Polymer Nanocomposite Containing Palladium Nanoparticles: Synthesis, Characterization, and Properties.

Composite nanomaterials have been prepared through thermal decomposition of palladium diacetate. The composite contains palladium nanoparticles embedded in high-pressure polyethylene. The materials were studied by a number of different physico-chemical methods, such as transmission electron microscopy, X-ray diffraction, X-ray absorption spectroscopy, electron paramagnetic resonance, and EXAFS. The average size of the nanoparticles is 7.0 ± 0.5 nm. It is shown that with the decrease of metal content in the polymer matrix the average size of nanoparticles decreased from 7 to 6 nm, and the coordination number of palladium also decreased from 7 to 5.7. The mean size of palladium particles increases with the growing concentration of palladium content in the matrix. It is shown that the electrophysical properties of the material obtained depend on the filler concentration. The chemical composition of palladium components includes metallic palladium, palladium (III) oxide, and palladium dioxide. All samples have narrow lines (3-5 Oe) with a g factor of around two in the electron paramagnetic resonance (EPR) spectra. It is shown that EPR lines have uneven boarding by saturation lines investigation. The relaxation component properties are different for spectral components. It leads to the spectrum line width depending on the magnetic field value. At first approximation, the EPR spectra can be described as a sum of two Lorentzian function graphs, corresponding to the following two paramagnetic centers: one is on the surface, and one is inside the palladium particles. Some of the experimental characteristics were measured for the first time. The data obtained indicate interesting properties of palladium-based nanocomposites, which will be useful for obtaining products based on these materials.

Nanoformulations - Insights Towards Characterization Techniques.

BACKGROUND: Drug-loaded novel nanoformulations are gaining importance due to their versatile properties compared to conventional pharmaceutical formulations. Nanomaterials, apart from their multifactorial benefits, have a wider scope in the prevention, treatment, and diagnosis of cancer. Understanding the chemistry of drug-loaded nano-formulations to elicit its behaviour both at molecular and systemic levels is critical in the present scenario. Drug-loaded nanoformulations are controlled by their size, shape, surface chemistry, and release behavior. The major pharmaceutical drug loaded nanocarriers reported for anticancer drug delivery for the treatment of various forms of cancers such as lung cancer, liver cancer, breast cancer, colon cancer, etc include nanoparticles, nanospheres, nanodispersions, nanocapsules, nanomicelles, cubosomes, nanoemulsions, liposomes and niosomes. The major objectives in designing anticancer drug-loaded nanoformulations are to manage the particle size/morphology correlating with the drug release to fulfil the specific objectives. Hence, nano characterizations are very critical both at in vitro and in vivo levels. OBJECTIVE: The main objective of this review paper is to summarise the major characterization techniques used for the characterization of drug-loaded nanoformulations. Even though information on characterization techniques of various nano-formulations is available in the literature, it is scattered. The proposed review will provide a comprehensive understanding of nanocharacterization techniques. CONCLUSION: To conclude, the proposed review will provide insights towards the different nano characterization techniques along with their recent updates, such as particle size, zeta potential, entrapment efficiency, in vitro release studies (chromatographic HPLC, HPTLC, and LC-MS/MS analysis), EPR analysis, X-ray diffraction analysis, thermal analysis, rheometric, morphological analysis etc. Additionally, the challenges encountered by the nano characterization techniques will also be discussed.

EPR of Type I photosynthetic reaction centers.

Light-induced reactions in photosynthetic reaction centers are initiated by the absorption of a photon, which results in the transfer of a single electron and the generation of radical ions in the donor and acceptor molecules involved in the charge-separated state. Electron paramagnetic resonance (EPR) spectroscopy is the ideal method for the study of such reactions. In addition to measuring spectra of the electron transfer cofactors in continuous light, reactions can be initiated by brief flashes of light, thereby allowing the kinetics of forward electron transfer as well as recombination reactions to be obtained. Because the donor and acceptor pairs are so closely spaced and because light induced charge separation is so rapid, the donor and early acceptors are in a quantum mechanically spin entangled state, which confers properties such as increased sensitivity, the ability to measure reactions on the nanosecond timescale, and the determination of bond angles between cofactors. Additionally, distances between pairs of cofactors can be measured by detecting the modulation of a phase shifted "out-of-phase" electron spin echo signal. In this methods article, we will describe how continuous wave EPR, time resolved EPR, and pulsed EPR can be used to measure these properties in Type I photosynthetic reaction centers. Methods of analysis are described for the bound electron transfer cofactors in the heterodimeric Photosystem I reaction center of plants and cyanobacteria and in the homodimeric reaction centers found in phototrophic members of the phyla Bacillota, Chlorobiota, and Acidobacteriota.

