Spectral Calculations with DFT

Spectra calculations are an important branch of theoretical modeling, and due to the significant improvements of high-level computational methods, the calculated spectra can be used directly and sometimes help to correct the errors of experimental observations. On the other hand, theoretical computations assist the experimental assignments. The authors discuss three spectral calculations (UV-Vis, IR and NMR) that are the most widely used. UV-Visible spectrum can be carried out employing time-dependent density functional theory (TDDFT) with B3LYP/631G(d,p) and CAM-B3LYP functional method to illustrate the characteristics of vertical electronic excitations. The vibrational spectra can be generated from a list of frequencies and intensities using a Gaussian broadening function method. NMR chemical shifts can be calculated by density functional theory individual gauge for localized orbitals (DFTIGLO) method and by gauge including atomic orbitals (GIAO) approach

N-(4-Ferrocenylphenyl)benzamide

In the title compound, [Fe(C5H5)(C18H14NO)], the unsubstituted cyclo­penta­dienyl ring is disordered over two sets of sites with occupancy ratio of 0.55 (1):0.45 (1). One conformation has the rings eclipsed and the other staggered. An intra­molecular C—H⋯O hydrogen bond forms an S(6) ring motif. In the crystal, inter­molecular C—H⋯O and N—H⋯O hydrogen bonds lead to R 2 1(7) ring motifs. The mol­ecules are linked into polymeric chains extending along the b axis

Catalytic removal of Alizarin Red using chromium manganese oxide nanorods: degradation and kinetic studies

Dye removal through photocatalytic degradation employing nanomaterials as catalysts is a growing research area. In current studies, photocatalytic alizarin red (AR) dye degradation has been investigated by designing a series of Cr based manganese oxide nanomaterials (MH1–MH5). Synthesized nanomaterials were characterized by powder X-ray diffraction, scanning electron microscopy/energy dispersive x-ray, Brunauer–Emmett–Teller, and photoluminescence techniques and were utilized for photocatalytic AR dye degradation under UV light. AR dye degradation was monitored by UV–visible spectroscopy and percent degradation was studied for the effect of time, catalyst dose, different dye concentrations, and different pH values of dye solution. All the catalysts have shown more than 80% dye degradation exhibiting good catalytic efficiencies for dye removal. The catalytic pathway was analyzed by applying the kinetic model. A pseudo second-order model was found the best fitted kinetic model indicating a chemically-rate controlled mechanism. Values of constant R2 for all the factors studied were close to unity depicting a good correlation between experimental data

i-Propylammonium lead chloride based perovskite photocatalysts for depolymerization of lignin under UV light

Lignin depolymerization for the purpose of synthesizing aromatic molecules is a growing focus of research to find alternative energy sources. In current studies, the photocatalytic depolymerization of lignin has been investigated by two new iso-propylamine-based lead chloride perovskite nanomaterials (SK9 and SK10), synthesized by the facile hydrothermal method. Characterization was done by Powder X-Ray Diffraction (PXRD), Scanning Electron Microscopy (SEM), UV-Visible (UV-Vis), Photoluminescence (PL), and Fourier-Transform Infrared (FTIR) Spectroscopy and was used for the photocatalytic depolymerization of lignin under UV light. Lignin depolymerization was monitored by taking absorption spectra and catalytic paths studied by applying kinetic models. The %depolymerization was calculated for factors such as catalyst dose variation, initial concentration of lignin, and varying temperatures. Pseudo-second order was the best suited kinetic model, exhibiting a mechanism for lignin depolymerization that was chemically rate controlled. The activation energy (Ea) for the depolymerization reaction was found to be 15 kJ/mol, which is remarkably less than conventional depolymerization of the lignin, i.e., 59.75 kJ/mol, exhibiting significant catalytic efficiencies of synthesized perovskites. Products of lignin depolymerization obtained after photocatalytic activity at room temperature (20 °C) and at 90 °C were characterized by GC-MS analysis, indicating an increase in catalytic lignin depolymerization structural subunits into small monomeric functionalities at higher temperatures. Specifically, 2-methoxy-4-methylphenol (39%), benzene (17%), phenol (10%) and catechol (7%) were detected by GC-MS analysis of lignin depolymerization products

Supramolecular Chemistry and DNA Interaction Studies of Ferrocenyl Ureas and Thioureas

