Structural, optical and thermal investigations on Dy doped NaF–Li2O–B2O3 glasses

Structural, optical and thermal properties of Dy³⁺ doped lithium fluoroborate glasses have been studied for various concentrations of Dy³⁺ from 0.5 to 5 wt%. The XRD studies confirm the amorphous nature of the glasses while the FTIR spectra reveal the presence of BO₃ and BO₄ local structural units. The UV–VIS–NIR absorption studies were carried out to calculate the bonding parameters ( and δ), to identify the ionic/covalent nature of the glasses. The JO parameters, experimental and theoretical oscillator strengths were also determined and reported. The luminescence spectra have been studied to determine the radiative transition probability (A), stimulated emission cross section () and the experimental and calculated branching ratios (β_R) for the excited levels that include ⁴F_9/2→⁶H_11/2, ⁶H_13/2, and ⁶H_15/2 transitions. The variation of optical properties with varying concentrations of dysprosium oxide content in the glasses are reported and discussed. The thermal behavior of Dy³⁺ doped lithium fluoroborate glasses have been reported by recording DSC thermograms.     

Large-volume sample stacking for analysis of ethylenediaminetetraacetic acid by capillary electrophoresis

A simple, quick, and sensitive capillary electrophoretic technique-large volume stacking using the electroosmotic flow (EOF) pump (LVSEP) - has been developed for determining ethylenediaminetetraacetic acid (EDTA) in drinking water for the first time. It is based on a precapillary complexation of EDTA with Fe(III) ions, followed by large-volume sample stacking and direct UV detection at 258 nm. The curve of peak response versus concentration was linear from 5.0 to 600.0 microg/L, and 0.7 to 30.0 mg/L. The regression coefficients were 0.9988 and 0.9990, respectively. The detection limit of the current technique for EDTA analysis was 0.2 microg/L with an additional 10-fold preconcentration procedure, based on the signal-to-noise ratio of 3. As opposed to the classical capillary zone electrophoresis (CE) method, the detection limit was improved about 1000-fold by using this LVSEP method. To the best of our knowledge, it represents the highest sensitivity for EDTA analysis via CE. Several drinking water samples were tested by this novel method with satisfactory results.     

Large-volume sample stacking combined with separation by 2-hydroxypropyl-beta-cyclodextrin for analysis of isoxyzolylpenicillins by capillary electrophoresis

A simple, quick and sensitive capillary electrophoretic technique has been developed for the pharmaceutical analysis of isoxazolylpenicillins (oxacillin, cloxacillin and dicloxacillin) at trace levels for the first time. This method comprises large-volume sample stacking using the electroosmotic flow (EOF) pump (LVSEP), separation using 2-hydroxypropyl-beta-cyclodextrin (HP-beta-CD) as selective complex-forming background electrolyte additive, and direct UV detection. A complete resolution was achieved in the optimal background electrolyte containing 5.2 mM HP-beta-CD. LVSEP was successfully applied in their determinations to improve the sensitivity, where the EOF in the buffer zone was suppressed by using an acidic buffer with pH 3.6. The detection limits of the current technique were found to be 2.0 microg/L for each of the isoxazolylpenicillins based on the signal-to-noise ratio of 3. The curves of peak response versus concentration were linear from 5.0 to 400.0 microg/L with regression coefficients of 0.9982, 0.9986 and 0.9976, respectively. The interaction of isoxazolylpenicillins with HP-beta-CD was discussed. The association constants for complexes of HP-beta-CD with isoxazolylpenicillins were determined by electrophoretic method. The obtained association constants were 27.3, 34.9, and 48.5 M(-1), respectively, being proportional to their hydrophobic properties and steric hindrances. A simple and easy-manipulative sample preparation method was developed and validated by analyzing commercially available milk samples. It was found that with current sample preparation process and instrumentation system, 0.1 mL of milk sample is enough for the analysis of isoxazolylpenicillins to meet European Union (EU) guideline of 30 microg/kg.     

Radiolysis of aqueous cesium iodide

In hypothetical accident scenarios for Light Water reactors, the extent of release of iodine upon irradiation needs to be assessed for the purpose of evaluation of the applicable source term. In this context, an understanding of the behaviour of aqueous cesium iodide solutions subjected to high gamma-ray fluxes acquires significant importance. In the present work, gamma radiolysis of a cesium iodide solution (10^–2M I^–) with and without boron additive is investigated by irradiating with⁶⁰Co source at ambient temperature. Upon irradiation of the CsI solution, iodine is liberated, and the concentration of iodide in the KOH trap present in the radiolysis vessel increases with dose. The radiolytic products I ₃ ^– , IO ₃ ^– and H₂O₂ formed in the irradiated solution are also estimated and G values obtained are reported. G(I ₃ ^– ) and G(IO ₃ ^– ) are of the order of 10^–3 and 10^–4, respectively. G(H₂O₂) decreases with increase in dose. Addition of boron up to 200 ppm, does not appear to alter significantly the release fraction of iodine.     