EPR Study of KO2 as a Source of Superoxide and •BMPO-OH/OOH Radical That Cleaves Plasmid DNA and Detects Radical Interaction with H2S and Se-Derivatives.

Superoxide radical anion (O2•-) and its derivatives regulate numerous physiological and pathological processes, which are extensively studied. The aim of our work was to utilize KO2 as a source of O2•- and the electron paramagnetic resonance (EPR) spin trapping 5-tert-butoxycarbonyl-5-methyl-1-pyrroline N-oxide (BMPO) technique for the preparation of •BMPO-OOH and/or •BMPO-OH radicals in water solution without DMSO. The method distinguishes the interactions of various compounds with •BMPO-OOH and/or •BMPO-OH radicals over time. Here, we show that the addition of a buffered BMPO-HCl mixture to powdered KO2 formed relatively stable •BMPO-OOH and •BMPO-OH radicals and H2O2, where the •BMPO-OOH/OH ratio depended on the pH. At a final pH of ~6.5-8.0, the concentration of •BMPO-OOH radicals was ≥20 times higher than that of •BMPO-OH, whereas at pH 9.0-10.0, the •BMPO-OH radicals prevailed. The •BMPO-OOH/OH radicals effectively cleaved the plasmid DNA. H2S decreased the concentration of •BMPO-OOH/OH radicals, whereas the selenium derivatives 1-methyl-4-(3-(phenylselanyl) propyl) piperazine and 1-methyl-4-(4-(phenylselanyl) butyl) piperazine increased the proportion of •BMPO-OH over the •BMPO-OOH radicals. In conclusion, the presented approach of using KO2 as a source of O2•-/H2O2 and EPR spin trap BMPO for the preparation of •BMPO-OOH/OH radicals in a physiological solution could be useful to study the biological effects of radicals and their interactions with compounds.

New Solids in As-O-Mo, As(P)-O-Mo(W) and As(P)-O-Nb(W) Systems That Exhibit Nonlinear Optical Properties.

Interactions between well-mixed fine powders of As2O3, P2O5, MoO3, WO3 and Nb2O5 at different stoichiometry in quartz ampoules under vacuum at ~1000 °C in the presence of metallic molybdenum (or niobium), over several weeks, led to shiny dichroic crystalline materials being formed in cooler parts of the reaction vessel. An addition of small quantities of metals-Mo or Nb-was made with the aim of partially reducing their highly oxidized Mo(VI), W(VI) or Nb(V) species to corresponding Mo(V), W(V) and Nb(IV) centers, in order to form mixed valence solids. Sublimed crystals of four new compounds were investigated using a variety of techniques, with prime emphasis on the X-ray analysis, followed by spectroscopy (diffusion reflectance, IR, Raman and EPR), second harmonic generation (SHG), thermal analysis under N2 and air atmosphere, and single crystals electrical conductivity studies. The results evidenced the formation of new complex solids of previously unknown compositions and structures. Three out of four compounds crystallized in non-centrosymmetric space groups and represent layered 2D polymeric puckered structures that being stacked on each other form 3D lattices. All new solids exhibit strong second-harmonic-generation (SHG effect; based on YAG 1064 nm tests with detection of 532 nm photons), and a rare photosalient effect when crystals physically move in the laser beam. Single crystals' electrical conductivity of the four new synthesized compounds was measured, and the results showed their semiconductor behavior. Values of band gaps of these new solids were determined using diffusion reflectance spectroscopy in the visible region. Aspects of new solids' practical usefulness are discussed.

Nitroxide radicals appended to phthalonitriles: synthesis, structural characterization and photophysical properties.

