A Formal γ-C-H Functionalization of Carboxylic Acids Guided by Metal-Nitrenoids as an Unprecedented Mechanistic Motif.

Harnessing the key intermediates in metal-catalyzed reactions is one of the most essential strategies in the development of selective organic transformations. The nitrogen group transfer reactivity of metal-nitrenoids to ubiquitous C-H bonds allows for diverse C-N bond formation to furnish synthetically valuable aminated products. In this study, we present an unprecedented reactivity of iridium and ruthenium nitrenoids to generate remote carbocation intermediates, which subsequently undergo nucleophile incorporation, thus developing a formal γ-C-H functionalization of carboxylic acids. Mechanistic investigations elucidated a unique singlet metal-nitrenoid reactivity to initiate an abstraction of γ-hydride to form the carbocation intermediate that eventually reacts with a broad range of carbon, nitrogen, and oxygen nucleophiles, as well as biorelevant molecules. Alternatively, the same intermediate can lead to deprotonation to afford ß,γ-unsaturated amides in a less nucleophilic solvent.

Manganese(I)-Catalyzed Sustainable Synthesis of Quinoxaline and Quinazoline Derivatives with the Liberation of Dihydrogen.

Direct synthesis of N-heterocycles via the acceptorless dehydrogenative coupling is very challenging and scarcely reported under 3d transition-metal catalysis. Here, we have developed an efficient Mn(I)-catalyzed sustainable synthesis of various quinoxalines from 1,2-diaminobenzenes and 1,2-diols via the acceptorless dehydrogenative coupling reaction. Further, this strategy was successfully applied for the unprecedented synthesis of quinazolines by the reaction of 2-aminobenzyl alcohol with primary amides. The present protocol provides an atom-economical and sustainable route for the synthesis of various quinoxaline and quinazoline derivatives by employing an earth-abundant manganese salt and simple phosphine-free NNN-tridentate ligand.

Dynamics of expression of antibacterial and antioxidant defence genes in Indian major carp, Labeo rohita in response to Aeromonas hydrophila infection.

Cells produce large number of antioxidant molecules to prevent reactive oxygen species-induced self-damage during microbial assault while generating simultaneously number of antimicrobial molecules to target the pathogen. The present study was aimed at looking into molecules involved in antibacterial and self-protection mechanism of a host Labeo rohita when challenged with a pathogenic bacterium Aeromonas hydrophila. Expression profiles of few of the important host antibacterial genes viz., inducible nitric oxide synthase (iNOS), lysozyme G (LysoG), apolipoprotein A-I (ApoA-I) and hepcidin, and self-defence anti-oxidant genes viz., manganese superoxide dismutase (MnSOD), catalase and glutathione peroxidases (GPx3) were examined in skin and muscle tissues of bacteria challenged fish. Transcription levels of iNOS, LysoG, ApoA-I, hepcidin, catalase, GPx3 and MnSOD were significantly upregulated (P < 0.05) in both tissues at different time points post-bacterial challenge. Increased expression of antibacterial genes in the muscle and skin clearly explains strong defensive mechanism activated in fish tissues in terms of both oxygen-dependent (iNOS) and independent (lysozyme) ways of microbe reduction, and bacterial lysis via production of antimicrobial molecules (ApoA-I and hepcidin) in the host. Simultaneous upregulation of MnSOD, GPx3 and catalase genes explains their involvement in patrolling the cells with regulated production of reactive oxygen species and keeping at a safe level to protect the host's own cells from oxidative damage.

Risk factors of suicide among patients admitted with suicide attempt in Tata main hospital, Jamshedpur.

BACKGROUND: More than one lakh lives are lost every year due to suicide in India. In the last three decades (from 1975 to 2005), the suicide rate has increased by 43%. Jamshedpur is an Industrial town, which is rapidly growing and having population with mixed cultural background. Recently, there has been increasing trend in a number of suicide attempt across various age groups; there are around 300 cases of suicide attempt admitted to Tata Main Hospital each year. OBJECTIVE: To study the risk factors associated with suicide attempts. METHODS: The study was carried out in the Tata Main Hospital, Jamshedpur. Over a period of 6 months, we gathered data of 101 suicide attempters referred from medical, surgical departments and casualties and taken up for the study. Data were collected on specific pro forma was prepared to collect various others risk factors. RESULTS: More number of female patients compared to male, younger age, lower-middle income group, urban background, school educated, and unemployed were more represented in this study. In 70% of patients, psychiatric disorder was found, but few among them had prior treatment. Increased family conflicts, marital problems, financial difficulties, and perceived humiliations are some of the risk factors. CONCLUSION: The early identification and treatment of vulnerable populations with risk factors for suicide across the lifespan will help in planning and implementing strategies for prevention.

Suicide Attempt by Hanging - A Study on Patients Admitted in Tertiary Care Hospital in Eastern India.

