Anodic voltage performance of conducting polymer-functionalized boron nitride nanosheets: a DFT assessment.

The search for low-diffusion barriers and high-capacity anode materials is considered a key step in boosting the efficiency of metal-ion batteries. Herein, we investigate the impact of a series of conducting polymers (CPs), namely, polyacetylene (PA), polypyrrole (PP), poly-p-phenylene (PPPh), and polythiophene (PT), on enhancing the material design and anodic performance of boron nitride nanosheet (BNNS)-based Li-ion and Na-ion batteries. For this purpose, first principle DFT simulations, utilizing both clustered and periodic models, are systematically performed to assess the stability of such nanostructures and their electronic behavior as potential anodic materials. It is revealed that frontier molecular orbitals calculated for BNNSs are stabilized upon association with the series of CPs, resulting in a reduction in the energy gaps of CP-BNNSs by nearly 50%, which in turn improves the charge transfer properties and cell reaction kinetics. A remarkable improvement in the cell voltage is predicted for PP and PT functionalized BNNSs, reaching approximately 3.5 V for Li+ and 3.0 V for Na+ ions. The outcome of the study emphasizes the influence of the size of metal ions, whether mono- or di-valent, and the nature of adsorbed conducting polymers. Manipulating the electronic features of boron nitride nanostructured surfaces through non-covalent functionalization with conducting polymers could pave the way for the design of highly efficient energy storage anodic CP-BNNS-based systems.

Computational analysis of anti-cancer drug hydroxyurea adsorption on nanocages of gold, silver and copper: SERS and DFT assessment.

The use of nanostructures in targeted drug delivery is effective in decreasing anticancer drug toxicity. Here, we discuss the theoretically predicted adsorption and interaction behavior of hydroxyurea [HU] with nano metal cages (nmC). HU interact the nmC through the N4 in primary amine with energies of -29.776, -30.684 and -22.105 kcal/mol for Au, Ag and Cu cage, respectively. As a result of reactivity studies, HU complexes with nmC (Au/Ag/Cu) are becoming more electrophilic and this gives the nmC system their bioactivity. It is suggested that nanocage is going to change the FMO's energy levels by means of absorption, so that it is used in drug administration. DOS and MEP were accomplished to gain additional understandings into the reactivity of proposed complexes. Method for improving the Raman signal of biomolecules is surface enhanced Raman scattering (SERS), which uses nanosized metal substrates. Chemical enhancement is evidenced by Mulliken charge distributions of all systems for detection and chemical compositions and exerts a significant role in determining them. In HU complexes containing nmC (Au/Ag/Cu), electron density was detected via ELF and LOL calculations. Based on the results of a non-covalent interaction (NCI) analysis, Van der Waals/hydrogen bonds/repulsive steric - interactions have been found. The title compound will also be analyzed in order to determine its bioactivity and drug likeness parameters, as a result, we will able to create a molecule with a highly favorable pharmacological profile and use the docking method to determine the values of the interaction energies for drug delivery. This study suggests that adsorption of drugs on nanocage surface occurs physically and functionalizing the nanocage has increased adsorption energy.

One-step Formation of Urea from Carbon Dioxide and Nitrogen Using Water Microdroplets.

Water (H2O) microdroplets are sprayed onto a graphite mesh covered with a CuBi2O4 coating using a 1:1 mixture of N2 and CO2 as the nebulizing gas. The resulting microdroplets contain urea [CO(NH2)2] as detected by both mass spectrometry and 13C nuclear magnetic resonance. This gas-liquid-solid heterogeneous catalytic system synthesizes urea in one step on the 0.1 ms time scale. The conversion rate reaches 2.7 mmol g-1 h-1 at 25 °C and 12.3 mmol g-1 h-1 at 65 °C, with no external voltage applied. Water microdroplets serve as the hydrogen source and the electron transfer medium for N2 and CO2 in contact with CuBi2O4. Water-gas and water-solid contact electrification are speculated to drive the reaction process. This strategy couples N2 fixation and CO2 utilization in an ecofriendly process to produce urea, converting a greenhouse gas into a value-added product.

Light-induced synthesis of silver nanoprisms as a surface-enhanced Raman scattering substrate for N-acetyl procainamide drug quantification.

