Reactions of Cadmium(II) Halides and Di-2-Pyridyl Ketone Oxime: One-Dimensional Coordination Polymers.

The coordination chemistry of 2-pyridyl ketoximes continues to attract the interest of many inorganic chemistry groups around the world for a variety of reasons. Cadmium(II) complexes of such ligands have provided models of solvent extraction of this toxic metal ion from aqueous environments using 2-pyridyl ketoxime extractants. Di-2-pyridyl ketone oxime (dpkoxH) is a unique member of this family of ligands because its substituent on the oxime carbon bears another potential donor site, i.e., a second 2-pyridyl group. The goal of this study was to investigate the reactions of cadmium(II) halides and dpkoxH in order to assess the structural role (if any) of the halogeno ligand and compare the products with their zinc(II) analogs. The synthetic studies provided access to complexes {[CdCl2(dpkoxH)∙2H2O]}n (1∙2H2O), {[CdBr2(dpkoxH)]}n (2) and {[CdI2(dpkoxH)]}n (3) in 50-60% yields. The structures of the complexes were determined by single-crystal X-ray crystallography. The compounds consist of structurally similar 1D zigzag chains, but only 2 and 3 are strictly isomorphous. Neighboring CdII atoms are alternately doubly bridged by halogeno and dpkoxH ligands, the latter adopting the η1:η1:η1:µ (or 2.0111 using Harris notation) coordination mode. A terminal halogeno group completes distorted octahedral coordination at each metal ion, and the coordination sphere of the CdII atoms is {CdII(η1 - X)(µ - X)2(Npyridyl)2(Noxime)} (X = Cl, Br, I). The trans-donor-atom pairs in 1∙2H2O are Clterminal/Noxime and two Clbridging/Npyridyl; on the contrary, these donor-atom pairs are Xterminal/Npyridyl, Xbridging/Noxime, and Xbridging/Npyridyl (X = Br, I). There are intrachain H-bonding interactions in the structures. The packing of the chains in 1∙2H2O is achieved via π-π stacking interactions, while the 3D architecture of the isomorphous 2 and 3 is built via C-H∙∙∙Cg (Cg is the centroid of one pyridyl ring) and π-π overlaps. The molecular structures of 1∙2H2O and 2 are different compared with their [ZnX2(dpkoxH)] (X = Cl, Br) analogs. The polymeric compounds were characterized by IR and Raman spectroscopies in the solid state, and the data were interpreted in terms of the known molecular structures. The solid-state structures of the complexes are not retained in DMSO, as proven via NMR (1H, 13C, and 113Cd NMR) spectroscopy and molar conductivity data. The complexes completely release the coordinated dpkoxH molecule, and the dominant species in solution seem to be [Cd(DMSO)6]2+ in the case of the chloro and bromo complexes and [CdI2(DMSO)4].

Effect of Peptides on the Synthesis, Properties and Wound Healing Capacity of Silver Nanoparticles.

The aim of this study is the synthesis of novel peptide-silver nanoparticle conjugates with enhanced wound healing capacity. Peptide-silver nanoparticle conjugates were synthesized using myristoyl tetrapeptide 6 (MT6) or copper tripeptide 1 (CuTP1). Peptide-free silver nanoparticles (AgNP) were synthesized using NaBH4 and sodium citrate and were used as control. The addition of the peptides during or after the synthesis of nanoparticles and its impact on the properties of the synthesized peptide-silver nanoparticle conjugates were assessed. The monitoring of the synthesis of nanoparticles was achieved using ultraviolet-visible spectrophotometry (UV-/Vis). The characteristics and colloidal stability of the nanoparticles (size and ζ-potential distribution, morphology, composition and structure) were monitored using dynamic laser scattering (DLS), transmission electron microscopy (TEM), atomic absorption spectroscopy (AAS) and X-ray diffraction (XRD). The wound healing capacity of the peptide-silver nanoparticle conjugates was assessed using scratch test assay on fibroblasts (NIH/3T3). The results indicated that the addition of the peptides during the synthesis of nanoparticles lead to better yield of the reaction and more effective capping while the size distribution and ζ-potential of the conjugates indicated long-term colloidal stability. The MT6-AgNP conjugate exhibited 71.97 ± 4.35% wound closure, which was about 5.48-fold higher (p < 0.05) than the corresponding free MT6. The CuTP1-AgNP conjugate exhibited 62.37 ± 18.33% wound closure that was better by 2.82 fold (p < 0.05) compared to the corresponding free CuTP1. Both peptides led to the synthesis of silver nanoparticle conjugates with enhanced wound healing capacity compared to the respective free peptide or to the peptide-free AgNP (29.53 ± 4.71% wound closure, p < 0.05). Our findings demonstrated that the synthetized peptide-silver nanoparticle conjugates are promising ingredients for wound care formulation.

