Electronic Absorption Spectroscopy Research Articles

ОСОБЕННОСТИ ВЗАИМОДЕЙСТВИЯ ГЕМИНА И ZnII-КОМПЛЕКСА ТЕТРА(4 ПИРИДИЛ) ПОРФИРИНА С ГЕКСАМОЛИБДЕНОНИКЕЛАТ-ПОЛИАНИОНОМ В ВОДНЫХ СРЕДАХ

This work presents a method for producing new hybrid supramolecular organic-inorganic systems based on tetrapyrrole compounds (natural and artificially synthesized porphyrins) and hexamolibdenonicelate anion to create highly ordered supramolecular complexes based on porphyrins with the possibility of using them in medicine. In particular, the reaction of natural porphyrin (hemin) and the ZnII-complex of tetra(4-pyridyl)porphyrin with the heteropoly compound sodium hexamolibdenonicelate crystalline hydrate Na4[Ni(OH)6Mo6O18]·8H2O in an aqueous medium is considered. This heteropoly compound due to its physicochemical and biological properties can be considered as a part of photochromic materials and pharmacological agent. The optical absorption spectra of the obtained hybrid supramolecular organic-inorganic systems were investigated with the help of electronic absorption spectroscopy. Both the transformation of the bands which are the characteristics of porphyrins and the appearance of new bands indicating the formation of hybrid supramolecular organic-inorganic complexes are observed in the electron absorption spectra. The work traces the role of structural features of porphyrins in the process of their interaction with the heteropolyanions. Differences in the spectral behavior of the two metalloporphyrins when interacting them with the heteropoly compound have been shown and explained by variability in their structure. The data obtained will be useful when developing new hybrid materials as antibacterial components for medical use.

Antibacterial potentials and DNA study of cobalt(II) complexes containing aminophenol Schiff base moiety

The present study was carried out to investigate the effect of substituent groups on the antibacterial activities of 2-aminophenol Schiff bases and their cobalt (II) complexes. Development of new compounds with potential effects against pathogenic organisms has become necessary due to the increase in microbial resistance reported for existing antiseptics and disinfectants. In line with this, new cobalt (II) complexes with Schiff bases derived from 2-aminophenol and p-substituted benzaldehydes were synthesized. The compounds were characterized using elemental analysis, mass spectrometry, atomic absorption spectroscopy, electrospray ionization mass spectrometry, infrared spectroscopy, 1H NMR and electronic absorption spectroscopy. Results indicate that all metal complexes had a 1:2 metal ligand ratio with magnetic moments characteristic of tetrahedral geometry around the metal ion. The Schiff bases and their metal complexes were screened for in-vitro antibacterial activities against 6 human pathogenic bacteria usually found around the hospitals and homes; Escherichia coli (ATCC 8739), Staphylococcus aureus (ATCC 6538), Pseudomonas aeruginosa (ATCC 19582), Bacillus cereus (10702), Enterococcus faecalis (ATCC 29212) and Kribsella pneumonia (ATCC 10031) with ampicillin used as the reference compound. DNA binding study using calf thymus DNA revealed intercalative mode of activity. The result showed that Schiff bases exhibited moderate inhibitory activity against the tested microorganisms while Schiff base metal complexes exhibited higher antibacterial activity when compared to ampicillin. Our results indicate that these complexes can be employed as active ingredients in development of broad-spectrum antibacterial agents.

Nanostructured systems based on pluronics to carry gold nanoparticles and methylene blue aiming for multimodal therapy