Triangle-shaped silver nanoprisms (AgNPMs) were prepared by a photo-induced method through a seed-mediated growth process and were successfully employed as an ultra-sensitive surface-enhanced Raman scattering (SERS) substrate for the detection of the chemotherapeutic N-acetyl procainamide (NAPA) compound. The transformation of the morphology of the nanoprisms substrate could be noted with a remarkable change in color, possessing an average size of 95 nm. The shape-modified AgNPMs exhibited interesting optical characteristics owing to the truncated dual edges, which led to a pronounced longitudinal localized surface plasmonic resonance (LLSPR) behavior. The nanoprisms-based SERS substrate demonstrated an outstanding sensitivity for NAPA in aqueous solutions with the lowest ever reported detection limit of 0.5 × 10-13 M corresponding to excellent recovery and stability. A steady linear response with a broad dynamic range (10-4-10-12 M) and an R2 of 0.945 was also achieved. The results proved that the NPMs demonstrated excellent efficiency, reproducibility (97%), and stability (30 days) with a superior Raman signal enhancement reaching an ultralow detection limit of 0.5 × 10-13 M compared to the nanosphere particles which could show an LOD of 0.5 × 10-9 M.

Non-covalent interaction, adsorption characteristics and solvent effect of procainamide anti-arrhythmias drug on silver and gold loaded silica surfaces: SERS spectroscopy, density functional theory and molecular docking investigations.

First-principle calculations were systematically carried out to explore the structural and electronic properties of the non-covalent interaction of procainamide (PA) anti-arrhythmias drug molecules on silver-loaded and gold-loaded silica nanostructures. Computed adsorption energies presented a higher affinity of PA towards the Ag-SiO2 as compared with Au-SiO2 surfaces. The non-covalent interaction analysis revealed a weak van der Waals type of forces and hydrogen bonding, associated with a noticeable repulsive steric interaction. It was conceived that silver and gold decorated silica can be used for drug administration in biological systems due to the fact that their frontier molecular orbital energy levels were considerably altered upon absorption, decreasing the pertinent energy gaps. Moreover, the electronic spectra of PA⋯Ag-SiO2 and PA⋯Au-SiO2 structures investigated in different solvents display a notable blue shift, suggesting that noble metal-loaded silica can be effective in the context of drug delivery systems. Therefore, silver- and gold-decorated silica of three possible drug adsorption scenarios was fully analyzed to realize the associated bioactivity and drug likeness. Theoretical findings suggest that Ag- and Au-SiO2 nanocomposites can be considered potential drug delivery platforms for procainamide in medication protocols.

SERS and EC-SERS detection of local anesthetic procaine using Pd loaded highly reduced graphene oxide nanocomposite substrate.

The localized surface plasmon resonance (LSPR) excitations are critical towards achieving sizable spectral enhancements of the Raman scattered light. Herein, the synthesis of palladium-based highly reduced graphene oxide (Pd-HRG) with LSPR properties as an effective surface-enhanced Raman scattering (SERS) substrate and its utility in the highly sensitive detection of procaine are reported. The concentration detection of procaine samples was optimized by applying a set of pre-concentration parameters. The Pd-HRG nanocomposite showed a remarkable LSPR response with a Raman enhancement factor of 8.7 × 102. The Pd-HRG is employed to modify fluorine doped tin oxide electrode (Pd-HRG/FTO), resulted with an enhancement factor of 7.5 × 104 corresponding to the EC-SERS technique. The electronic and surface properties of synthesized Pd-HRG and functionalized FTO electrode were evaluated using Raman, infrared, EIS, XRD, FESEM and EDX techniques. Quantum chemical calculations were carried out to elaborate on the nature of interaction of procaine molecules with a nanostructured surface model. Pd-HRG, with an efficient and cost-effective fabrication, can be considered as a promising EC-SERS substrate for the detection of organic therapeutic drugs.

A First-Principles Study on the Multilayer Graphene Nanosheets Anode Performance for Boron-Ion Battery.