Background: Suicide is defined as a fatal self-injurious act with some evidence of intent to die. Despite the evolution of sophisticated methods to commit suicide, hanging remains one of the commonest methods to commit suicide across the world. To evaluate the individuals using hanging as a method of suicide and identify the contributing factors for this behaviour. Material and Methods: The study was carried out in a tertiary care hospital, over a period of 1 year on the suicide attempters using the method of hanging. Semi-structured in-depth interviews were conducted with all the 46 attempters. The questions focused on the precipitating events present before the attempt. After the in interview the risk factors of the conversations were identified, tabulated and categorized using descriptive analysis. Results: Findings from descriptive analysis reveals that significant age group using this method was below 19 years followed by 20-29 age group, female attempters were more compared to male. Psychiatric diagnosis was present in 8 attempters and 4 attempters had alcohol/substance dependence. The most common personality component in attempters was impulsivity. The most common immediate stressor found were financial stress, conflict with family, spouse, humiliation, substance abuse, exam stress and domestic violence. Conclusion: This study demonstrates that the reasons for suicide attempt by hanging is multifactorial. which includes, psychiatric diagnosis, personality factors, immediate stressors, ease of use, and accessibility, Overall, our study adds to understanding the intricates of this method and will help in developing effective suicide prevention strategies.

Isolation and Reactivity of Arylnickel(II) Complexes in Nickel-Catalyzed Borylation of Aryl Fluorosulfates.

Aryl fluorosulfates have emerged as versatile SuFExable substrates, harnessing the reactivity of the S-F bond. In this study, we unveil their alternative synthetic utility in nickel-catalyzed borylation via C-O bond activation. This method highlights mild reaction conditions, a broad substrate scope, and moderate functional group tolerance, rendering it a practical and appealing approach for synthesizing a diverse array of aryl boronate esters. Furthermore, computational analysis sheds light on the reaction pathways, uncovering the participation of LNi(0) and LNi(II)ArX species. This insight is supported by the 31P NMR reaction monitoring along with isolation and single-crystal X-ray structural elucidation of well-defined arylnickel(II) intermediates obtained from the oxidative addition of aryl fluorosulfates. A comprehensive investigation, merging experimental and computational approaches, deepens our understanding of the alternative reactivity of SuFExable substrates.

A study on psychiatric conditions in children with school refusal- A clinic based study.

Introduction: School refusal is a broad term that encompasses a child-motivated refusal to attend or remain at school, or a clear and apparent difficulty in doing so. Different factors that may influence the development of school refusal include a genetic predisposition, the home and family environment, the school environment, and social pressures. the present study aimed at examining, the psychiatric diagnostic status of children and adolescents who presented with school refusal. Materials and Methods: 92 consecutive subjects who attended the Child guidance clinic at Tata Main Hospital Jamshedpur were taken up for this study. The Clinical Diagnosis was based on the classificatory system of the International classification of diseases-10(ICD-10) through interviews. Results: findings show that the mean age of the patient was 9.6 years. The prominent psychiatric co-morbidity present was Childhood emotional disorder unspecified, separation anxiety, conversion disorder, over-anxiety disorder, and somatoform disorder. Conclusion: Among children who refuse school, emotional reasons and anxiety disorders are most prevalent. This calls for early recognition and appropriate culturally relevant intervention to ensure early return to school.

Safety Profile of Aripiprazole During Pregnancy and Lactation: Report of 2 Cases. / Gebelik ve Emzirme Döneminde Aripiprazol Kullaniminin Güvenlik Profili: 2 Olgu Sunumu.

Aripiprazole, a second-generation antipsychotic (SGA) medication, is an efficacious treatment for schizophrenia and bipolar disorder. However, its effects on pregnancy and lactation are not yet fully documented. Despite aripiprazole being available since 2002, there is only limited information on the risks and benefits of this treatment during pregnancy. Most of the information is limited to populationbased studies examining malformation risk or case studies or small case series. The knowledge in this topic is still insufficient and there is a need to expand the literature. In this report, we present 2 cases exposed to aripiprazole during pregnancy and lactational period. In both our cases of aripiprazole exposure, no teratogenic effects were reported, and it was reassuring that the mothers did not develop gestational diabetes. However, both patients reported lactation failure. Keyword: Mental illness, antipsychotics, aripiprazole, pregnancy.

Double-outlet left ventricle: A rare case.

Double-outlet left ventricle (DOLV) is a rare cardiac malformation in which both great arteries originate from the morphological left ventricle. DOLV is associated with high mortality, generally due to heart failure, myocardial infarction, or aortic thrombosis. With surgery, the 5-year survival rate is estimated at 70%-75%. Most patients will continue to present with residual cardiac anomalies, such as aortic or mitral valve regurgitation, arrhythmias, or hypertension. Here, we report a 25-year-old male with DOLV with pulmonary stenosis and patent ductus arteriosus who presented to us with hemoptysis, which was due to respiratory tract infection. He improved with standard therapy.

Study on risk factors in adolescents admitted with deliberate self-harm in Tata main hospital, Jamshedpur.

