Synthesis and Characterization,Including Cancer Cell Line Inhibition,of Group VA (Group 15)-Containing Polyesters from Reaction with Camphoric Acid

Polyesters were rapidly synthesized employing interfacial polymerization from reaction of the salt of camphoric acid with Group VA (Group 15) triphenylmetallic dihalides. Yields range from 25 to 46 percent with chain lengths about 250. Infrared spectroscopy shows the formation of two new bands one assigned to the symmetrical M–O stretching and the second assigned to the asymmetrical M–O stretching. The bridging structure about the metal atom increases as the metal atom size increases. MALDI MS and proton NMR are consistent with the formation of the polyester structure. Ion fragment clusters to four to six units are identified. The polymers show good inhibition of a group of cancer cell lines including two pancreatic human cancer cell lines. In comparison with other metal/camphoric acid polymers, the metallocene polymers exhibit low EC₅₀ to the nanogram/ml range, and CI₅₀ values greater than one thousand for the hafnocene and zirconocene products. If this trend continues, the emphasis should be on the Group IVB metallocenes with respect to efforts to create anticancer drugs.     

Nano-to-macroporous TiO2 (anatase) by cold sintering process

Cold Sintering Process (CSP) was applied on commercial nanopowders to produce nanostructured TiO₂ anatase with nano-to-macro porosity. Nanoporous TiO₂ based materials were obtained by applying CSP at 150 °C and pressures up to 500 MPa on three TiO₂ nanopowders with different specific surface area (s.s.a. = 50, 90 and 370 m²/g), using water as transient aqueous environment. Although TiO₂ is insoluble in water, a density of 68% and s.s.a. = 117 m²/g were achieved from the powder with the highest specific surface area. A post annealing process at 500 °C increased the density up to 73% with a s.s.a. = 59 m²/g, and the crystallites dimensions passed from 110 Å in the powder to 130 Å in CSP material and 172 Å after post annealing. Finally, macroporosity was produced by using thermoplastic polymer beads as sacrificial templates within TiO₂ nanopowder during CSP, followed by a debonding at 500 °C.     

Alumina/Silicon Carbide Laminated Composites by Spark Plasma Sintering

Ceramic laminates composed of alumina/silicon carbide composite layers were produced by spark plasma sintering (SPS). Monolithic composite disks containing up to 30 vol% of silicon carbide were fabricated by stacking together and cosintering by SPS green layers prepared by tape casting water-based suspensions. An engineered laminate with a specific layer combination that is able to promote the stable growth of surface defects before final failure was also designed and produced. Fully dense materials with an optimum adhesion between the constituting layers and a homogeneous distribution of the two phases were obtained after SPS. Monolithic composites showed an increasing strength with SiC load, and biaxial strength values as high as 700 MPa were observed for a SiC content of 30 vol%. The engineered laminate showed a peculiar crack propagation that is responsible for the high strength value of about 600 MPa and for the evident insensitivity to surface defects.     

Vicia faba–Lygus rugulipennis Interactions: Induced Plant Volatiles and Sex Pheromone Enhancement

The profiles of volatile chemicals emitted by Vicia faba plants damaged by Lygus rugulipennis feeding, and by feeding plus oviposition, were shown to be quantitatively different from those released by undamaged plants. Samples of volatile chemicals collected from healthy plants, plants damaged by males as a consequence of feeding, plants damaged by females as a consequence of feeding and oviposition, plants damaged by feeding with mated males still present, and plants damaged by feeding and oviposition with gravid females still present, showed significant differences in the emission of hexyl acetate, (Z)-β-ocimene, (E)-β-ocimene, (E)-β-caryophyllene, and methyl salicylate. In particular, treatments with mated females present on plants had a significant increase in emission levels of the above compounds, possibly due to eggs laid within plant tissues or active feeding, compared with undamaged plants and plants damaged by males feeding, with or without insects still present. Furthermore, the pheromonal blend released by mated L. rugulipennis females, mainly comprising hexyl butyrate, (E)-2-hexenyl butyrate, and (E)-4-oxo-2-hexenal, was enhanced when females were active on broad bean plants, whereas such an increase was not observed in males. Both sexes gave electroantennogram responses to green leaf volatiles from undamaged plants and to methyl salicylate and (E)-β-caryophyllene emitted by Lygus-damaged plants, suggesting that these compounds may be involved in colonization of host plants by L. rugulipennis. In addition, mated males and females were responsive to hexyl butyrate, (E)-2-hexenyl butyrate, and (E)-4-oxo-2-hexenal released by mated females on V. faba, indicating that these substances could have a dual function as a possible aggregation pheromone in female–female communication, and as a sex pheromone in female–male communication. An erratum to this article can be found at     