Advanced battery materials are urgently desirable to meet the rapidly growing demand for portable electronics and power. The development of a high-energy-density anode is essential for the practical application of B3+ batteries as an alternative to Li-ion batteries. Herein, we have investigated the performance of B3+ on monolayer (MG), bilayer (BG), trilayer (TG), and tetralayer (TTG) graphene sheets using first-principles calculations. The findings reveal significant stabilization of the HOMO and the LUMO frontier orbitals of the graphene sheets upon adsorption of B3+ by shifting the energies from -5.085 and -2.242 eV in MG to -20.08 and -19.84 eV in 2B3+@TTG. Similarly, increasing the layers to tetralayer graphitic carbon B3+@TTG_asym and B3+@TTG_sym produced the most favorable and deeper van der Waals interactions. The cell voltages obtained were considerably enhanced, and B3+/B@TTG showed the highest cell voltage of 16.5 V. Our results suggest a novel avenue to engineer graphene anode performance by increasing the number of graphene layers.

Surface-enhanced Raman scattering (SERS) spectroscopy for prostate cancer diagnosis: A review.

The present review focuses on the diagnosis of prostate cancer using surface enhanced Raman scattering (SERS) spectroscopy. On the basis of literature search, SERS-based analysis for prostate cancer detection of different sample types is reported in the present study. Prostate cancer is responsible for nearly one-tenth of all cell cancer deaths among men. Significant efforts have been dedicated to establish precise and sensitive monitoring techniques to detect prostate cancer biomarkers in different types of body samples. Among the various spectro-analytical techniques investigated to achieve this objective, SERS spectroscopy has been proven as a promising approach that provides noticeable enhancements of the Raman sensitivity when the target biomolecules interact with a nanostructured surface. The purpose of this review is to give a brief overview of the SERS-basedapproach and other spectro-analytical strategies being used for the detection and quantification of prostate cancer biomarkers. The revolutionary development of SERS methods for the diagnosis of prostate cancer has been discussed in more details based on the reported literature. It has been noticed that the SERS-based immunoassay presents reliable results for the prostate cancer quantification. The EC-SERS, which integrates electrochemistry with the SERS model, could also offer a potential ultrasensitive strategy, although its application in prostate cancer analysis has been still limited.

Porous Fluorocarbon from Rice Husk for the Efficient Separation of Gases.

A porous fluorocarbon sorbent is synthesized from rice husk (RH) in a microwave reactor and then evaluated for the adsorption of different gases (CH4, CO2, and N2). The fluorocarbon is characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), Raman spectroscopy, Thermal gravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS). Significant enhancement in the surface area of activated carbon material is obtained from 29 to 531 m2 g-1 after removing naturally present silica in RH. Results reveal that rice husk fluorocarbon (RHF) has a higher adsorption affinity for CO2 (1.8 mmol g-1) than that of the sulfonated rice husk (RHS) (1.4 mmol g-1) at 298 K while the corresponding separation factor of CO2/CH4 is 4 and 3; respectively. Higher separation factors of 12 and 10 are observed for the binary system of CO2/N2, respectively. Quantum chemical density functional theory (DFT) calculations agree with the experimental observations. They reveal that RHF exhibits strong columbic interactions with considerable interaction energies of -87.85, -76.75, and -55.65 kcal mol-1 with CO2, CH4, and N2 gases; respectively. Finally, the adsorption process results are highly reproducible, with a small decrease in the adsorption capacity of less than 5% after repeated trials.

Conformational analysis and concentration detection of linuron: Spectroscopic NMR and SERS study.

Linuron is a commonly used organic herbicide which is used in plant growth control. Due to its potential health concerns, the characterization and monitoring of linuron have been a subject of several studies. In this work, we employed nuclear magnetic resonance (NMR) and Raman spectroscopic techniques supported with the density functional theory (DFT) to investigate the conformational behavior and electronic aspects of linuron. The selective nuclear Overhauser effect (SelNOE) spectra confirmed that linuron exists predominantly in the anti configuration and is facilitated with a weak intramolecular hydrogen bonding between the acidic amide proton and oxygen of methoxy moiety. Quantum chemical results showed that the corresponding syn form of the molecule is 8.5 kcal/mol less stable. Further, the surface enhanced Raman scattering (SERS) technique using gold nanoparticles (AuNPs) was implemented as a potential spectroscopic protocol for the concentration monitoring of trace linuron. The Raman responses of four vibrational modes, namely CC stretching, CN stretching, N-H rocking and ring deformation, were successfully enhanced with an excellent linear concentration-intensity dependency. The aromatic CC stretching vibration at 1595 cm-1 in the Raman spectra has demonstrated the highest enhancement factor (6.5 × 104) and the lowest limit of detection (10-7 M). The interaction of linuron with the gold nanocluster was simulated by establishing a simple DFT model which predicted that the most pronounced binding with the gold atom takes place at the benzene ring.