The rise of multidrug-resistant microorganisms has become a cause of concern in the biomedical field. In this sense, this study focuses on the development of an effective treatment for infectious diseases mediated by Multimodal Therapy, combining Photodynamic Therapy (PDT), and Photothermal Therapy (PTT). The system involves the synthesis and stabilization of gold nanoparticles (AuNPs) in Pluronic® micelles of F-127 and P-84, combined with the Methylene Blue (MB) aiming effects against microorganisms. It is noteworthy that the AuNPs were synthesized in situ in the copolymer using the solid dispersion technique. These copolymers were strategically chosen for evaluation purposes with our study involving P-123 previously published in this journal. Thus, the effect of the length of the PEO and PPO blocks can be delineated concerning the synthesis of AuNPs. In this case, copolymer F127 has PPO blocks identical to P-123 while P-84 has PEO blocks compatible with P-123. Characterization of the formulations included electronic absorption spectroscopy, dynamic light scattering, and transmission electron microscopy. Fluorescence quenching studies by Stern Volmer plots indicated the location of the MB in the hydrophilic corona of the micelles. In general, was verified that reducing the PEO/PPO ratio favors the formation of AuNPs, possibly due to the greater number of reducing sites per unit mass of the polymer. The formulations remained stable for at least 15 days, and photothermal studies showed a temperature increase of at least 11 °C. The photothermal effect proved reversible after three heating–cooling cycles, revealing a synergy between MB and AuNPs in heat generation, hindered by increased irradiance and rapid photobleaching of MB. The in vitro susceptibility tests with Candida albicans and Staphylococcus aureus demonstrated effective inhibition of the microorganisms. The result shows that AuNPs for itself do not affect the fungal/bacteria lineage. However, the MB/AuNPs combination samples, showed excellent fungal and bacterial inhibition at low drug concentrations.

A study on poly(indene)

Indene was polymerized to polyindene (PI) through a cationic mechanism using TiCl4•2THF complex as initiator. The cationic mechanism was investigated through electronic absorption spectroscopy and either the indanyl cation as well as the polyindenyl cation absorption bands were distinguished and assigned. The PI structure was investigated through the indane model compound and the indene reference compound electronic absorption spectra. Furthermore, the Raman spectrum of PI was recorded for the first time and the complete Raman and FT-IR absorption bands of PI are reported with the assignment of the main bands. The glass transition (Tg) of cationic, radiation-induced and thermally initiated PI were measured through DSC and the corresponding molecular weight estimated. DSC and TGA-FTIR analysis were used to study the thermal decomposition of PI. It was assessed that PI is pyrolyzed back into indene monomer in almost theoretical yield with an activation enthalpy of E# = 164 kJ/mol while the decomposition enthalpy of PI was determined at 101.6 kJ/mol a value very close to the theoretical value of 108.9 kJ/mol. It was assessed that PI is a fully recyclable polymer which could be decomposed back to the monomer and re-polymerized at will.

α-Cleavage of 2,2-Diazido-2,3-dihydroinden-1-one in Solution and Cryogenic Matrices.

The Norrish type I (α-cleavage) reaction is an excellent photochemical method for radical-pair formation in solution. However, in cryogenic matrices, the starting material typically re-forms before the radical pair diffuses apart. This study focused on N2 extrusion from an azido alkyl radical to prevent radical-pair recombination. Irradiation of 2,2-diazido-2,3-dihydroinden-1-one (1) in methanol mainly yielded methyl 2-cyanomethylbenzoate (2) and 2-cyanomethylbenzoic acid (3) via α-cleavage. Laser flash photolysis of 1 in argon-saturated acetonitrile resulted in α-cleavage to form triplet biradical 31Br1 (λmax ∼ 410 nm, τ ∼ 400 ns). In contrast, upon irradiation in glassy 2-methyltetrahydrofuran matrices, triplet alkylnitrene 31N was directly detected using electron spin resonance (D/hc = 1.5646 cm-1, E/hc = 0.00161 cm-1) and absorption spectroscopy (λmax = 276 and 341 nm). Irradiation of 1 in argon matrices generated 31N, benzoyl azide 4, singlet benzoylnitrene 14N, and isocyanide 5, as revealed by IR spectroscopy. The experimental results supported by density functional theory calculations [B3PW91/6-311++G(d,p)] suggest that irradiation of 1 in matrices results in α-cleavage to form biradical 31Br1, which extrudes N2 to yield 31Br2. Rearrangement of 31Br2 into 31N competes with cleavage of a N3 radical to form radical 1Ra3. The N3/1Ra3 radical pair combines to form 4, which upon irradiation yields 14N and 5.