The syntheses of 4-[4-(4,4,5,5-tetramethyl-2-imidazoline-3-oxide-1-oxyl-2-yl)phenoxy]phthalonitrile (3, C21H19N4O3) and 4-[4-(4,4,5,5-tetramethyl-2-imidazoline-1-oxyl-2-yl)phenoxy]phthalonitrile (4) were carried out by microwave-assisted nucleophilic aromatic substitution of 4-nitrophthalonitrile (2) by the pre-formed 2-(4-hydroxyphenyl)-4,4,5,5-tetramethyl-2-imidazoline-3-oxide-1-oxyl (1). Compounds 3 and 4 were characterized unambiguously by a rich array of analyses, such as melting point, FT-IR, MALDI-TOF MS, elemental analysis, UV-Vis, CV, EPR, magnetic measurements and single-crystal X-ray diffraction. Structural studies demonstrate that the C-H...X and C-X...π (X = O and N) interactions in the radical nitronyl nitroxide groups play an important role in the assembly of the crystal structures. Moreover, cyclic voltammetry analyses show that the phthalonitrile substituent retains the redox properties of the Ullman radicals.

•BMPO-OOH Spin-Adduct as a Model for Study of Decomposition of Organic Hydroperoxides and the Effects of Sulfide/Selenite Derivatives. An EPR Spin-Trapping Approach.

Lipid hydroperoxides play an important role in various pathophysiological processes. Therefore, a simple model for organic hydroperoxides could be helpful to monitor the biologic effects of endogenous and exogenous compounds. The electron paramagnetic resonance (EPR) spin-trapping technique is a useful method to study superoxide (O2•-) and hydroxyl radicals. The aim of our work was to use EPR with the spin trap 5-tert-butoxycarbonyl-5-methyl-1-pyrroline-N-oxide (BMPO), which, by trapping O2•- produces relatively stable •BMPO-OOH spin-adduct, a valuable model for organic hydroperoxides. We used this experimental setup to investigate the effects of selected sulfur/selenium compounds on •BMPO-OOH and to evaluate the antioxidant potential of these compounds. Second, using the simulation of time-dependent individual BMPO adducts in the experimental EPR spectra, the ratio of •BMPO-OH/•BMPO-OOH-which is proportional to the transformation/decomposition of •BMPO-OOH-was evaluated. The order of potency of the studied compounds to alter •BMPO-OOH concentration estimated from the time-dependent •BMPO-OH/•BMPO-OOH ratio was as follows: Na2S4 > Na2S4/SeO32- > H2S/SeO32- > Na2S2 ~Na2S2/SeO32- ~H2S > SeO32- ~SeO42- ~control. In conclusion, the presented approach of the EPR measurement of the time-dependent ratio of •BMPO-OH/•BMPO-OOH could be useful to study the impact of compounds to influence the transformation of •BMPO-OOH.

Free radical formation in chloramphenicol heated at different temperatures and the best thermal sterilization conditions - application of EPR spectroscopy and UV spectrophotometry.

Free radicals in thermally treated chloramphenicol were examined by electron paramagnetic resonance (EPR) spectroscopy. The parameters and shape of EPR spectra were analysed and free radical concentrations were obtained in the tested drug samples. Chloramphenicol was thermally sterilized at pharmacopeia conditions: 100 °C (120 min). Sterilization was also carried out at different conditions, 110 °C (60 min) and 120 °C (30 min), for comparison with pharmacopeia settings. Microbiological analysis was performed on the samples to confirm sterility. The aim of this work was to determine the concentration of free radicals in chloramphenicol following thermal sterilization at pharmacopeia conditions and compare this with other sets of conditions [110 °C (60 min) and 120 °C (30 min)]. The best conditions of thermal sterilization are determined as those that kill microorganisms and produce the lowest amounts of free radicals in this drug. It was concluded that the optimal temperatures and times for the thermal sterilization of chloramphenicol are 100 °C and 120 min and 110 °C and 60 min. A temperature of 120 °C coupled with a heating time of 30 min was rejected for thermal sterilization because of the high amount of free radicals produced by the drug samples.

Tyrosine or Tryptophan? Modifying a Metalloradical Catalytic Site by Removal of the Cys-Tyr Cross-Link in the Galactose 6-Oxidase Homologue GlxA.