Comparative Exposure Assessment of Potential Health Risks through the Consumption of Vegetables Irrigated by Freshwater/Wastewater: Gujranwala, Pakistan.

The motive of this study is the rapid increase of industrial and domestic wastewater application for the growth of agricultural crops, which is closely associated with human health. In this study, the accumulation of eight heavy metals (Zn, Cu, Fe, Mn, Pb, Cr, Ni, and Cd) in the edible parts of five different species of common vegetables-cauliflower, bitter gourd, radish, pumpkin, and apple gourd-irrigated by two different water irrigation sources (wastewater/freshwater) grown in Pakistan's industrial and agricultural city Gujranwala and human health risks associated with the consumption of vegetables were evaluated. The mean concentration of each metal (Zn, Cu, Fe, Mn, Pb, Cr, Ni, and Cd) in five selected freshwater irrigated vegetables was observed as 48.91, 38.47, 133, 87.5, 4.62, 0.92, 1.46, and 0.36 mg/kg, respectively, while the mean concentration of each corresponding metal in wastewater irrigated vegetables was found to be 59.2, 49.5, 188, 90.9, 6.08, 2.66, 3.98, and 1.76 mg/kg, respectively. The estimated daily intake of metals (EDI), target health quotient (THQ), hazard index (HI), and target cancer risk (TCR) were computed to assess the impact of a raised level of metals in vegetables on human health. The grand THQ (G-THQ) values of individual freshwater irrigated vegetables were lower than the G-THQ values of individual wastewater irrigated vegetables and the G-THQ values of Cu, Cr, Pb, and Cd were found to be greater than the safety limit in wastewater irrigated vegetables. The HI values were found to be 7.94 and 4.01 for the vegetables irrigated with wastewater and freshwater, respectively. The TCR data reveal adverse carcinogenic risks induced by Ni, Cr, and Cd through the consumption of wastewater irrigated vegetables and Ni and Cd from the consumption of freshwater fed vegetables. The principal component analysis (PCA) to predict the sources of metals and Monte Carlo simulation were conducted to reduce the uncertainty in the data. The results indicate that higher significant health risks (carcinogenic and non-carcinogenic) would be posed to the adult population through the consumption of wastewater irrigated vegetables comparatively.

Piloty's acid and its hydrazide analogue: Insights from the density functional theory and vibrational spectroscopy on the conformational stability and chemical reactivity.

N-hydroxybenzenesulfonamide (commonly known as Piloty's acid) is considered a major source for nitroxyl (HNO) species which has potential biological and medicinal applications. In the present study, the conformational preferences and chemical reactivity of Piloty's acid (PA) and its hydrazide analogue (benzenesulfonylhydrazide, BSH) were studied using spectroscopic and computational tools. Six stable conformations of each molecule were theoretically identified, and their structures were fully optimized at the DFT-B3LYP and MP2 levels. Both molecules in their most stable forms adopt the anti configuration with the NH bond of the secondary amine pointing away from the terminal hydroxyl and amine moieties in the acid and hydrazide molecules, respectively. Three stable gauche states facilitated by weak intramolecular interactions of the SO⋯HO and SO⋯HN types arise due to the internal rotation about the SN linkage. Reliable assignments of the vibrational modes and the calculated reaction coordinates support a two-step mechanistic pathway of the Piloty's acid dissociation leading to the production of the nitroxyl (HNO) intermediate with moderate transition state barriers. Frontier molecular orbitals distributions, molecular electrostatic potential maps and condensed Fukui functions analysis of the molecules were employed to elucidate the agility of PA to dissociate to produce HNO and the absence of such a dissociation of BSH that would produce diazene (N2H2).

In Silico Modeling of New "Y-Series"-Based Near-Infrared Sensitive Non-Fullerene Acceptors for Efficient Organic Solar Cells.

