A Pd(II) complex of a β-cyclodextrin-based polydentate ligand: an efficient catalyst for the Suzuki reaction in aqueous media

Molecular assembly has become a promising strategy for designing new polydentate ligands. But very often such ligands and their complexes are sparingly soluble in aqueous phase due to their intrinsic hydrophobic character. Pd(II) complexes are good homogeneous catalysts but their poor solubility in aqueous phase may limit their catalytic efficacy in the universal green solvent water. However, solubility related challenges especially in aqueous phase can be mitigated through the formation of inclusion complexes by exploiting the hydrophobic nature of the β-cyclodextrin (β-CD) cavity. Hence, an ionic liquid ChCD (1) was synthesized from β-CD and Choline bromide (ChBr). Next a supramolecular N, N^′, O-tridentate ligand 1?2 (3) was synthesized by the inclusion of 2,6-diaminopyridine (2) in the hydrophobic β-CD cavity of the ionic liquid ChCD (1) and was well characterized by elemental analysis, UV-visible, FTIR, ¹H NMR spectroscopy, etc. The stoichiometry of the inclusion complex 1?2 (3) was found to be 1:1 based on UV-visible spectrophotometric study. A new air stable, highly water soluble Pd²⁺-complex [κ³-N, N^′, O-Pd(1?2)H₂O]OAc (4) was then synthesized from the supramolecular ligand (3) with 1:1 stoichiometry and used as a catalyst for Suzuki cross-coupling reactions in water at ambient temperature with good to excellent yields. The catalyst can be removed and recycled. Additionally, the use of non-toxic solvent water makes the methodology green, sustainable, and economically viable.     

Highly Converged Valence Bands and Ultralow Lattice Thermal Conductivity for High‐Performance SnTe Thermoelectrics

A two‐step optimization strategy is used to improve the thermoelectric performance of SnTe via modulating the electronic structure and phonon transport. The electrical transport of self‐compensated SnTe (that is, Sn_1.03Te) was first optimized by Ag doping, which resulted in an optimized carrier concentration. Subsequently, Mn doping in Sn_1.03?xAg_xTe resulted in highly converged valence bands, which improved the Seebeck coefficient. The energy gap between the light and heavy hole bands, i.e. ΔE_v decreases to 0.10 eV in Sn_0.83Ag_0.03Mn_0.17Te compared to the value of 0.35 eV in pristine SnTe. As a result, a high power factor of ca. 24.8 μW cm^?1 K^?2 at 816 K in Sn_0.83Ag_0.03Mn_0.17Te was attained. The lattice thermal conductivity of Sn_0.83Ag_0.03Mn_0.17Te reached to an ultralow value (ca. 0.3 W m^?1 K^?1) at 865 K, owing to the formation of Ag₇Te₄ nanoprecipitates in SnTe matrix. A high thermoelectric figure of merit (z T≈1.45 at 865 K) was obtained in Sn_0.83Ag_0.03Mn_0.17Te.     

Porous Solids Arising from Synergistic and Competing Modes of Assembly: Combining Coordination Chemistry and Covalent Bond Formation

Design and synthesis of porous solids employing both reversible coordination chemistry and reversible covalent bond formation is described. The combination of two different linkage modes in a single material presents a link between two distinct classes of porous materials as exemplified by metal–organic frameworks (MOFs) and covalent organic frameworks (COFs). This strategy, in addition to being a compelling material‐discovery method, also offers a platform for developing a fundamental understanding of the factors influencing the competing modes of assembly. We also demonstrate that even temporary formation of reversible connections between components may be leveraged to make new phases thus offering design routes to polymorphic frameworks. Moreover, this approach has the striking potential of providing a rich landscape of structurally complex materials from commercially available or readily accessible feedstocks.     

Divergence in photoinduced electron transfer (PET) reactions: a useful strategy towards identifying route-selectivity in mixed ketones

The work utilized photoinduced electron transfer (PET) reactions to identify the preferred photoreaction route in molecules having juxtaposed α,β and β,γ-enones. Such process directly converted 2-hydroxyimino derivatives of 5-benzoylbicyclo[2.2.2]octenones to the corresponding bicyclo[3.2.1]octane derivatives. First evidence of Type B rearrangement in α,β-enones having acyl substitution at Cγ-position has been depicted in this work. In rigid mixed enones, this has been found to be generally the preferred photoreaction route.     