Preparation and characterization of MnIIMnIII complexes with relevance to class Ib ribonucleotide reductases

The Mn2 complex [MnII2(TPDP)(O2CPh)2](BPh4) (1, TPDP = 1,3-bis(bis(pyridin-2-ylmethyl)amino)propan-2-ol, Ph =phenyl) was prepared and subsequently characterized via single-crystal X-ray diffraction, X-ray absorption, electronic absorption, and infrared spectroscopies, and mass spectrometry. 1 was prepared in order to explore its properties as a structural and functional mimic of class Ib ribonucleotide reductases (RNRs). 1 reacted with superoxide anion (O2•–) to generate a peroxido-MnIIMnIII complex, 2. The electronic absorption and electron paramagnetic resonance (EPR) spectra of 2 were similar to previously published peroxido-MnIIMnIII species. Furthermore, X-ray near edge absorption structure (XANES) studies indicated the conversion of a MnII2 core in 1 to a MnIIMnIII state in 2. Treatment of 2 with para-toluenesulfonic acid (p-TsOH) resulted in the conversion to a new MnIIMnIII species, 3, rather than causing O—O bond scission, as previously encountered. 3 was characterized using electronic absorption, EPR, and X-ray absorption spectroscopies. Unlike other reported peroxido-MnIIMnIII species, 3 was capable of oxidative O—H activation, mirroring the generation of tyrosyl radical in class Ib RNRs, however without accessing the MnIIIMnIV state.

A novel Pt2+ complex containing 1,4-benzodioxan-6-amine: Stability, DNA binding, and antitumor effects against human breast cancer cells

In this work, a new platinum(II) complex was prepared by the reaction of K2PtCl4 with 1,4-benzodioxan-6-amine (bda) at room temperature in the molar ratio 2:1 (L:M). The complex was characterized by physicochemical (elemental analysis, TGA/DTA, and conductivity measurements) and spectroscopic methods (UV–Vis, FTIR, 1H, 13C and 195Pt NMR). According to the spectroscopic data, two bda ligands coordinate to the platinum ion in a monodentate manner through the nitrogen atom to give the complex cis-[PtCl2(bda)2]. Stability studies were carried out under different conditions and showed that the complex is stable in pure DMF, although it undergoes slow solvolysis in DMSO. The interaction of this complex with calf thymus DNA (CT-DNA) was studied using circular dichroism (CD), electronic absorption and fluorescence spectroscopy. The complex binds to CT-DNA with a Kb value of 1.06 ​× ​103 ​M−1 and according to data from CD and fluorescence spectroscopy, appears to interact with DNA by electrostatic forces and or other no intercalative binding mode. Compared to cisplatin, the complex exhibited good cytotoxic activity and selectivity against the MCF-7 tumor cell line, displaying an IC50 value of 17.33 ​± ​1.1 ​μM, as well as inhibited MCF-7 ​cells migration.

Square-planar nickel/copper(II) complexes of (E)-2-(((2-ethylphenyl)imino)(phenyl)methyl)phenol: Supramolecular analysis, keto-enol tautomerism, polymorphism and antibacterial activities

A new Schiff base proligand, (E)-2-(((2-ethylphenyl)imino)(phenyl)methyl)phenol (HL), was synthesized from 2-hydroxybenzophenone and 2-ethylaniline and its coordination chemistry with nickel(II) and copper(II) acetate explored. In solution, the proligand HL undergoes ketoimine-enolimine tautomerism which settles exclusively into an enolimine form in the solid-state. Interestingly, while a single crystalline habit was obtained for the nickel complex 1 (block-shaped single crystals), the copper species 2 was found to solidify in two detectable polymorphs: block-shaped crystals (2a, monoclinic space group P21/c) and rhombic crystals (2b, triclinic space group P-1). Single-crystal X-ray diffraction studies reveal that the N,O Schiff base ligand chelates the divalent metal ions with square-planar geometry in the isostructural 1 and 2a and in a distorted square-planar geometry with a dihedral chelate-plane angle of 27.9° in 2b. The copper complex 2 exhibits significant antibacterial activity against the E. coli and medium activity against S. aureus bacteria. The physical properties of the complexes were further probed using thermal techniques, while their electronic structure was investigated by electrochemistry and electronic absorption spectroscopy.

A CoII-Hydroxide Complex That Converts Directly to a CoII-Acetamide during Catalytic Nitrile Hydration.

