Structure, magnetism and photomagnetism of mixed-ligand tris(pyrazolyl)methane iron(ii) spin crossover compounds

A range of bis-facial tridentate chelate complexes of type [Fe((R-pz)(3)CH)((3,5-Me(2)pz)(3)CH)](BF(4))(2) has been characterised that contain two different tris-pyrazolylmethane ligands, with variations in R being H (complex crystallised as polymorphs and ) and 4-Me (), as well as R = H with a CH(2)OH arm off the methane carbon (). A tris(pyridyl)methane analogue is also described (). The tris(3,5-dimethylpyrazolyl)methane co-ligand (3,5-Me(2)pz), and the BF(4)(-) counterion, are constant throughout. The spin-crossover properties of these Fe(ii) d(6) compounds have been probed in detail by variable temperature magnetic, M?ssbauer spectral and crystallographic methods. The effects of distortions from octahedral symmetry around the Fe(ii) centres, of crystal solvate molecules (1.5 MeCN in and 2 MeCN in ) and of supramolecular/crystal packing, are discussed. In the case of , subtle twisting of pyrazole rings occurs, as a function of temperature, that has a greater effect upon the relative positions of the Fe(ii) chelate molecules in polymorph than in polymorph ; this is thought to drive the cooperativity differences observed in the magnetism of the polymorphs. Comparisons are also made between to and their homoleptic, parent [Fe(L)(2)] (2+) materials. The complexes were screened for the LIESST (light induced excited spin state trapping) effect by measurements of diffuse absorption spectra on the surface of powder samples, at different temperatures. One example, , showed a 2-step thermal spin crossover transition and it was probed in detail for its photomagnetic features. The T(LIESST) and T(1/2) values for did not obey an empirical relationship, T(LIESST) = 150 - 0.3T(1/2) followed by many Fe(ii)(N-donor)(6) crossover compounds of the bis-tridentate (meridional) type, and possible reasons for this are discussed.     

A Robust Electrochemical Sensor Based on Butterfly-shaped Silver Nanostructure for Concurrent Quantification of Heavy Metals in Water Samples

Heavy metals in drinking water have become a severe threat to human health. Detection of heavy metals has been achieved by electrochemical sensors that are modified with complex nanocomposites; however, reproducibility of these sensors is still a big challenge when applied in commercial settings. Here, a simple, very robust, and sensitive electrochemical sensor based on a screen-printed carbon electrode modified with butterfly-shaped silver nanostructure (AgNS/SPCE) has been developed for the concurrent determination of cadmium (II), lead (II), copper (II), and mercury (II) in water samples. The electrochemical behavior of the modified electrodes was investigated using cyclic voltammetry and differential pulse anodic stripping voltammetry. The AgNS/SPCE showed distinct peak potentials and a significant increase in the peak currents for all heavy metals, attributed to the high electrical conductivity and electrocatalytic activity of the synthesized butterfly-shaped AgNS. Moreover, the excellent stability and sensitivity towards simultaneous quantification of heavy metals have been obtained with detection limits of 0.4 ppb, 2.5 ppb, 7.3 ppb, and 0.7 ppb for Cd (II), Pb (II), Cu (II), and Hg (II), respectively. Besides, the constructed sensor was successfully applied to simultaneously quantify target heavy metals in spiked water samples. Owing to excellent sensitivity, high robustness, affordability, and fast response, the presented electrochemical sensor could be incorporated into a portable and miniaturized potentiostat device, making it a promising method for on-site water analysis.     

Waterborne epoxy adhesive derived from epoxidized soybean oil and dextrin: Synthesis and characterization

In the present study, waterborne epoxy (WBE) was prepared and the parameters involved in the synthesis of WBE have been optimized based on physicochemical analysis. A dextrin-based curing agent (DCA) was synthesized from dextrin and trimellitic anhydride at variable molar ratios, reaction temperature, reaction duration, and solvent. Furthermore, the optimized composition of DCA and WBE system was used as adhesive in wood bonding. A comparative analysis of DCA-cured-bonded system was studied with phenol-formaldehyde (PF)-bonded adhesive system. From all the analyses, the performance characteristic WBE–DCA adhesive system was found comparable with that of PF-bonded system.     

Density of Deep Eutectic Solvents: The Path Forward Cheminformatics-Driven Reliable Predictions for Mixtures

Deep eutectic solvents (DES) are often regarded as greener sustainable alternative solvents and are currently employed in many industrial applications on a large scale. Bearing in mind the industrial importance of DES—and because the vast majority of DES has yet to be synthesized—the development of cheminformatic models and tools efficiently profiling their density becomes essential. In this work, after rigorous validation, quantitative structure-property relationship (QSPR) models were proposed for use in estimating the density of a wide variety of DES. These models were based on a modelling dataset previously employed for constructing thermodynamic models for the same endpoint. The best QSPR models were robust and sound, performing well on an external validation set (set up with recently reported experimental density data of DES). Furthermore, the results revealed structural features that could play crucial roles in ruling DES density. Then, intelligent consensus prediction was employed to develop a consensus model with improved predictive accuracy. All models were derived using publicly available tools to facilitate easy reproducibility of the proposed methodology. Future work may involve setting up reliable, interpretable cheminformatic models for other thermodynamic properties of DES and guiding the design of these solvents for applications.     