The concerted redox action of a metal ion and an organic cofactor is a unique way to maximize the catalytic power of an enzyme. An example of such synergy is the fungal galactose 6-oxidase, which has inspired the creation of biomimetic copper oxidation catalysts. Galactose 6-oxidase and its bacterial homologue, GlxA, possess a metalloradical catalytic site that contains a free radical on a covalently linked Cys-Tyr and a copper atom. Such a catalytic site enables for the two-electron oxidation of alcohols to aldehydes. When the ability to form the Cys-Tyr in GlxA is disrupted, a radical can still be formed. Surprisingly, the radical species is not the Tyr residue but rather a copper second-coordination sphere Trp residue. This is demonstrated through the introduction of a new algorithm for Trp-radical EPR spectra simulation. Our findings suggest a new mechanism of free-radical transfer between aromatic residues and that the Cys-Tyr cross-link prevents radical migration away from the catalytic site.

Radiolytic studies of cefozopran hydrochloride in the solid state

Background: The radiation sterilization is one of the best methods for sterilizing vulnerable degradation drugs like cefozopran hydrochloride. Results: Chemical stability of radiosterylized cefozopran hydrochloride, was confirmed by spectrophotometric and chromatographic methods. EPR studies showed that radiation has created some radical defects whose concentration was no more than several dozen ppm. The antibacterial activity of cefozopran hydrochloride irradiated with a dose of 25 kGy was unaltered for Gram-positive bacteria but changed for two Gram-negative strains. The radiation sterilized cefozopran hydrochloride was not in vitro cytotoxic against human CCD39Lu normal lung fibroblast cell line. Conclusions: Cefozopran hydrochloride in solid state is not resistant to radiation sterilization and this method cannot be used for sterilization of this compound.

Interactions of short-acting, intermediate-acting and pre-mixed human insulins with free radicals--Comparative EPR examination.

Electron paramagnetic resonance (EPR) spectroscopy was used to examine insulins interactions with free radicals. Human recombinant DNA insulins of three groups were studied: short-acting insulin (Insuman Rapid); intermediate-acting insulins (Humulin N, Insuman Basal), and pre-mixed insulins (Humulin M3, Gensulin M50, Gensulin M40, Gensulin M30). The aim of an X-band (9.3GHz) study was comparative analysis of antioxidative properties of the three groups of human insulins. DPPH was used as a stable free radical model. Amplitudes of EPR lines of DPPH as the paramagnetic free radical reference, and DPPH interacting with the individual tested insulins were compared. For all the examined insulins kinetics of their interactions with free radicals up to 60 min were obtained. The strongest interactions with free radicals were observed for the short-acting insulin - Insuman Rapid. The lowest interactions with free radicals were characteristic for intermediate-acting insulin - Insuman Basal. The pre-mixed insulins i.e. Humulin M3 and Gensulin M50 revealed the fastest interactions with free radicals. The short acting, intermediate acting and premixed insulins have been found to be effective agents in reducing free radical formation in vitro and should be further considered as potential useful tools in attenuation of oxidative stress in diabetic patients.

Spectroscopic characterization, antioxidant and antitumour studies of novel bromo substituted thiosemicarbazone and its copper(II), nickel(II) and palladium(II) complexes.

A new, slightly distorted octahedral complex of copper(II), square planar complexes of nickel(II) and palladium(II) with 2,4'-dibromoacetophenone thiosemicarbazone (DBAPTSC) are synthesized. The ligand and the complexes are characterized by FT-IR, FT-Raman, powder X-ray diffraction studies. The IR and Raman data are correlated for the presence of the functional groups which specifically helped in the confirmation of the compounds. In addition, the free ligand is unambiguously characterized by (1)H and (13)C NMR spectroscopy while the copper(II) complex is characterized by electron paramagnetic resonance spectroscopy (EPR). The g values for the same are found to be 2.246 (g1), 2.012 (g2) and 2.005 (g3) which suggested rhombic distortions. The HOMO-LUMO band gap calculations for these compounds are found to be in between 0.5 and 4.0 eV and these compounds are identified as semiconducting materials. The synthesized ligand and its copper(II), nickel(II) and palladium(II) complexes are subjected to antitumour activity against the HepG2 human hepatoblastoma cell lines. Among all the compounds, nickel(II) complex is found to exert better antitumour activity with 57.6% of cytotoxicity.