In exploring structural and functional mimics of nitrile hydratases, we report the synthesis of the pseudo-trigonal bipyramidal CoII complexes (K)[CoII(DMF)(LPh)] (1(DMF)), (NMe4)2[CoII(OAc)(LPh)] (1(OAc)), and (NMe4)2[CoII(OH)(LPh)] (1(OH)) (LPh = 2,2',2''-nitrilo-tris-(N-phenylacetamide; DMF = N,N-dimethylformamide; -OAc = acetate)). The complexes were characterized using NMR, FT-IR, ESI-MS, electronic absorption spectroscopy, and X-ray crystallography, showing the LPh ligand to bind in a tetradentate tripodal fashion alongside the respective ancillary donor. One of the complexes, 1(OH), is an unusual structural and functional mimic of the Co active site in Co nitrile hydratases. 1(OH) reacted with acetonitrile to yield the CoII-acetamide complex (NMe4)2[CoII(NHC(O)CH3)(LPh)], 2, which was also thoroughly characterized. In the presence of excess hydroxide, 1(OH) was found to catalyze quantitative conversion of the added hydroxide into acetamide. Despite the differences in Co oxidation state in nitrile hydratases and 1(OH) (CoIII versus CoII, respectively), 1(OH) was nonetheless an effective nitrile hydration catalyst, selectively producing acetamide over multiple turnovers.

Comparing industrial and analytical kraft lignins as biobased UV-protective additives in coatings

Lignin as the second most abundant biopolymer on Earth has the potential to become the alternative to petroleum-derived materials. It exhibits excellent UV absorption ability due to its aromatic structure and the presence of numerous phenolic, ketone, and intramolecular hydrogen bonds. Due to its complex nature, it is important to investigate its properties which is a very important step towards the valorization of lignin. Revealing its structural complexity allows for a better examination of its influence on the properties of the final lignin-based materials. In our research, we used two different kraft lignins: commercial analytical kraft lignin (AL) and industrial LignoBoost kraft lignin (KL) as UV-protect additives in BPA(Bisphenol A)-free polymer coatings based on diurethane dimethacrylate (DIUR). The maximum addition of KL and AL was 2 wt%. Both lignin samples were characterized in detail (composition analysis, ash content, molar mass and polydispersity, surface morphology, thermal properties, and quantitative measurement of hydroxyl group content). We investigated the influence of lignins on the textural and thermal properties of the coatings. Finally, we studied the application of lignin as a value-added UV-protective component by UV-Vis electronic absorption spectroscopy. KL with a higher purity and lower number of aliphatic OH had a better dispersion in the polymer matrix than AL lignin which had more agglomeration in the polymer matrix. The better dispersion resulted in producing a smoother surface in the coatings made from KL. Finally, a noticeable and significant impact of KL additive on the photoprotective properties of the coating material was demonstrated. These results showed a potential application and opportunity in the valorization of available industrial lignins toward sustainable and value-added products.

A comprehensive study on synthesis and crystal structures of Cu(II) and Ni(II) complexes: In vitro and in silico evaluation of biomolecular interactions, antiproliferative activities and molecular docking

Cu(II) and Ni(II) complexes, [Cu(NNN)2](NO3)2 (1) and [Ni(NNN)2](NO3)2 (2) (NNN-donor ligand: 2,2′:6′,2″-terpyridine), have been synthesized and characterized by electronic absorption spectroscopy, CHN analysis, FTIR, ESI-MS and X-ray crystallography techniques. Interaction of the complexes 1 and 2 with biomolecules (calf thymus DNA (CT-DNA) and bovine serum albumin (BSA)) has been investigated by electronic absorption and fluorescence spectroscopy. The results show that the complexes 1 and 2 can bind to CT-DNA via a moderate intercalation mode. Moreover, the fluorescence quenching mechanism between the complexes 1 and 2 and BSA is a static quenching process. The antiproliferative activities of the complexes 1 and 2 against human breast cancer (MCF-7) and lung cancer (A549 and H1299) cell lines were investigated. The complex 1 was found to have promising antiproliferative activity in selected cell line, with lower IC50 values than cisplatin. Molecular docking studies conducted across the complexes 1 and 2 have provided their potential as prospective chemotherapeutic agents against tumors. The complexes 1 and 2 demonstrated spontaneous binding with targets including anaplastic lymphoma kinase (ALK), heat shock protein 90 (Hsp90), epidermal growth factor receptor (EGFR), bovine hemoglobin (BHb), human epidermal growth factor receptor 2 (HER2), and B-DNA. These interactions are primarily driven by van der Waals forces and π-π interactions. Determining binding constants and the multiplicity of binding sites enhances understanding of these molecular interactions.

