Noncovalent Modulation of Chemoselectivity in the Gas Phase Leads to a Switchover in Reaction Type from Heterolytic to Homolytic to Electrocyclic Cleavage

In the gas phase, thermal activation of supramolecular assemblies such as host-guest complexes leads commonly to noncovalent dissociation into the individual components. Chemical reactions, for example of encapsulated guest molecules, are only found in exceptional cases. As observed by mass spectrometry, when 1-amino-methyl-2,3-diazabicyclo[2.2.2]oct-2-ene (DBOA) is complexed by the macrocycle β-cyclodextrin, its protonated complex undergoes collision-induced dissociation into its components, the conventional reaction pathway. Inside the macrocyclic cavity of cucurbit[7]uril (CB7), a competitive chemical reaction of monoprotonated DBOA takes place upon thermal activation, namely a stepwise homolytic covalent bond cleavage with the elimination of N2 , while the doubly protonated CB7⋅DBOA complex undergoes an inner-phase elimination of ethylene, a concerted, electrocyclic ring-opening reaction. These chemical reaction pathways stand in contrast to the gas-phase chemistry of uncomplexed monoprotonated DBOA, for which an elimination of NH3 predominates upon collision-induced activation, as a heterolytic bond cleavage reaction. The combined results, which can be rationalized in terms of organic-chemical reaction mechanisms and density-function theoretical calculations, demonstrate that chemical reactions in the gas phase can be steered chemoselectively through noncovalent interactions

Final technical report of the project on gender and migration : negotiating rights; a women’s movement perspective

The project devised a new method for assessing women’s work/employment situations through separation of paid and unpaid work, which has allowed for construction of a picture of female labour migration previously camouflaged in the official data by the dominance of marriage migration. At another level, the project investigated cross-region long distance marriage, to explore factors that determine movement of young brides to distant and different cultural regions. The research shows diverse patterns of migration and how migrant women workers are excluded from a range of citizenship rights: as migrant workers, as migrant women and as migrating citizens

Promoting the importance of aquatic foods on human nutrition and public health under APART in Assam

One of the key activities (Deliverable 7) under the APART project is “Improving impact of aquaculture and beel fisheries on human Nutrition”. WorldFish with partners is supporting the implementation of this activity. This consolidated report summarizes all the work done by WorldFish and partners as part of deliverable 7. The project has developed and tested several Social Behavioural Change Communication (SBCC) resources (e.g. banners, leaflets, brochures, calendars, TV spots, and videos) to promote the consumption of aquatic foods by vulnerable communities, PLM, adolescent girls, and children by targeting relevant stakeholders (e.g. Integrated Child Development Services programs, District Social Welfare (DSW) field functionaries, Anganwadi workers, Village communities, primary health centres, and the general public). We have trained 597 trainers to spread the message on the role of aquatic foods. We conducted 36 cluster-level awareness programs where 1994 numbers of women, adolescent girls and community people were given information on the benefits of fish consumption. We also organised 2 zonal workshops and 1 statelevel workshop for different stakeholders to build awareness of the importance of aquatic foods. Based on the demonstrations at the community level, the project documented all the small fish-based recipes cooked locally at the community level and produced a Small Fish Recipes book

Epidemiological and clinical profile of fatality in vulnerable road users at a high volume trauma center

Background: Motorized two-wheelers, pedestrians, and cyclists are termed vulnerable road users (VRUs).Globally up to 50% of road deaths involve VRU and up to 80% in developing and rapidly motorizing economies. Objective: The objective of this study is to study the prehospital and clinical profile of fatally injured VRU. This would help in informed decision-making regarding prevention and trauma care infrastructure. Materials and Methods: A hospital-based study was performed at a Trauma Centre in Puducherry from January 2013 to June 2014 (18 months). Puducherry is a union territory of India in the state of Tamil Nadu. A total of 193 deaths due to Road traffic accident were included in this study. The demographics, prehospital findings, and the clinical progress of fatally injured VRU are described. Results: More than 80% of road traffic collision/crash deaths involved VRU of which the elderly comprised a significant proportion. Alcohol was a serious issue even in the elderly pedestrian. This study revealed specific injury patterns and severity. Head injury was the most common cause of death. Early deaths, that is within 24 h of injury was common at 50%. Conclusion: The majority of deaths were in the early phase of trauma hence mandating a strong call for prevention, along with strengthening of trauma care

Synthesis of imidazo[1,2-a]pyridine derivatives and Zolimidine via a novel zinc/iodine-catalyzed Ortoleva-King type protocol

Imidazo[1,2-a]pyridines belong to a class of heterocyclic motifs possessing unique structural and pharmacological properties making them an interesting and promising domain in the fields of drug discovery and medicinal chemistry. These molecules have witnessed many fascinating strategies for their synthesis due to their versatile attribute. We herein put forward, the first zinc-catalyzed Ortoleva-King type reaction for the synthesis of imidazo[1,2-a]pyridines. The reaction design involves the use of easily accessible and economical nano zinc oxide and molecular iodine as the catalytic dyad. Diverse acetophenones and 2-aminopyridines were used as substrates and the reaction was observed to be general fostering moderate to good results. Furthermore, we could synthesize Zolimidine (a gastro-protectant) via this one-pot reaction design as a validation to its efficacy in the pharmaceutical world

