Aerogel-Based Single-Ion Magnets: A Case Study of a Cobalt(II) Complex Immobilized in Silica.

The chemical immobilization of cobalt(II) ions in a silica aerogel matrix enabled the synthesis of the first representative example of aerogel-based single-ion magnets. For the synthesis of the lyogels, methyl-trimethoxysilane and N-3-(trimethoxysilyl)propyl ethylenediamine were co-hydrolyzed, then the ethylenediamine groups that were immobilized on the silica matrix enabled the subsequent binding of cobalt(II) ions. Lyogels with various amounts of ethylenediamine moieties (0.1-15 mol %) were soaked in isopropanol solutions of cobalt(II) nitrate and further supercritically dried in carbon dioxide to obtain aerogels with a specific surface area of 210-596 m2·g-1, an apparent density of 0.403-0.740 cm3·g-1 and a porosity of 60-78%. The actual cobalt content in the aerogels was 0.01-1.50 mmol per 1 g of SiO2, which could easily be tuned by the concentration of ethylenediamine moieties in the silica matrix. The introduction of cobalt(II) ions into the ethylenediamine-modified silica aerogel promoted the stability of the diamine moieties at the supercritical drying stage. The molecular prototype of the immobilized cobalt(II) complex, bearing one ethylenediamine ligand [Co(en)(MeCN)(NO3)2], was synthesized and structurally characterized. Using magnetometry in the DC mode, it was shown that cobalt(II)-modified silica aerogels exhibited slow magnetic relaxation in a nonzero field. A decrease in cobalt(II) concentration in aerogels from 1.5 mmol to 0.14 mmol per 1 g of SiO2 resulted in a weakening of inter-ion interactions; the magnetization reversal energy barrier likewise increased from 4 to 18 K.

Aluminosilicate Nanosponges: Synthesis, Properties, and Application Prospects.

A simple one-step method is presented for fabricating inorganic nanosponges with a kaolinite [Al2Si2O5(OH)4] structure. The nanosponges were synthesized by the hydrothermal treatment of aluminosilicate gels in an acidic medium (pH = 2.6) at 220 °C without using organic cross-linking agents, such as cyclodextrin or polymers. The formation of the nanosponge morphology was confirmed by scanning electron microscopy, and the assignment of the synthesized aluminosilicates to the kaolinite group was confirmed by X-ray diffraction and infrared spectroscopy. The effect of the synthesis conditions, in particular, the nature (HCl, HF, NaOH, and H2O) and pH of the reaction medium (2.6, 7, and 12), as well as the duration of the synthesis (3, 6, and 12 days), on the morphology of aluminosilicates of the kaolinite group was studied. The sorption capacity of aluminosilicate nanosponges with respect to cationic (e.g., methylene blue) and anionic (e.g., azorubine) dyes in aqueous solutions was studied. The pH sensitivity of the surface ζ potential of the synthesized nanosponges was demonstrated. The dependence of the hemolytic activity (the ability to destroy erythrocytes) of aluminosilicate nanoparticles on the particle morphology (platy, spherical, and nanosponge) has been identified for the first time. Aluminosilicate nanosponges were not found to exhibit hemolytic activity. The prospects of using aluminosilicate nanosponges to prepare innovative functional materials for ecology and medicine applications, in particular, as matrices for drug delivery systems, were identified.

Crystal and Supramolecular Structure of Bacterial Cellulose Hydrolyzed by Cellobiohydrolase from Scytalidium Candidum 3C: A Basis for Development of Biodegradable Wound Dressings.

The crystal and supramolecular structure of the bacterial cellulose (BC) has been studied at different stages of cellobiohydrolase hydrolysis using various physical and microscopic methods. Enzymatic hydrolysis significantly affected the crystal and supramolecular structure of native BC, in which the 3D polymer network consisted of nanoribbons with a thickness T ≈ 8 nm and a width W ≈ 50 nm, and with a developed specific surface SBET ≈ 260 m2·g-1. Biodegradation for 24 h led to a ten percent decrease in the mean crystal size Dhkl of BC, to two-fold increase in the sizes of nanoribbons, and in the specific surface area SBET up to ≈ 100 m2·g-1. Atomic force and scanning electron microscopy images showed BC microstructure "loosening"after enzymatic treatment, as well as the formation and accumulation of submicron particles in the cells of the 3D polymer network. Experiments in vitro and in vivo did not reveal cytotoxic effect by the enzyme addition to BC dressings and showed a generally positive influence on the treatment of extensive III-degree burns, significantly accelerating wound healing in rats. Thus, in our opinion, the results obtained can serve as a basis for further development of effective biodegradable dressings for wound healing.