The influence of reed nanocellulose on the quality indicators of paper-basis for wallpapers

Improving the production technology of products with improved quality indicators and with less impact on the environment remains an urgent scientific and practical problem of paper industry enterprises. This refers to the technology for the production of paper-bases for wallpaper using environmentally safe chemical additives, in particular nanocellulose (NC), which was obtained by acid hydrolysis from reed cellulose. The production of cellulose was carried out in two stages - extraction from reed stalks with a solution of alkali and an organosolvent method of cooking in a solution of peracetic acid. The obtained organosolvent cellulose contained the remains of lignin and mineral substances, which allows it to be used for the preparation of NC. As a result of the hydrolysis of organosolvent cellulose, a time-stable NC suspension was extracted, the properties of which were investigated by scanning electron microscopy (morphological changes in the structure of reed cellulose-containing materials), atomic force microscopy (determination of topographic characteristics of NC), analysis of electronic absorption spectra (transparency of NC films). It was established that reed NC films had nanoparticles with a cross-sectional size of 5-25 nm, density up to 1.52 g/cm3, transparency up to 81.6 %, tensile strength up to 65 MPa. For the production of castings of paper-bases for wallpaper samples, sulfated pine bleached cellulose and polyester synthetic fiber were used, to the fibrous mass of which were added the following chemical additives: alkyl ketene dimer, reed NC, binder, and optical brightener. It has been shown that the use of nanocellulose at a rate of 0.35 % to 1.0 % of the paper mass leads to a significant improvement in the physical and mechanical quality indicators of the paper base for wallpaper. It was established that the replacement of 50 % of the synthetic chemical auxiliary substance alkyl ketene dimer with nanocellulose or additional application of nanocellulose at a rate of 0.5 g/m2 on the surface of the casting with 0.7 % alkyl ketene dimer allows to obtain paper that meets the requirements of the standard. The obtained results indicate the prospects of using reed nanocellulose for the production of other mass types of paper and cardboard.

Ionic Liquid Crystals Based on Loop-Shaped Copper(I) Complexes.

This paper describes the synthesis and characterization of liquid crystals based on loop-shaped cationic copper(I) complexes of a multidentate ligand. Their synthesis involves the one-pot reaction of an alkyloxy-decorated pyridine-aldehyde unit with a diamine (2,2'-(ethylenedioxy)bis(ethylamine)) spacer to form in situ a pyridine-imine quadridentate-N4-donor ligand, L, which is able to chelate a copper(I) center associated with various noncoordinating anions. All of these compounds were characterized by NMR, IR, and electronic absorption spectroscopy, and more particularly by X-ray diffraction and mass spectroscopy, enabling unambiguous assignment of the [ML]+ mononuclear nature of the cationic components. The presence of six flexible alkyloxy chains at each end of the ligand associated with the rigidity of the core complex causes induction of a liquid crystal state with a columnar self-organized architecture, where the columns are packed in a hexagonal two-dimensional network.

Temperature-dependent chlorosomal self-aggregation of bacteriochlorophyll-d analogs with a branched alkyl chain in a single 1-chlorooctane solvent

Abstract Recently, the supramolecular polymerization of chlorophyll pigments mimicking a natural light-harvesting apparatus (chlorosome) was demonstrated in low-polar organic solvents or aqueous solutions. To obtain the most aggregation models, a concentrated solution of the pigments in a polar organic solvent was diluted with a large amount of a nonpolar organic solvent or water. Here, bacteriochlorophyll-d analogs possessing branched alkyl chains of different lengths at the peripheral 17-propionate residue on the core chlorin π-system were prepared and their highly soluble chlorosomal supramolecules were produced in single 1-chlorooctane as a low-polar solvent. Temperature-dependent electronic absorption and circular dichroism spectroscopies were employed to analyze their self-aggregation and disaggregation mechanisms. The synthetic analogs were monomeric at high temperatures and self-aggregated during cooling of the hot solution through a non-sigmoidal pathway. The obtained chlorosomal self-aggregates were reversibly monomerized by heating the homogeneous solution. The disaggregation pathway was fitted to an isodesmic model whose melting points depended on the alkyl-chain lengths.