Three New Isoprenylated Flavones from Artocarpus chama Stem and Their Bioactivities

Phytochemical investigation of Artocarpus chama stem was performed by chromatographic techniques, resulting from the isolation and structure elucidation of three new compounds, namely 3′-farnesyl-apigenin (1), 3-(hydroxyprenyl) isoetin (2), and 3-prenyl-5,7,2′,5′-tetrahydroxy-4′-methoxyflavone (3), and five known compounds, namely homoeriodictyol (4), isocycloartobilo-xanthone (5), artocarpanone (6), naringenin (7), and artocarpin (8). From the screening result, A. chama extract showed a potent tyrosinase inhibitory effect. Ihe isolated compounds 1, 4 and 6 also exhibited tyrosinase inhibition with IC₅₀ of 135.70, 52.18, and 38.78 µg/mL, respectively. Moreover, compounds 3, 4, 5, 6, and 8 showed strong activity against Staphylococcus epidermidis, S. aureus, methicillin-resistant S. aureus, and Cutibacterium acnes. This study is the first report on phytochemical investigation with new compounds and biological activities of A. chama. Skin infection can cause dark spots or hyperpigmentation. The isolated compounds that showed both anityrosinase and antimicrobial activities will be further studied in in vivo and clinical trials in order to develop treatment for hyperpigmentation, which is caused by infectious diseases by microorganisms.     

Symmetry-adapted linear combinations for the eigenvalues and eigenvectors of reciprocal graphs

ABSTRACT

Three classes of reciprocal graphs, viz. monocycle (G^C_n), linear chain (G^L_n) and star (G^K_n) with reciprocal pairs of eigenvalues (λ, 1/λ), are well known. Reciprocal graphs of monocycle (G^C_n) and linear chain (G^L_n) are obtained by putting a pendant vertex to each vertex of simple monocycle (C_n) and simple linear chain (L_n), respectively. A star graph of such kind is obtained by attaching a pendant vertex to the central vertex and to each of the (n ? 1) peripheral vertices of the star graph (K_{1, (n?1)}). An n-fold rotational axis of symmetry for G^C_n and (n ? 1)-fold rotational axis of symmetry for G^K_n have been exploited for obtaining their respective condensed graphs. The condensed graph for G^L_n has been generated from that of G^C_n incorporating proper boundary conditions. Condensed graphs are lower dimensional graphs and are capable of keeping all eigeninformation in condensed form. Thus the eigensolutions (i.e. the eigenvalues and the eigenvectors) in analytical forms for such graphs are obtained by solving 2 × 2 or 4 × 4 determinants that in turn result in the charge densities and bond orders of the corresponding molecules in analytical forms. Some mathematical properties of the eigenvalues of such graphs have also been explored.     

A literature review on police patrolling problems

Annals of Operations Research - Police patrol is an effective crime prevention tool and boosts public confidence in urban security. Many interesting decision making problems appear in route design,...     

Stranski–Krastanow growth of multilayer In(Ga)As/GaAs QDs on Germanium substrate

We have described Stranski–Krastanow growth of multilayer In(Ga)As/GaAs QDs on Ge substrate by MBE. The growth technique includes deposition of a thin germanium buffer layer followed by migration-enhanced epitaxy (MEE) grown GaAs layer at 350°C. The MEE layer was overgrown by a thin low-temperature (475°C) grown GaAs layer with a subsequent deposition of a thick GaAs layer grown at 590°C. The sample was characterized by AFM, cross-sectional TEM and temperature-dependent PL measurements. The AFM shows dense formation of QDs with no undulation in the wetting layer. The XTEM image confirms that the sample is free from structural defects. The 8 K PL emission exhibits a 1051 nm peak, which is similar to the control sample consisting of In(Ga)As/GaAs QDs grown on GaAs substrate, but the observed emission intensity is lower. The similar slopes of Arrhenius plot of the integrated PL intensity for the as-grown QD sample grown on Ge substrate as well as for a reference QD sample grown on GaAs substrate are found to be identical, indicating a similar carrier emission process for both the samples. This in turn indicates coherent formation of QDs on Ge substrate. We presume due to the accumulated strain associated with the self-assembled growth of nanostructures on Ge that nonradiative recombination centers are introduced in the GaAs barrier in between the QD layers, which in turn degrades the overall optical quality of the sample.