BACKGROUND: Suicide ranks as the second cause of death worldwide among 15-19 years olds, with at least one lakh adolescents dying by suicide every year. Therefore, research on understanding the dynamics of suicide attempts in adolescents can be used as a means of suicide prevention. OBJECTIVE: The objective of this study is to understand the psychological, social, and personality factors contributing to deliberate self-harm/suicide attempt in patients of adolescent age group admitted to Tata Main Hospital, Jamshedpur. MATERIALS AND METHODS: This study was carried out at Tata Main Hospital Jamshedpur. Consecutive suicide attempters up to the age of 19 years referred from medical or surgical wards over a period of 1 year are taken up for study. Data were collected on socio-demographic sheet and specific pro forma to collect various risk factors contributing to this behavior specifically designed for this study. Data were analyzed using descriptive statistics and Chi-square test. RESULTS: Majority of the suicide attempters were females of younger age, lower-middle income status, urban background, and students. Two-third (68%) of the attempter had at least one psychiatric diagnosis. Nearly 75% of the suicide attempts were committed after a precipitating factor. The risk factors associated with suicide attempts in included increased family conflicts, peer-interpersonal problems, perceived humiliations and personality traits. CONCLUSION: The early identification and treatment of vulnerable populations with risk factors for suicide across the lifespan will help in planning and implementing strategies for prevention.

Neuroleptic malignant syndrome in a patient with stable dose of olanzapine.

Neuroleptic malignant syndrome (NMS), a potentially fatal consequence due to typical neuroleptics, has been described so far. In the past few years, there has been increased use of atypical antipsychotic drugs. Cases of NMS related to atypical neuroleptics, such as olanzapine, are less common in spite of increasing cases reported in literatures. Here, we report a case of NMS in a patient with bipolar affective disorder on maintenance treatment with 5 mg olanzapine for the last 7 year. He was successfully treated with bromocriptine and discharged in stable condition in 10 days.

Catatonia versus neuroleptic malignant syndrome: the diagnostic dilemma and treatment.

Catatonia is a syndrome, comprised of symptoms such as motor immobility, excessive motor activity, extreme negativism, and stereotyped movements. Neuroleptic is able to induce catatonia like symptoms, that is, the neuroleptic malignant syndrome (NMS). In NMS, patients typically show symptoms such as an altered mental state, muscle rigidity, tremor, tachycardia, hyperpyrexia, leukocytosis, and elevated serum creatine phosphorous kinase. Several researchers have reported studies on catatonia and the association between catatonia and NMS, but none were from this part of the eastern India. In our case, we observed overlapping symptoms of catatonia and NMS; we wish to present a case of this diagnostic dilemma in a patient with catatonia, where a detailed history, investigation, and symptom management added as a great contribution to the patient's rapid improvement.

Resting energy expenditure in subjects with fibro-calculous pancreatic diabetes.

BACKGROUND: Fibro-calculous pancreatic diabetes is an indigenous disorder present in populations largely in tropical regions. Energy expenditure through indirect calorimetry has not been studied in this disorder and may provide important clues as to the pathogenesis of diabetes in these patients. METHODS: A total of 51 males in three groups comprising fibrocalculous pancreatic diabetes (FCPD) (group 1; n = 24), type 2 diabetes (group 2; n = 15) and healthy controls (group 3; n = 12) were studied. The body composition was measured using Dual Energy X-ray Absorptiometry (DEXA) and the REE was estimated using indirect calorimetry. The predicted energy expenditure (PEE) was calculated using three different equations. RESULTS: Patients in both groups with diabetes had a higher mean waist-hip ratio than the controls (P = 0.002). However patients with type 2 diabetes alone had a significantly higher mean body mass index (P = 0.012), percentage of fat (P = 0.016) and total fat content (P = 0.031). There was no significant difference in REE among the three groups. After adjustment of body mass index (BMI), the REE was significantly higher in patients with FCPD than in those patients with Type 2 diabetes. PEE correlated poorly with indirect calorimetry. CONCLUSIONS: Energy expenditure in patients with diabetes varies according to the composition and distribution of body fat and is lower in patients with FCPD. Standard predictive equations were not accurate for the assessment of energy expenditure in patients with FCPD. Further research is required to recommend specific nutritional therapy for this group of patients.

Negative symptoms presenting as neuropsychiatric manifestation of vitamin B12 deficiency.

Long lists of psychiatric illness or symptoms have been documented to be caused by vitamin B12 deficiency. We describe an atypical case of a young adult who presented with predominant negative symptoms followed by neurological symptoms consistent with vitamin B12 deficiency. The symptoms showed complete remission after vitamin B12 supplementation. The uniqueness of this case is that vitamin B12 deficiency presented with predominant negative symptoms without other psychotic and manic symptoms, which has not been reported previously.

Psychiatric manifestations of Wilson's disease and treatment with electroconvulsive therapy.

Wilson's disease is a rare genetic disorder involving the liver and brain, with onset frequently in adolescence. Psychiatric symptoms are often the first manifestation of the disease and can obscure the diagnosis. Although such patients are more commonly seen in neurological and hepatological settings, mental health professionals must keep in mind a high level of suspicion, once first presentations may be of psychiatric nature. We present the case of a 20-year-old female patient who initially presented with psychiatric symptoms. The neuropsychiatric manifestations and treatment of this patient with electroconvulsive therapy is presented.