Physicochemical Studies on an All-Purpose Pesticide Spray Adjuvant-(APSA-80)

APSA-80, an useful pesticide spray adjuvant is a mixture of 2-[2-(4-nonylphenoxy) ethoxy] ethanol, 1-butanol and tall oil fatty acids. It is strongly surface active and can decrease the surface tension of water to ～20 mNm^?1 at its critical micelle concentration (CMC) of 0.006 g%. APSA-80 itself and its binary mixtures, (APSA-80 + water) and (APSA-80 + isopropylmyristate [IPM]) and ternary mixtures (APSA-80 + water +IPM) can undergo a number of physical changes with rise in temperature; the main changes are in color, turbidity and phases. The ternary mixtures of APSA-80/water/IPM with changing compositions can form mono-, bi-, and triphasic solutions as well as gels and viscous solutions. The gel and viscous phases show characteristic rheological properties of both shear thinning and thickening types. They also show permeation of hydrophilic and oleophilic dyes through them. SEM and optical microscopic measurements have shown interesting surface morphologies of the gels and their vertical projections in three-dimensional pictorial mode. Salts like LiCl, NaCl, KCl, CsCl, MgSO₄, and Al₂(SO₄)₃ can have both minor and major effects on the gel consistencies. The alkanols like ethanol, propanol, and isopropanol are also mild to fairly large gel influencing co solvents. The antibacterial properties of APSA-80 have been studied with two Gram positive bacteria and a yeast; the activities found were moderate.     

Anomalous behaviour in the SmA*–SmCA* pre‐transitional regime of a chiral swallow‐tailed antiferroelectric liquid crystal

The temperature‐ and electric field‐dependent dielectric relaxation and polarisation of a new chiral swallow tailed antiferroelectric liquid crystal, i.e. 1‐ethylpropyl (S)‐2‐{6‐[4‐(4′‐decyloxyphenyl)benzoyloxy]‐2‐naphthyl}propionate (abbreviated as EP10PBNP), were investigated. The electric field‐induced dielectric loss spectra of EP10PBNP revealed electroclinic and anomalous dielectric behaviour in the chiral smectic A (SmA*)–chiral antiferroelectric smectic C (SmC_A*) pre‐transitional regime. From an analysis of thermal hysteresis of the dielectric constant, electric field‐induced polarisation and dielectric loss spectra, the appearance of a ferrielectric‐like mesophase is observed followed by an unstable SmC_A* phase in the SmA*–SmC_A* pre‐transitional regime.     

Bioleaching of Nickel and Cobalt from Lateritic Chromite Overburden Using the Culture Filtrate of Aspergillus niger

Extraction of metals (Ni, Co) from chromite overburden of Sukinda mines of Orissa, India, with the culture filtrate of Aspergillus niger was studied. Results showed that the amounts of metals leached varied directly with reaction temperature and period of fermentation. The culture filtrate was analyzed for citric and oxalic acids, and contained only oxalic acid—the concentration of which increased with time. Although this acid played the major role in leaching of metals, other unidentified metabolites present in the culture filtrate influenced the dissolution of the metals significantly. Maximum recovery of metals from raw and roasted ore samples was achieved at 80 °C with the 21-day culture filtrate containing the highest amount of oxalic acid. Under identical experimental conditions, much higher amounts of the metals were leached from roasted ore. Microstructures of the ore particles were studied by scanning electron microscopy and transmission electron microscopy; the bonding behaviors of metal compounds were identified by Fourier transform infrared spectroscopy which showed that the metals were leached after chelation with oxalic acid.     

Odorless Preparation of Thioglycosides and Thio‐Michael Adducts of Carbohydrate Derivatives

A general, odorless, one‐pot methodology has been developed for the preparation of 1,2‐trans‐thioglycosides and thio‐Michael addition products of carbohydrate derivatives through triphenyl phosphine‐mediated cleavage of disulfides and reaction of the thiolate formed in situ with glycosyl bromides and glycosyl conjugated alkenes.     

Chemistry and Biology of Oligovalent β‐(1→2)‐Linked Oligomannosides: New Insights into Carbohydrate‐Based Adjuvants in Immunotherapy

A series of oligovalent carbohydrate assemblies (ranging from mono‐ to pentavalent), derived from three structurally different β‐linked or β‐(1→2)‐linked mannosides, has been chemically synthesized, and the respective compounds have been biologically evaluated in order to investigate their immunostimulatory properties. The Crich methodology for β‐mannosylation was successfully utilized to introduce the β‐linkages, and a click chemistry protocol was utilized to generate the oligovalent derivatives. A convenient protecting group strategy involving the simultaneous use of both p‐methoxybenzyl and benzylidene groups was employed, which allowed a simple and cost‐effective global deprotection step. The immunomodulatory properties of the synthesized multivalent mannosides were evaluated by assessing cytokine production in human white blood cell cultures. The Th2‐type cytokines interleukin‐4 and interleukin‐5 (IL‐4 and IL‐5), the Th1 cytokine interferon‐γ (IFN‐γ), the Treg cytokine IL‐10, and the pro‐inflammatory cytokine tumor necrosis factor (TNF) were included in the screening. A single trivalent acetylated mannobiose derivative was identified as a potent inducer of Treg and Th1 immune response, resulting in strong IL‐10 and moderate IFN‐γ productions dose‐dependently, while inducing no Th2 cytokine response. The immunomodulatory properties of this trivalent mannoside were further studied in vitro in allergen (Bet v)‐stimulated human peripheral blood mononuclear cell cultures of birch pollen allergic subjects. Stimulation with birch pollen induced strong IL‐4 and IL‐5 responses, which could be suppressed by the trivalent acetylated mannobiose derivative. The IL‐10 response was also suppressed, whereas the production of IFN‐γ was strongly enhanced. The results suggest that the identified lead compound has suppressive effects on the Th2‐type allergic inflammatory response and shows potential as a possible lead adjuvant for the specific immunotherapy of allergies.     