Supramolecular interactions in salts/cocrystals involving pyrimidine derivatives of sulfonate/carboxylic acid

The crystal structures of three compounds involving aminopyrimidine derivatives are reported, namely, 5-fluorocytosinium sulfanilate–5-fluorocytosine–4-azaniumylbenzene-1-sulfonate (1/1/1), C₄H₅FN₃O⁺·C₆H₆NO₃S⁻·C₄H₄FN₃O·C₆H₇NO₃S, I , 5-fluorocytosine–indole-3-propionic acid (1/1), C₄H₄FN₃O·C₁₁H₁₁NO₂, II , and 2,4,6-triaminopyrimidinium 3-nitrobenzoate, C₄H₈N₅⁺·C₇H₄NO₄⁻, III , which have been synthesized and characterized by single-crystal X-ray diffraction. In I , there are two 5-fluorocytosine (5FC) molecules (5FC-A and 5FC-B) in the asymmetric unit, with one of the protons disordered between them. 5FC-A and 5FC-B are linked by triple hydrogen bonds, generating two fused rings [two R₂²(8) ring motifs]. The 5FC-A molecules form a self-complementary base pair [R₂²(8) ring motif] via a pair of N—H…O hydrogen bonds and the 5FC-B molecules form a similar complementary base pair [R₂²(8) ring motif]. The combination of these two types of pairing generates a supramolecular ribbon. The 5FC molecules are further hydrogen bonded to the sulfanilate anions and sulfanilic acid molecules via N—H…O hydrogen bonds, generating R₄⁴(22) and R⁶₆(36) ring motifs. In cocrystal II , two types of base pairs (homosynthons) are observed via a pair of N—H…O/N—H…N hydrogen bonds, generating R₂²(8) ring motifs. The first type of base pair is formed by the interaction of an N—H group and the carbonyl O atom of 5FC molecules through a couple of N—H…O hydrogen bonds. Another type of base pair is formed via the amino group and a pyrimidine ring N atom of the 5FC molecules through a pair of N—H…N hydrogen bonds. The base pairs (via N—H…N hydrogen bonds) are further bridged by the carboxyl OH group of indole-3-propionic acid and the O atom of 5FC through O—H…O hydrogen bonds on either side of the R₂²(8) motif. This leads to a DDAA array. In salt III , one of the N atoms of the pyrimidine ring is protonated and interacts with the carboxylate group of the anion through N—H…O hydrogen bonds, leading to the primary ring motif R₂²(8). Furthermore, the 2,4,6-triaminopyrimidinium (TAP) cations form base pairs [R₂²(8) homosynthon] via N—H…N hydrogen bonds. A carboxylate O atom of the 3-nitrobenzoate anion bridges two of the amino groups on either side of the paired TAP cations to form another ring [R₃²(8)]. This leads to the generation of a quadruple DADA array. The crystal structures are further stabilized by π–π stacking ( I and III ), C—H…π ( I and II ), C—F…π ( I ) and C—O…π ( II ) interactions.     

Functionalized zinc(II) dithiocarbamate complexes: Synthesis,spectral and molecular structures of bis(N-cyclopropyl-N-4-methoxybenzyldithiocarbamato-S,S′)zinc(II) and (2,2′-bipyridine)bis(N-cyclopropyl-N-4-methoxybenzyldithiocarbamato-S,S′)zinc(II)

Two new zinc and dithiocarbamate integrated metal complexes such as bis(N-cyclopropyl-N-4-methoxybenzyldithiocarbamato-S,S′)zinc(II) (1) and (2,2′-bipyridine)bis(N-cyclopropyl-N-4-methoxybenzyldithiocarbamato-S,S′)zinc(II) (2) have been synthesized and their spectral investigations viz., FT-IR, ¹H and ¹³C NMR as well as single crystal X-ray diffraction studies have been accomplished. Single crystal X-ray analysis of the complex 1 reveals the presence of distorted trigonal bipyramidal and tetrahedral coordination geometry around the zinc. The dithiocarbamate motif acts as bidentate chelating and bidentate bridging ligands between the zinc ions furnishing centrosymmetric dimeric molecules. In the complex 2, the zinc is in a distorted octahedral environment with a ZnS₄N₂ chromophore. The supramolecular frameworks in the complexes 1 and 2 have been sustained by CH?S, CH?O and CH?π (ZnCS₂, and chelate) interactions. Computational studies on complexes 1 and 2 have been executed utilizing DFT-B3LYP/ LANL2DZ method. In both the cases, the HOMO-LUMO calculations imply the occurrence of effective charge transfer within the molecule. Further, the MEP analysis of 1 and 2 implies the negative potential sites are sulfur of NCS₂ and oxygen of OCH₃ and the positive potential sites are nitrogen of NCS₂ in both the complexes along with 2,2′-bipyridine for complex 2. The former sites are susceptible for electrophilic reactions while the latter for nucleophilic reactions.     