Novel Mn(II) and Cu(II) metal complexes with sulfa drug-derived ligands as potent antimicrobial and anticancer agents: In vitro studies, ADMET profile and molecular docking

The present work deals with the synthesis, characterization, and pharmaceutical potential evaluation of new biologically active Mn(II) and Cu(II) complexes with Schiff bases derived from sulfamethoxazole. The coordination mode of the complexes, geometry, and general formula were determined using elemental analysis, emission atomic spectroscopy, molar conductance, magnetic measurements, TGA, FTIR, electronic absorption spectroscopy, SEM-EDX, and EPR spectroscopy. The results indicate that the Schiff base act as bidentate ligands binding to the metal ions via the nitrogen atoms of the sulfonamide and oxazole groups which leads to a distorted octahedral geometry around the central metals.The in vitro antimicrobial properties of the Schiff base ligands and their respective Mn(II) and Cu(II) complexes were evaluated against Gram-negative and Gram-positive (Escherichia coli klebsiella pneumoniae, Staphylococcus aureus, and Bacillus subtilis)) bacteria, and two fungal strains (Candida albicans, Aspergillus niger). The results assert that the complexes display excellent antimicrobial properties with low MIC values. Additionally, DPPH-scavenging assay results suggest that the coordination compounds could act as efficient antioxidant species.The in vitro cytotoxicity assay conducted on chronic myelogenous leukaemia cell lines (K562) showed that the coordination compounds exhibit potent anticancer activities. Furthermore, the pharmaceutical properties, including pharmacokinetics and toxicity, were examined by ADMET simulations and molecular docking studies were employed to assess interactions between the complexes and drug targets. The in vitro experimental data and in silico computational analysis revealed that the ligands and their respective coordination compounds as noteworthy candidates for drug development.

Proximal ligand tunes active site structure and reactivity in bacterial L. monocytogenes coproheme ferrochelatase

Ferrochelatases catalyze the insertion of ferrous iron into the porphyrin during the heme b biosynthesis pathway, which is fundamental for both prokaryotes and eukaryotes. Interestingly, in the active site of ferrochelatases, the proximal ligand coordinating the porphyrin iron of the product is not conserved, and its catalytic role is still unclear. Here we compare the L. monocytogenes bacterial coproporphyrin ferrochelatase native enzyme together with selected variants, where the proximal Tyr residue was replaced by a His (i.e. the most common ligand in heme proteins), a Met or a Phe (as in human and actinobacterial ferrochelatases, respectively), in their Fe(III), Fe(II) and Fe(II)–CO adduct forms. The study of the active site structure and the activity of the proteins in solution has been performed by UV–vis electronic absorption and resonance Raman spectroscopies, biochemical characterization, and classical MD simulations.All the mutations alter the H-bond interactions between the iron porphyrin propionate groups and the protein, and induce effects on the activity, depending on the polarity of the proximal ligand. The overall results confirm that the weak or non-existing coordination of the porphyrin iron by the proximal residue is essential for the binding of the substrate and the release of the final product.

Biocompatible citrate-cysteine complexes of manganese as effective antioxidants: Experimental and computational studies

Many clinical studies have evaluated the ability of sulfur-containing antioxidants to prevent oxidative stress, a major cause of cancer, Parkinson's, and Alzheimer's disease. Cysteine complexes of manganese modified with citric acid were synthesized by a one-pot procedure in two molar ratios and at two different temperatures (90°C, 140°C). The synthesized complexes were studied using FT-IR, UV-Vis, NMR, and EDX. At the lower temperature, a hydrogel was formed, and a thiazolopyridine ring was formed at a temperature of 140°C which was complexed with manganese. Infrared and electronic absorption spectroscopy confirmed that manganese binding occurred via the oxygen atoms of COO. The complexes also exhibited strong fluorescence with excitation/emission peak wavelengths of 350/418 nm. The synthesized compounds showed efficient activity for superoxide scavenging (> 70%), which was evaluated by a pyrogallol autoxidation method. MTT assay studies confirmed the noncytotoxic nature of all the prepared samples. The Gaussian 09 program was used to optimize the structural configurations of the ligands and complexes based on DFT by the B3LYP/6-31+G(d) basis set. To evaluate the softness of both the ligand and the complex, an investigation of the HOMO-LUMO gaps was carried out. In addition, UV-vis spectra of Mn complexes obtained from the time-dependent DFT calculations show a strong peak in the range of 380-390 nm, which is in good agreement with our experimental findings. The results revealed that the oxygen atoms of citrate and cysteine are the most potential sites to interact with the Mn atom. Besides, the calculated average local ionization energies showed that the Mn atom is the most energetically favored and vulnerable site to an electrophilic or free radical attack.