DFT calculations and experimental FT-IR, dispersive-Raman and EPR spectral studies of Copper (II) chloride complex with 3-amino-1-methylbenzene.

In this study, we present the synthesis and the characterization of Copper (II) chloride complex with 3-amino-1-methylbenzene (3A1MB). This complex was characterized by vibrational and EPR spectroscopic techniques and elemental analysis. The molecular structure and spectrometry of this complex: Cu(3A1MB)2Cl2 and its ligand: 3A1MB have been investigated theoretically by performing DFT/B3LYP calculations. Cu(3A1MB)2Cl2 has been optimized as two conformers and the more stable conformer is determined. The optimized geometries and calculated vibrational frequencies have been evaluated via comparison with experimental values, and the normal modes were assigned on the basis of the percent potential energy distribution (PED). A good agreement between calculated and experimental data is observed.

Copper(II) complexes of N-(2-{[(2E)-2-(2-Hydroxy-(5-substituted)-benzylidene)-hydrazino]carbonyl}phenyl)benzamide ligands and heterocyclic coligands.

Some copper(II) complexes of the type [Cu(L1-3)(phen]·CH2Cl2 (1a-3a) and [Cu(L1-3) (bipy)]·CH2Cl2 (1b-3b) (where L1=N-(2-{[(2E)-2-(2-Hydroxy-benzylidene)-hydrazino]carbonyl}phenyl)benzamide, L2=N-(2-{[(2E)-2-(2-Hydroxy-(5-bromo)-benzylidene)-hydrazino]carbonyl}phenyl)benzamide, L3=N-(2-{[(2E)-2-(2-Hydroxy-(5-methoxy)-benzylidene)-hydrazino]carbonyl}phenyl)benzamide; phen=1,10-phenanthroline, bipy=2,2'-bipyridine) have been prepared and characterized on the basis of elemental analyses, IR, UV-Vis and EPR spectral studies. IR spectra indicate that the ligand L1-3 exists in the keto form in the solid state, while at the time of complexation, it tautomerises into enol form. The single crystal X-ray diffraction study of the representative complex [Cu(L1) (phen)]·CH2Cl2 (1a) reveals the distorted square pyramidal geometry around copper(II). Crystal data of (1a): space group=P21/n, a=11.5691(16) Å, b=11.0885(15) Å, c=24.890(4) Å, V=3166.2(8) Å(3), Z=4. The electrochemical behavior of all the complexes indicate that the phen complexes appears at more positive potential as compared to those for bipy complexes, as a consequence of its stronger π acidic character. All the complexes exhibit blue-green emission as a result of the fluorescence from the intra-ligand (π→π(*)) emission excited state.

Binary and ternary copper(II) complexes of a tridentate ONS ligand derived from 2-aminochromone-3 carboxaldehyde and thiosemicarbazide: synthesis, spectral studies and antimicrobial activity.

A tridentate ONS donor ligand, HL, was synthesized by the condensation of 2-aminochromone-3-carboxaldehyde with thiosemicarbazide. The structure of the ligand was elucidated by elemental analyses, IR, (1)H and (13)C NMR, electronic and mass spectra. Reaction of the ligand with several copper(II) salts, including AcO(-), NO3(-), SO4(2-), Cl(-), Br(-) and ClO4(-) afforded different metal complexes that reflect the non-coordinating or weakly coordinating power of the ClO4(-) and Br(-) anions as compared to the strongly coordinating power of AcO(-), SO4(2-), Cl(-) and NO3(-) anions. Also, the ligand was allowed to react with Cu(II) ion in the presence of a secondary ligand (L') [N,O-donor; 8-hydroxyquinoline or N,N-donor; 1,10-phenanthroline]. Characterization and structure elucidation of the prepared complexes were achieved by elemental and thermal analyses, IR, electronic, mass and EPR spectra as well as conductivity and magnetic susceptibility measurements. The EPR spin Hamiltonian parameters of some complexes were calculated. The metal complexes exhibited octahedral and square planar geometrical arrangements depending on the nature of the anion. The ligand and most of its metal complexes showed antibacterial activity towards Gram-positive bacteria (Staphylococcus aureus and Bacillus subtilis), Gram-negative bacteria (Salmonella typhimurium and Escherichia coli), yeast (Candida albicans) and fungus (Aspergillus fumigatus).