In this chapter, we have discussed the characteristics and bioapplicabilities of different ferrocene derivatives, for example, amides, amines, sulfonamide, and polymers, focusing mainly on urea and thiourea derivatives due to their autonomous and widespread spectroscopic action and bioactivities. Supramolecular chemistry of ferrocenyl ureas and thioureas is described owing to exploring their mode of interactions within and among the molecules and the role of these supramolecular structures in enhancing the DNA intercalation. DNA interaction studies of these ferrocenyl-based ureas and thioureas are explored with approaches like electrochemical study, viscosity measurements, molecular docking, electronic spectroscopy, dynamic light scattering (DLS), and radical scavenging activity. Attachment of ferrocene moiety to ureas an thiouereas closer to DNA is very promising strategy which most possibly boosts the probability of DNA damage and cell apoptosis which is responsible for enormous biological activities

Synthesis, antibacterial activity and docking studies of chloroacetamide derivatives

Structural modification of lead compounds is a great challenge in organic synthesis. Introduction of different functional groups not only modify the structure of starting material but also improve their biological activeness. Small synthetic molecules are favored in spite of the reality that majority of drug molecules derived from natural sources, are in vogue. In the present work, acetamide derivatives were synthesized using chloroacetyl chloride. After synthesizing targeted series of acetamide derivatives these compounds were further modified using different amines including 2-aminobenzene thiol, benzyl amine, benzene 1,4-diamine, 4-amino-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one, 4-aminophenol, hydrazine and 4-amino-N-(5-methylisoxazol-3-yl)benzenesulfonamide. All of these synthesized compounds were characterized by FT-IR, 1H NMR, 13C NMR and X-ray crystallography. The compounds were assessed for their anti-bacterial activity using disc diffusion method against Staphylococcus aureus and Escherichia coli. The compounds were found to exhibit comparable activity to the standard drug used. This was further supported by molecular docking studies using bacterial DNA gyrase and Topoisomerase II targets causing bacterial death as they are major bacterial proteins known to be involved in transcription and replication process. Results proved that the compound 2b was the most efficacious antimicrobial compound among the synthesized set of compounds. To tackle the growing drug resistance acetamide based functionalities can be regarded as the active lead compounds to target different drug resistance microorganism

Solvothermal preparation of ZnO nanorods as anode material for improved cycle life Zn/AgO batteries.

Nano materials with high surface area increase the kinetics and extent of the redox reactions, thus resulting in high power and energy densities. In this study high surface area zinc oxide nanorods have been synthesized by surfactant free ethylene glycol assisted solvothermal method. The nanorods thus prepared have diameters in the submicron range (300 ~ 500 nm) with high aspect ratio. They have uniform geometry and well aligned direction. These nanorods are characterized by XRD, SEM, Specific Surface Area Analysis, solubility in alkaline medium, EDX analysis and galvanostatic charge/discharge studies in Zn/AgO batteries. The prepared zinc oxide nanorods have low solubility in alkaline medium with higher structural stability, which imparts the improved cycle life stability to Zn/AgO cells

Assessment and Removal of Heavy Metals and Other Ions from the Industrial Wastewater of Faisalabad, Pakistan

The contamination of surface and groundwater is of major concern around the globe due to the fast industrialization and urbanization. The groundwater and water quality of rivers, Ravi and Chenab in Faisalabad, Pakistan are contaminated due to the industrial wastewater. The aim of this study was the assessment of the physiochemical contaminants of Faisalabad’s industrial wastewater area and the adsorptive removal of ions present in high concentrations following the National Environmental Quality Standards (NEQS) for the municipal and industrial liquid effluents of Pakistan. One of the two samples was collected from a drain carrying wastewater from different industries and other from the outlet of a drain discharging wastewater into river Chenab. The analysis results obtained indicate that most of the contaminants were below the acceptable limit of industrial wastewater NEQS, Pakistan. However, contaminants like sulfate ions (714 mg/L), total dissolved solids (33,951–34,620 mg/L) and barium ions (11–15 mg/L) were found to be higher than the allowable level of NEQS for the municipal and industrial liquid effluents for Pakistan. A novel biosorbent synthesized indigenously from Monotheca buxifolia seeds was used for the removal of sulfate, barium and TDS from the wastewater effluent samples. This biosorbent successfully reduced the sulfate ion concentration in the wastewater sample from 714 to 420 mg/L at pH 6 in 1 h. Similarly, the concentration of TDS reduced to 33,951 from 6295 mg/L at pH 4, whereas barium ions were removed from 15 to 1 mg/L at pH 10 in 1 h. Treatment of wastewater through the synthesized biosorbent efficiently removed the high concentration ions and could potentially be applied to reduce the toxic effects of these contaminants on local public health