This work was inspired by a previous report [Janjua, M. R. S. A. Inorg. Chem. 2012, 51, 11306-11314] in which the optoelectronic properties were improved with an acceptor bearing heteroaromatic rings. Herein, we have designed four novel Y-series non-fullerene acceptors (NFAs) by end-capped acceptor modifications of a recently synthesized 15% efficient Y21 molecule for better optoelectronic properties and their potential use in solar cell applications. Density functional theory (DFT) along with time-dependent density functional theory (TDDFT) at the B3LYP/6-31G(d,p) level of theory is used to calculate the band gap, exciton binding energy along with transition density matrix (TDM) analysis, reorganizational energy of electrons and holes, and absorption maxima and open-circuit voltage of investigated molecules. In addition, the PM6:YA1 complex is also studied to understand the charge shifting from the donor polymer PM6 to the NFA blend. Results of all parameters suggest that the DA'D electron-deficient core and effective end-capped acceptors in YA1-YA4 molecules form a perfect combination for effective tuning of optoelectronic properties by lowering frontier molecular orbital (FMO) energy levels, reorganization energy, and binding energy and increasing the absorption maximum and open-circuit voltage values in selected molecules (YA1-YA4). The combination of extended conjugation and excellent electron-withdrawing capability of the end-capped acceptor moiety in YA1 makes YA1 an excellent organic solar cell (OSC) candidate owing to promising photovoltaic properties including the lowest energy gap (1.924 eV), smallest electron mobility (λe = 0.0073 eV) and hole mobility (λh = 0.0083 eV), highest λmax values (783.36 nm (in gas) and 715.20 nm (in chloroform) with lowest transition energy values (E x) of 1.58 and 1.73 eV, respectively), and fine open-circuit voltage (V oc = 1.17 V) with respect to HOMOPM6-LUMOacceptor. Moreover, selected molecules are observed to have better photovoltaic properties than Y21, thus paving the way for experimentalists to look for future developments of Y-series-based highly efficient solar cells.

Droplet flow-assisted heterogeneous electro-Fenton reactor for degradation of beta-blockers: response surface optimization, and mechanism elucidation.

In this study, we report an effective degradation method for trace level beta-blockers (propranolol and acebutolol) in hospital wastewater using a new droplet flow-assisted heterogeneous electro-Fenton reactor (DFEF) system. Biogenic iron-carbon nanocomposites (RHS/C-x% Fe) as eco-friendly and low-cost heterogeneous Fenton catalysts were synthesized from rice husk via hydrolytic sol-gel routes. Here, we demonstrate the use of natural air as a nebulizing agent for fast and continuous catholyte air saturation and Fenton catalyst transfer to the cathode electrode. The effects of key operational parameters were evaluated and optimized using central composite design. Results clearly indicated that enhanced beta-blocker degradation was mainly dependent on the interactive effects of electrolysis time, current density, and catalyst dosage. Fast degradation efficiencies (≥ 99.9%) was recorded at neutral pH conditions. The decay followed pseudo-first-order kinetics with degradation rates of up to 2.72 × 10-2 and 2.54 × 10-2 min-1 for acebutolol and propranolol, respectively. The synergistic contribution of •OHbulk attributable to DFEF process and •OHadsorbed for anodic oxidation (AO) at the anode electrode significantly enhanced the degradation process. Compared to AO, the conventional flow-assisted electro-Fenton (FEF), and the batch electro-Fenton (BEF), DFEF degradation efficiency followed a decreasing order: DFEF ˃ FEF ˃ BEF˃ AO. This trend in performance was mainly due to the fast and continuous cathodic electro-generation of H2O2 and Fe2+ regeneration. Additionally, in order to elucidate degradation mechanism, we used a combination of DFEF approach with liquid chromatography-tandem mass spectrometry analysis. This approach demonstrates a simple, cleaner, and highly efficient degradation approach for trace level recalcitrant pollutants in a complex aquatic matrix, without the need for external chemical addition and pH adjustment.

Silver-loaded graphene as an effective SERS substrate for clotrimazole detection: DFT and spectroscopic studies.