Orchids as Sources of Novel Nanoinsecticides? Efficacy of <Emphasis Type="Italic">Bacillus sphaericus</Emphasis> and <Emphasis Type="Italic">Zeuxine gracilis</Emphasis>-Fabricated Silver Nanoparticles Against Dengue,Malaria and Filariasis Mosquito Vectors

Mosquitoes are the most critical group of insects in the context of public health, since they transmit key parasites and pathogens, causing millions of deaths annually. Insecticides from natural products may boost the effectiveness of vector control programs. In this study, we tested silver nanoparticles (AgNPs) fabricated using the leaf extract of the orchid Zeuxine gracilis as reducing agent, and the microbial pesticide Bacillus sphaericus, against the mosquitoes Anopheles stephensi, Aedes aegypti and Culex quinquefasciatus. The synthesis of AgNP was confirmed analyzing the excitation of surface Plasmon resonance using ultraviolet–visible (UV–Vis) spectrophotometry. SEM and TEM showed the irregular shapes of AgNPs. EDX spectroscopy, FTIR spectroscopy, X-ray diffraction and dynamic light scattering analysis were carried out. AgNPs were highly effective against the larvae of An. stephensi (LC₅₀ = 8.48 µg/mL), Ae. aegypti (LC₅₀ = 10.39 µg/mL) and Cx. quinquefasciatus (LC₅₀ = 13.21 µg/mL), respectively. Combined treatments testing B. sphaericus with AgNPs were also effective against An. stephensi (LC₅₀ = 12.32 µg/mL), Ae. aegypti (LC₅₀ = 14.78 µg/mL) and Cx. quinquefasciatus (LC₅₀ = 19.19 µg/mL). Overall, this study suggests that the orchid-synthesized AgNPs can be a rapid, environmentally safer bio-pesticide to be used in synergy with B. sphaericus to control mosquito vectors.     

Single Step Fabrication of Chitosan Nanocrystals Using <Emphasis Type="Italic">Penaeus semisulcatus</Emphasis>: Potential as New Insecticides,Antimicrobials and Plant Growth Promoters

In this study, chitosan nanoparticles (CH-NPs) were synthesized using Penaeus semisulcatus shrimp shells and characterized using UV–Vis and FT-IR spectroscopy, as well as XRD and HR-TEM analyses. CH-NPs were investigated for growth inhibition properties against selected species of bacterial and fungal pathogens, showing performances higher or comparable over positive controls, respectively. Furthermore, CH-NPs were tested on three important mosquito vectors, achieving LC₅₀ from 12.27 to 14.62 µg/ml. In addition, CH-NPs were evaluated using in vitro plant tissue culture by rooting gel method, to enhance the vegetative growth of the medicinal plant species Sphaeranthus indicus. With the simple technique presented here, large-scale industrial production of CH-NPs is possible. They can be used to develop pesticides highly effective against mosquito vectors of high medical and veterinary importance, as well as for plant tissue culture and food packaging applications.     

A Facile Synthesis of New 4,6‐Dichloropyridine Derivatives,Their Biological Evaluation for Antimicrobial and Antioxidant Activity,and Docking Studies

A facile synthesis of new 4,6‐dichloropyridine derivatives 5 ( a–f ), 6 ( a–c ), and 7 ( a–c ) were synthesized using both conventional heating and solvent‐free microwave irradiation techniques. The results revealed that the latter method is superior to the conventional heating method. The easy work‐up of the products, rapid reaction, and mild conditions are noticeable features of this protocol. Structural elucidation of the synthesized compounds was made on the basis of various spectroscopic methods. The synthesized compounds were evaluated for their in vitro antimicrobial activity (minimum inhibitory concentration; MIC) against various microbial strains using the agar well‐diffusion method. Among the compounds, 5c showed best antimicrobial activity against most of the employed strains, especially against Staphylococcus aureus, Escherichia coli, Rhizopus arrhizus, and Candida albicans. Compounds 5a , 6a , 6c , 7a , and 7c showed significant antioxidant activity when compared to the other compounds. In addition to this, theoretical docking studies were performed for the highly potent compounds 5a , 6a , 6c , 7a , and 7c against three different drug targets belonging to the oxidoreductase family, and the results were found to be highly satisfactory.     

A novel method for the synthesis and characterization of 10-hexyl-3-(1-hexyl-4, 5-diphenyl-1H-imidazol-2-yl)-10H-phenothiazine: DFT computational,in vitro anticancer and in silico molecular docking studies

Research on Chemical Intermediates - This study aimed to newly synthesized compound 10-hexyl-3-(1-hexyl-4, 5-diphenyl-1H-imidazol-2-yl)-10H-phenothiazine (abbreviated as HHDIP) by direct and...