Brief survey on phytochemicals to prevent COVID-19

BackgroundThe recent pandemic by COVID-19 is a global threat to human health. The disease is caused by SARS-CoV-2 and the infection rate is increased more quickly than MERS and SARS as their rapid adaptation to varied climatic conditions through rapid mutations. It becomes more severe due to the lack of proper therapeutic drugs, insufficient diagnostic tool, scarcity of appropriate drug, life supporting medical facility and mostly lack of awareness. Therefore, preventive measure is one of the important strategies to control. In this context, herbal medicinal plants received a noticeable attention to treat COVID-19 in Indian subcontinent. Here, 44 Indian traditional plants have been discussed with their novel phytochemicals that prevent the novel corona virus. The basic of SARS-CoV-2, their common way of transmission including their effect on immune and nervous system have been discussed. We have analysed their mechanism of action against COVID-19 following in-silico analysis. Their probable mechanism and therapeutic approaches behind the activity of phytochemicals to stimulate immune response as well as inhibition of viral multiplication discussed rationally. Thus, mixtures of active secondary metabolites/phytochemicals are the only choice to prevent the disease in countries where vaccination will take long time due to overcrowded population density.     

Atomistic De-novo Inhibitor Generation-Guided Drug Repurposing for SARS-CoV-2 Spike Protein with Free-Energy Validation by Well-Tempered Metadynamics

Computational drug design is increasingly becoming important with new and unforeseen diseases like COVID-19. In this study, we present a new computational de novo drug design and repurposing method and applied it to find plausible drug candidates for the receptor binding domain (RBD) of SARS-CoV-2 (COVID-19). Our study comprises three steps: atom-by-atom generation of new molecules around a receptor, structural similarity mapping to existing approved and investigational drugs, and validation of their binding strengths to the viral spike proteins based on rigorous all-atom, explicit-water well-tempered metadynamics free energy calculations. By choosing the receptor binding domain of the viral spike protein, we showed that some of our new molecules and some of the repurposable drugs have stronger binding to RBD than hACE2. To validate our approach, we also calculated the free energy of hACE2 and RBD, and found it to be in an excellent agreement with experiments. These pool of drugs will allow strategic repurposing against COVID-19 for a particular prevailing conditions.     

Modification of Extended Open Frameworks with Fluorescent Tags for Sensing Explosives: Competition between Size Selectivity and Electron Deficiency

Three new electron‐rich metal–organic frameworks ( MOF‐1 – MOF‐3 ) have been synthesized by employing ligands bearing aromatic tags. The key role of the chosen aromatic tags is to enhance the π‐electron density of the luminescent MOFs. Single‐crystal X‐ray structures have revealed that these MOFs form three‐dimensional porous networks with the aromatic tags projecting inwardly into the pores. These highly luminescent electron‐rich MOFs have been successfully utilized for the detection of explosive nitroaromatic compounds (NACs) on the basis of fluorescence quenching. Although all of the prepared MOFs can serve as sensors for NACs, MOF‐1 and MOF‐2 exhibit superior sensitivity towards 4‐nitrotoluene (4‐NT) and 2,4‐dinitrotoluene (DNT) compared to 2,4,6‐trinitrotoluene (TNT) and 1,3,5‐trinitrobenzene (TNB). MOF‐3 , on the other hand, shows an order of sensitivity in accordance with the electron deficiencies of the substrates. To understand such anomalous behavior, we have thoroughly analyzed both the steady‐state and time‐resolved fluorescence quenching associated with these interactions. Determination of static Stern–Volmer constants (K_S) as well as collisional constants (K_C) has revealed that MOF‐1 and MOF‐2 have higher K_S values with 4‐NT than with TNT, whereas for MOF‐3 the reverse order is observed. This apparently anomalous phenomenon was well corroborated by theoretical calculations. Moreover, recyclability and sensitivity studies have revealed that these MOFs can be reused several times and that their sensitivities towards TNT solution are at the parts per billion (ppb) level.     

Insights into the AIEE of 1,8‐Naphthalimides (NPIs): Inverse Effects of Intermolecular Interactions in Solution and Aggregates

Systematic structural perturbation has been used to fine‐tune and understand the luminescence properties of three new 1,8‐naphthalimides (NPIs) in solution and aggregates. The NPIs show blue emission in the solution state and their fluorescence quantum yields are dependent upon their molecular rigidity. In concentrated solutions of the NPIs, intermolecular interactions were found to quench the fluorescence due to the formation of excimers. In contrast, upon aggregation (in THF / H₂O mixtures), the NPIs show aggregation‐induced emission enhancement (AIEE). The NPIs also show moderately high solid‐state emission quantum yields (ca. 10–12.7 %). The AIEE behaviour of the NPIs depends on their molecular rigidity and the nature of their intermolecular interactions. The NPIs 1 – 3 show different extents of intermolecular (π–π and C?H???O) interactions in their solid‐state crystal structures depending on their substituents. Detailed photophysical, computational and structural investigations suggest that an optimal balance of structural flexibility and intermolecular communication is necessary for achieving AIEE characteristics in these NPIs.