Vibrational infrared, Raman and surface-enhanced Raman scattering (SERS) spectra of clotrimazole (CTZ) were documented and evaluated. Density-functional theory, B3LYP/6-311++G(d,p), approach was implemented to identify the possible conformations, develop the electrostatic potential map, evaluate frontier molecular orbitals and calculate the vibrational spectra of the target compound. The silver-loaded graphene was shown to be an effective SERS substrate for CTZ trace detection. The SERS spectrum showed two enhanced bands at 670 cm-1 and 700 cm-1 which confirmed the absorption of the silver substrate through chlorine and nitrogen atoms. A detection limit as low as 5 nM could be reached with a determination coefficient of 0.9988 using the band at 670 cm-1. The protein-ligand interaction with Secreted Aspartic Proteinase 2 (SAP2) of C. albicans showed that the four stable forms of CTZ maintain a free energy of binding of 6-7 kcal/mol, which could give insights into the mode of action in treating Candidiasis.

A selective detection approach for copper(ii) ions using a hydrazone-based colorimetric sensor: spectroscopic and DFT study.

The development of an efficient and miniaturized analytical approach to determine trace levels of toxic ions in aqueous fluids presents a current research challenge. Hydrazone-based chemosensors are considered potential candidates due to their high sensitivity and selectivity towards heavy metal ions. Computational techniques can be properly implemented to elucidate possible modes of ligand-metal interaction and provide an in-depth understanding of the chemistry involved. The present study reports the use of 3-hydroxy-5-nitrobenzaldehyde-4-hydroxybenzoylhydrazone (3-HNHBH) ligand for highly sensitive, quick and re-usable colorimetric sensing of copper(ii) ions in aqueous media. DFT calculations suggest that the complexation of 3-HNHBH with copper(ii) ions adopts a seesaw coordination geometry and results in the largest HOMO-LUMO gap and most effective coulombic interaction compared to Zn and Ni counterparts. It demonstrated a high selectivity towards copper ions with a detection limit of 0.34 µg L-1. The ligand was readily regenerated using a 0.5 M HCl solution, indicating its feasibility to be used as a re-usable sensor for the convenient detection of copper ions in aqueous media. The influence of metal interference, pH and solvents on the selectivity and regeneration of the ligand was also investigated.

Spherical silver nanoparticles as substrates in surface-enhanced Raman spectroscopy for enhanced characterization of ketoconazole.

A new method was developed for the characterization and detection of ketoconazole using surface enhanced Raman spectroscopy (SERS) by designing substrates and performing the bands' assignments. Thus, spherical silver nanoparticles (Ag-NPs) were synthesized by a reduction method and designed as substrates for SERS application. The Ag-NPs were characterized using a scanning electron microscope, Fourier transformed infrared spectroscopy and a high-resolution transmission electron microscope. TEM results indicated that the average size of the Ag-NPs was 15nm. The UV spectrum showed a maximum absorbance of Ag-NPs at about 400nm. When Ag-NPs were used as substrates in SERS, the Raman spectra of KCZ showed a significant enhancement of the Raman bands. An important finding is a linear relationship between the logarithmical scale of KCZ concentration and the intensity of the SERS bands, for example at 1050cm-1 of KCZ, which is due to the CN vibration. This was optimized and utilized to develop a calibration curve, which was then used for the detection of the KCZ in real pharmaceutical samples. The method has the advantages of a wide dynamic range with a high coefficient of determination and detection limit calculated based on the signal-to-noise ratio of 3, was 2.6×10-10M and the limit of quantification was 7.8×10-10M. The potential applications that take advantage of the high SERS sensitivity of this method are discussed for practical KCZ analysis where were quantified with this method.

Dimethylphosphinate bridged binuclear Rh(i) catalysts for the alkoxycarbonylation of aromatic C-H bonds.