Synthesis, characterization of Schiff base metal complexes with 1, 3 propanediamine as secondary chelates and their DNA binding, DNA cleavage, cytotoxicity, antioxidant and activities

A series of Cu(II), Co(II), Ni(II), and Zn(II) complexes were synthesised from ternary Schiff base ligand (ts) and 1,3-propanediamine (pda). These complexes were characterised using analytical and spectroscopic techniques. All these metal complexes have an octahedral geometry, which is supported by spectro-analytical experimental data. The fabricated Schiff base coordinates with the metal via imine nitrogen, a phenolic oxygen atom, and carboxylate anion as a monobasic tridentate. Thermal properties were also investigated. Antimicrobial studies were carried out against fungi and pathogenic (bacterial) organisms and a good zone of inhibition was observed irrespective of complexes. Free radical scavenging assays were performed by DPPH and H2O2 methods. The results of these two studies revealed that the Cu(II) and Zn(II) complexes were more active. The binding mode of calf thymus (Ct-DNA) to the metal complexes was analysed by the electronic absorption spectroscopy and viscosity measurement study. The findings revealed that the complex bound with DNA via a groove with electrostatic interactionand the copper complex showed a higher binding constant value. Cytotoxicity of the Schiff base and its complexes were evaluated with the breast cancer (MCF-7) cell line and all complexes exhibited moderate toxicity.

Synthesis and Characterization of Isostructural Th(IV) and U(IV) Pyridine Dipyrrolide Complexes.

A series of pyridine dipyrrolide actinide(IV) complexes, (MesPDPPh)AnCl2(THF) and An(MesPDPPh)2 (An = U, Th, where (MesPDPPh) is the doubly deprotonated form of 2,6-bis(5-(2,4,6-trimethylphenyl)-3-phenyl-1H-pyrrol-2-yl)pyridine), have been prepared. Characterization of all four complexes has been performed through a combination of solid- and solution-state methods, including elemental analysis, single crystal X-ray diffraction, and electronic absorption and nuclear magnetic resonance spectroscopies. Collectively, these data confirm the formation of the mono- and bis-ligated species. Time-dependent density functional theory has been performed on all four An(IV) complexes, providing insight into the nature of electronic transitions that are observed in the electronic absorption spectra of these compounds. Room temperature, solution-state luminescence of the actinide complexes is presented. Both Th(IV) derivatives exhibit strong photoluminescence; in contrast, the U(IV) species are nonemissive.

Redox Chemistries for Vacancy Modulation in Plasmonic Copper Phosphide Nanocrystals.

Copper phosphide (Cu3-xP) nanocrystals are promising materials for nanoplasmonics due to their substoichiometric composition, enabling the generation and stabilization of excess delocalized holes and leading to localized surface plasmon resonance (LSPR) absorption in the near-IR. We present three Cu-coupled redox chemistries that allow postsynthetic modulation of the delocalized hole concentrations and corresponding LSPR absorption in colloidal Cu3-xP nanocrystals. Changes in the structural, optical, and compositional properties are evaluated by powder X-ray diffraction, electronic absorption spectroscopy, 31P magic-angle spinning solid-state nuclear magnetic resonance spectroscopy, and elemental analysis. The redox chemistries presented herein can be used to access nanocrystals with LSPR energies of 660-890 meV, a larger range than has been possible through synthetic tuning alone. In addition to utilizing previously reported redox chemistries used for copper chalcogenide nanocrystals, we show that the largest structural and LSPR modulation is achieved using a divalent metal halide and trioctylphosphine. Specifically, nanocrystals treated with zinc iodide and trioctylphosphine have the smallest unit-cell volume (295.2 Å3) reported for P63cm Cu3-xP, indicating more Cu vacancies than have been previously observed. Overall, these redox chemistries present valuable insight into controlling the optical and structural properties of Cu3-xP.