-hole strengths of N-haloimides, which agree with DFT and crystallography data. The haloimide:2-(N,N-dimethylamino)pyridine complex undergoes a halogenation reaction resulting in 5-iodo-2-dimethylaminopyridine.

The Impact of ortho-substituents on Bonding in Silver(I) and Halogen(I) Complexes of 2-Mono- and 2,6-Disubstituted Pyridines: An In-Depth Experimental and Theoretical Study.

The coordination nature of 2-mono- and 2,6-disubstituted pyridines with electron-withdrawing halogen and electron-donating methyl groups for [N-X-N]+ (X=I, Br) complexations have been studied using 15 N NMR, X-ray crystallography, and Density Functional Theory (DFT) calculations. The 15 N NMR chemical shifts reveal iodine(I) and bromine(I) prefer to form complexes with 2-substituted pyridines and only 2,6-dimethylpyridine. The crystalline halogen(I) complexes of 2-substituted pyridines were characterized by using X-ray diffraction analysis, but 2,6-dihalopyridines were unable to form stable crystalline halogen(I) complexes due to the lower nucleophilicity of the pyridinic nitrogen. In contrast, the halogen(I) complexes of 2,6-dimethylpyridine, which has a more basic nitrogen, are characterized by X-crystallography, which complements the 15 N NMR studies. DFT calculations reveal that the bond energies for iodine(I) complexes vary between -291 and -351 kJ mol-1 and for bromine between -370 and -427 kJ mol-1 . The bond energies of halogen(I) complexes of 2-halopyridines with more nucleophilic nitrogen are 66-76 kJ mol-1 larger than those of analogous 2,6-dihalopyridines with less nucleophilic nitrogen. The experimental and DFT results show that the electronic influence of ortho-halogen substituents on pyridinic nitrogen leads to a completely different preference for the coordination bonding of halogen(I) ions, providing new insights into bonding in halogen(I) chemistry.