A variety of binuclear rhodium(i) complexes featuring two bridging dimethylphosphinate ligands ((CH3)2PO2-) have been prepared and tested in the alkoxycarbonylation of aromatic C-H bonds. The complex [Rh(µ-κO,O'-(CH3)2PO2)(cod)]2 has been prepared by a reaction of [Rh(µ-MeO)(cod)]2 with 2 equivalents of dimethylphosphinic acid. Binuclear complexes [Rh(µ-κO,O'-(CH3)2PO2)(CO)L]2 (L = PPh3, P(OMe)Ph2 and P(OPh)3) were obtained by carbonylation of the related mononuclear complexes [Rh(κO-(CH3)2PO2)(cod)(L)], which were prepared in situ by the reaction of [Rh(µ-κO,O'-(CH3)2PO2)(cod)]2 with 2 equivalents of L. Conversely, if L = IPr, the reaction of [Rh(µ-κO,O'-(CH3)2PO2)(CO)L]2 with carbon monoxide affords the mononuclear complex [Rh(κO-(CH3)2PO2)(CO)2IPr]. The subsequent reaction with trimethylamine N-oxide gives the corresponding binuclear complex [Rh(µ-κO,O'-(CH3)2PO2)(CO)(IPr)]2 by abstraction of one of the carbonyl ligands. Complexes [Rh(µ-κO,O'-(CH3)2PO2)(cod)]2 and [Rh(κO-(CH3)2PO2)(cod)(L)] (L = IPr, PPh3, P(OMe)Ph2, P(OPh)3) are active precatalysts in the alkoxycarbonylation of C-H bonds, with the ligand system playing a key role in the catalytic activity. The complexes that feature more labile Rh-L bonds give rise to better catalysts, probably due to the more straightforward substitution of L by a second carbonyl ligand, since a more electrophilic carbonyl carbon atom is more susceptible toward aryl migration. In fact, complexes [Rh(µ-κO,O'-(CH3)2PO2)(CO)2]2 and [Rh(µ-Cl)(CO)2]2, generated in situ from [Rh(µ-κO,O'-(CH3)2PO2)(cod)]2 and [Rh(µ-Cl)(cod)2]2, respectively, are the most active catalysts tested in this work.

Graphene Dendrimer-stabilized silver nanoparticles for detection of methimazole using Surface-enhanced Raman scattering with computational assignment.

Graphene functionalized with polyamidoamine dendrimer, decorated with silver nanoparticles (G-D-Ag), was synthesized and evaluated as a substrate with surface-enhanced Raman scattering (SERS) for methimazole (MTZ) detection. Sodium borohydride was used as a reducing agent to cultivate silver nanoparticles on the dendrimer. The obtained G-D-Ag was characterized by using UV-vis spectroscopy, scanning electron microscope (SEM), high-resolution transmission electron microscope (TEM), Fourier-transformed infrared (FT-IR) and Raman spectroscopy. The SEM image indicated the successful formation of the G-D-Ag. The behavior of MTZ on the G-D-Ag as a reliable and robust substrate was investigated by SERS, which indicated mostly a chemical interaction between G-D-Ag and MTZ. The bands of the MTZ normal spectra at 1538, 1463, 1342, 1278, 1156, 1092, 1016, 600, 525 and 410 cm(-1) were enhanced due to the SERS effect. Correlations between the logarithmical scale of MTZ concentrations and SERS signal intensities were established, and a low detection limit of 1.43 × 10(-12) M was successfully obtained. The density functional theory (DFT) approach was utilized to provide reliable assignment of the key Raman bands.

FT-IR, HOMO-LUMO, NBO, MEP analysis and molecular docking study of 3-Methyl-4-{(E)-[4-(methylsulfanyl)-benzylidene]amino}1H-1,2,4-triazole-5(4H)-thione.

FT-IR spectrum of 3-Methyl-4-{(E)-[4-(methylsulfanyl)-benzylidene]amino}1H-1,2,4-triazole-5(4H)-thione was recorded and analysed. The vibrational wavenumbers were computed and at HF and DFT levels of theory. The data obtained from wavenumber calculations are used to assign the vibrational bands obtained in the IR spectrum. The NH stretching wavenumber is red shifted in the IR spectrum from the computed value, which indicates the weakening of the NH bond. The geometrical parameters of the title compound are in agreement with the XRD results. NBO analysis, HOMO-LUMO, first and second order hyperpolarizability and molecular electrostatic potential results are also reported. From the MEP map it is evident that the negative regions are localized over the sulphur atoms and N3 atom of triazole ring and the maximum positive region is localized on NH group, indicating a possible site for nucleophilic attack. Prediction of Activity Spectra analysis of the title compound predicts anti-tuberculostic activity with probability to be active value of 0.543. Molecular docking studies reveal that the triazole nitrogen atoms and the thione sulphur atom play vital role in bonding and results draw us to the conclusion that the compound might exhibit anti-tuberculostic activity.