Covalent cucurbit[7]uril–dye conjugates for sensing in aqueous saline media and biofluids

Non-covalent chemosensing ensembles of cucurbit[n]urils (CBn) have been widely used in proof-of-concept sensing applications, but they are prone to disintegrate in saline media, e.g. biological fluids. We show here that covalent cucurbit[7]uril–indicator dye conjugates are buffer- (10× PBS buffer) and saline-stable (up to 1.4 M NaCl) and allow for selective sensing of Parkinson''s drug amantadine in human urine and saliva, where the analogous non-covalent CB7⊃dye complex is dysfunctional. The in-depth analysis of the covalent host–dye conjugates in the gas-phase, and deionized versus saline aqueous media revealed interesting structural, thermodynamic and kinetic effects that are of general interest for the design of CBn-based supramolecular chemosensors and systems. This work also introduces a novel high-affinity indicator dye for CB7 through which fundamental limitations of indicator displacement assays (IDA) were exposed, namely an impractical slow equilibration time. Unlike non-covalent CBn⊃dye reporter pairs, the conjugate chemosensors can also operate through a S_N2-type guest–dye exchange mechanism, which shortens assay times and opens new avenues for tailoring analyte-selectivity.

Unimolecular chemosensor shows superior stability and detection capabilities in biofluids compared to bimolecular reporter pairs.     

Green synthesis of AgNPs from aqueous extract of Oxalis corniculata and its antibiofilm and antimicrobial activity

The silver nanoparticles OC-AgNPs, synthesized from the aqueous extract of Oxalis corniculata (OC), showed antiviral activity against Herpes Simplex Virus-1 (HSV-1), and anti-biofilm, and antibacterial activities against human isolates of six multi-drug resistant (MDR) bacteria - Staphylococcus aureus, Streptococcus pyogenes, Escherichia coli, Klebsiella pneumoniae, Salmonella typhi, and Pseudomonas aeruginosa. The OC-AgNP was characterized by UV-Vis and FTIR spectroscopy; while its morphology and distribution were determined by transmission electron microscopy (TEM). The results revealed that the biogenic OC-AgNPs are spherical with an average diameter of 40 nm and has shown UV-Vis peak at 445 nm. The cytotoxicity and safety of OC-AgNP has been evaluated by MTT assay in Vero cells and triple-negative human breast cancer MDA-MB-468 cells. The plaque reduction assay has been used to test the antiviral activity against HSV-1F. The anti-biofilm activity was assessed by crystal violet staining, followed by light and confocal microscopy; while the antibacterial activity was determined by conventional disk-diffusion and broth-dilution methods. Moreover, the mechanism of anti-biofilm and antibacterial activity was examined by Field Emission Scanning Electron Microscopy (FESEM). The CC₅₀ (cytotoxicity) on Vero cells was 300 μg/ml; while the survival percentage of MDA-MB-468 cells was 27.12% at 20 μM and 80.97% at 100 μM of, respectively. The OC-AgNP showed moderate antiviral activity against HSV-1F at EC₅₀ of 25 μg/ml; but significantly inhibited the biofilm produced by Pseudomonus aeruginosa and Escherichia coli at 25-50 μg/ml; while at 30-50 μM we observed the dose-dependent lowering of fluorescence intensity under light and confocal microscope. Interestingly, the OC-AgNPs demonstrated significant antibacterial activity against Pseudomonas aeruginosa (20 mm), Klebsiella pneumoniae (15 mm), Escherichia coli (12 mm), Salmonella typhi (10 mm), Streptococcus pyogenes (11 mm) and Staphylococcus aureus (10 mm) with Minimum Inhibitory Concentration (MIC) of 0.65–0.90 μM (0.11- 0.153 μg), respectively. Further, the FESEM micrograph showed disruption of membrane structure with the damage of cell membrane integrity of Pseudomonus aeruginosa at its MIC.     

Differential electrochemical behaviour of phytofabricated and chemically synthesized silver nanoparticles towards hydrogen peroxide sensing**

Silver nanoparticles (AgNPs) are one of the most widely used nanomaterials for biomedical applications. However, the impact of its synthesis by chemical and plant-mediated routes on its differential electrochemical behaviour has not been examined till date. Here, we report for the first time the differential study of the electrochemical behaviour of the AgNPs synthesized by different routes. First, the AgNPs were obtained by different routes (chemical and phytofabrication) and extensively characterized to compare their physical properties. Thereafter, a comparison of electron transfer kinetics between chemically synthesized (Ag−C) and phyto-fabricated (Ag-Phy) nanoparticles (NPs) has been studied by electrochemical techniques such as potentiodynamic cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). To further investigate the electrocatalytic properties of both types of AgNPs, we have used the peroxide moieties (H₂O₂), and the Ag−C NPs-based sensor probe has been reported to have four times better sensitivity than the Ag−Phy NPs-based sensor. The AgNPs modified sensor probes have also been tested in real-world environments to explore the consistency of their performance in complex matrices by using clinical urine samples, where we found comparable sensitivity to the standard conditions.