Stimuli-responsive spin crossover nanoparticles for drug delivery and DNA-binding studies.

Aminated silica hybrid, spin-crossover (SCO) nanoparticles (AmNPs) coupled with (S)-naproxen (NAP) were proposed for potential drug nanocarriers through drug release experiments at various pH values. DNA- and albumin-binding studies were also carried out using diverse techniques in order to investigate the interaction of the nanoparticles with calf-thymus DNA and serum albumins and to determine the corresponding binding constants.

A facile approach to prepare silica hybrid, spin-crossover water-soluble nanoparticles as potential candidates for thermally responsive MRI agents.

A reverse micelle method was used for the synthesis of water-soluble silica hybrid, spin-crossover (SCO) nanoparticles (NPs). MRI experiments provided temperature dependent T2 values, indicating their potential use as smart MRI agents, while lyophilization of NP dispersions in water yielded powders with a preserved but modified thermal hysteretic magnetic profile.

2-D spin crossover materials at the nanometric scale: the effects of the size-reduction on the magnetic properties.

Spin Crossover (SCO) particles at the nanometric scale provide an alternative point of view and a new perspective concerning the development of a new generation of spintronic, electronic, photonic and mechanical devices. The coexistence of the SCO phenomenon with the accompanying hysteresis loop enhances the functionality of future devices for storing and processing information. Despite all promising facts, the SCO phenomena are greatly affected by cooperativity issues resulting in a direct relation between the decrease of the size of nanopatricle and the overall decrease of cooperativity towards more gradual spin transitions. This minireview aims to summarise the synthetic techniques for the synthesis of 2-D FeII SCO particles at the nanometric scale, an underexplored area of research, highlighting the effects of the size-reduction on the magnetic properties of the corresponding nanoparticles and hopefuly showcasing the importance of studying in the context of 2D limit the SCO phenomena.

Effect of Plant Extracts on the Characteristics of Silver Nanoparticles for Topical Application.

Silver nanoparticles (AgNPs) were synthesized using hydroalcoholic extracts of dittany (Origanum dictamnus), sage (Salvia officinalis), sea buckthorn (Elaeagnus rhamnoides, syn. Hippophae rhamnoides), and calendula (Calendula officinalis) as reducing agents. AgNPs synthesized using NaBH4 and citric acid were used as control. The impact of the origin of the extract and preparation conditions (light, temperature, reaction time) on the properties of the synthesized AgNPs was investigated. The structure, morphology, composition, physicochemical characteristics, and colloidal stability were characterized using dynamic laser scattering (DLS), ultraviolet-visible spectrophotometry (UV-/Vis), XRD, X-ray fluorescence (XRF), TEM, and FTΙR. The reduction of total phenolic and flavonoid content of the extracts after the reaction of AgNPs synthesis was also determined. Low IC50 values for all types of AgNPs revealed good antioxidant activity, attributable to the phenolic and flavonoid content of their surface. The results suggest that plant extract selection is important to the green synthesis of AgNPs because it affects the kinetics of their synthesis as well as their morphology, physicochemical characteristics, and colloidal stability. In vitro permeation studies on porcine skin revealed that AgNPs remained at the upper layers of stratum corneum and did not penetrate the skin barrier after 4 h of cutaneous application suggesting the safety of their application on intact skin for a relatively short time.