A Molecular Electrostatic Potential Analysis of Hydrogen, Halogen, and Dihydrogen Bonds

Hydrogen, halogen, and dihydrogen bonds in weak, medium and strong regimes (<1 to ∼60 kcal/mol) have been investigated for several intermolecular donor–acceptor (D‑A) complexes at ab initio MP4//MP2 method coupled with atoms-in-molecules and molecular electrostatic potential (MESP) approaches. Electron density ρ at bond critical point correlates well with interaction energy (<i>E</i>_nb) for each homogeneous sample of complexes, but its applicability to the entire set of complexes is not satisfactory. Analysis of MESP minimum (<i>V</i>_min) and MESP at the nuclei (<i>V</i>_n) shows that in all D-A complexes, MESP of A becomes more negative and that of D becomes less negative suggesting donation of electrons from D to A leading to electron donor–acceptor (eDA) interaction between A and D. MESP based parameter ΔΔ<i>V</i>_n measures donor–acceptor strength of the eDA interactions as it shows a good linear correlation with <i>E</i>_nb for all D-A complexes (<i>R</i>² = 0.976) except the strongly bound bridged structures. The bridged structures are classified as donor–acceptor–donor complexes. MESP provides a clear evidence for hydrogen, halogen, and dihydrogen bond formation and defines them as eDA interactions in which hydrogen acts as electron acceptor in hydrogen and dihydrogen bonds while halogen acts as electron acceptor in halogen bonds

Electrostatic Potential Topology for Probing Molecular Structure, Bonding and Reactivity

Following the pioneering investigations of Bader on the topology of molecular electron density, the topology analysis of its sister field viz. molecular electrostatic potential (MESP) was taken up by the authors’ groups. Through these studies, MESP topology emerged as a powerful tool for exploring molecular bonding and reactivity patterns. The MESP topology features are mapped in terms of its critical points (CPs), such as bond critical points (BCPs), while the minima identify electron-rich locations, such as lone pairs and π-bonds. The gradient paths of MESP vividly bring out the atoms-in-molecule picture of neutral molecules and anions. The MESP-based characterization of a molecule in terms of electron-rich and -deficient regions provides a robust prediction about its interaction with other molecules. This leads to a clear picture of molecular aggregation, hydrogen bonding, lone pair–π interactions, π-conjugation, aromaticity and reaction mechanisms. This review summarizes the contributions of the authors’ groups over the last three decades and those of the other active groups towards understanding chemical bonding, molecular recognition, and reactivity through topology analysis of MESP

Anion Receptors Based on Highly Fluorinated Aromatic Scaffolds

Mono-, di-, and tri-pentafluorobenzyl-substituted hexafluorobenzene (HFB) scaffolds, <i>viz</i>., <b>R</b>_<b>I</b>, <b>R</b>_<b>II</b>, and <b>R</b>_<b>III</b> are proposed as promising receptors for molecules of chemical, biological, and environmental relevance, <i>viz</i>., N₂, O₃, H₂O, H₂O₂, F^–, Cl^–, BF₄^–, NO₃^–, ClO^–, ClO₂^–, ClO₃^–, ClO₄^–, and SO₄^2–. The receptor–guest complexes modeled using M06L/6-311++G­(d,p) DFT show a remarkable increase in the complexation energy (<i>E</i>_int) with an increase in the number of fluorinated aromatic moieties in the receptor. Electron density analysis shows that fluorinated aromatic moieties facilitate the formation of large number of lone pair−π interactions around the guest molecule. The lone pair strength of the guest molecules quantified in terms of the absolute minimum (<i>V</i>_min) of molecular electrostatic potential show that <i>E</i>_int strongly depends on the electron deficient nature of the receptor as well as strength of lone pairs in the guest molecule. Compared to HFB, <b>R</b>_<b>I</b> exhibits 1.1–2.5-fold, <b>R</b>_<b>II</b> shows 1.6–3.6-fold, and the bowl-shaped <b>R</b>_<b>III</b> gives 1.8–4.7-fold increase in the magnitude of <i>E</i>_int. For instance, in the cases of HFB···<b>F</b>^<b>–</b>, <b>R</b>_<b>I</b>···<b>F</b>^<b>–</b>, <b>R</b>_<b>II</b>···<b>F</b>^<b>–</b>, and <b>R</b>_<b>III</b>···<b>F</b>^<b>–</b> the <i>E</i>_int values are −21.1, −33.7, −38.1, and −50.5 kcal/mol, respectively. The results strongly suggest that tuning lone pair−π interaction provides a powerful strategy to design receptors for small molecules and anions