Study of Some Experimental Parameters in the Synthesis of Triacylglycerols with CLA Isomers and Structural Analysis

The present research deals with the synthesis of structured triacylglycerols (TAG) by enzymatic treatment of sn-1,3-diacylglycerol (sn-1,3-DAG) with conjugated linoleic acid (CLA) isomers using the immobilized lipase from Rhizomucor miehei (Lipozyme^® IM) under different experimental conditions. In particular, the influence of reaction parameters, such as temperature, enzymatic load, reaction time and DAG/CLA ratio has been evaluated using an experimental design software with a screening objective. Two responses have been selected, they are the percentage of CLA isomers in total TAG and in the sn-2- position and a three-level-4-factor fractional factorial experimental design was used to screen the variables. The results showed that the selected experimental variables have an influence on the enzymatic reaction, in particular, the DAG/CLA substrate ratio and the temperature, both of which inversely correlated with CLA incorporation, but also the enzymatic load and the reaction time, both directly correlated with CLA incorporation. The best results for CLA isomer % content both in total TAG (46.3%) and in the sn-2- position (52.2%) were obtained at 40 °C for 96 h, with 20% enzymatic load and a 0.5 reactive ratio.     

Cathodic protection of carbon steel in natural seawater: Effect of sunlight radiation

Cathodic protection of metals in seawater is known to be influenced by chemical–physical parameters affecting cathodic processes (oxygen discharge, hydrogen evolution and calcareous deposit precipitation). In shallow seawater, these parameters are influenced by sunlight photoperiod and photosynthetic activity. The results presented here represent the first step in studies dedicated to cathodic protection in shallow photic seawater. This paper reports on carbon steel protected at −850 mV vs. Ag/AgCl (oxygen limiting current regime) in the presence of sunlight radiation but in the absence of biological and photosynthetic activity, the role of which deserves future research. Comparison of results obtained by exposing electrochemical cells to daylight cycles in both biologically inactivated natural seawater and in NaCl 3.5 wt.% solutions showed that sunlight affects current densities and that calcareous deposit interfere with light-currents effects. Sunlight radiation and induced heating of the solution have been separated, highlighting results not otherwise obvious: (1) observed current waves concomitant with sunlight radiation depend fundamentally on solar radiation, (2) solar radiation can determine current enhancements from early to late phases of aragonite crystal growth, (3) a three-day-old CaCO₃ layer reduces but does not eliminate the amplitude of the current waves. Theoretical calculations for oxygen limiting currents and additional field tests showed that sunlight, rather than bulk solution heating, is the main cause of daily current enhancements. This was confirmed by polarizations performed at −850 and −1000 mV vs. Ag/AgCl (constant bulk temperature), during which the electrode was irradiated with artificial lighting. This test also confirmed O₂ discharge to be the cathodic process involved. A mechanism of radiation conversion to heat in the oxygen diffusion layer region is proposed.     

Phase separation kinetics of maya asphaltene emulsion and free-to-bound water transformation

Differential scanning calorimetry (DSC) and inelastic neutron scattering were applied to study the phase separation kinetics of Maya asphaltene water-in-oil emulsion by following the water separation from the upper phase. In addition, transformation of the separated water from the free state to the bound and/or restricted state was also investigated. Maya asphaltene in toluene with 0.1 M HCl forms emulsion following ultrasonic or high speed mechanical emulsification. Initially, water molecules in the emulsion are largely free water. The emulsion gradually separates into two phases and at the 7th day over 90% of water molecules have situated at the bottom phase. In the mean time water molecules at the free state initially slowly transform into bound state in a much slower pace (over 100 days) than the phase separation kinetics.     

Supramolecular Bioconjugates for Protein and Small Drug Delivery

Supramolecular conjugation techniques have been developed to produce novel nanosized systems by assembling materials with diverse physicochemical and biological features. These techniques have been adapted to obtain innovative bioconjugates to deliver drugs with poor biopharmaceutical properties and nano-devices with potential “theranostic” activity. Supramolecular drug delivery systems include polymer therapeutics such as drug–polymer bioconjugates, and colloidal carriers such as micelles, liposomes, polyplexes, and organic and inorganic nanoparticles. By virtue of their wide array of chemical composition and properties, polymers represent key elements for the construction of novel supramoelcular formulations. Polymer bioconjugation is a fledged technique for fabrication of protein–polymer conjugates. PEGylation, in particular, produces derivatives with enhanced pharmacokinetic, immunological, and stability properties as compared to the parent protein. Over the years, new methods have been set up to obtain site-directed polymer conjugation. In this review we report few grafting to and growing from PEGylation examples for the preparation of therapeutically effective protein bioconjugates. Supramolecular formulations with unique properties can be also obtained by assembling functional polymers, targeting agents, physicochemical modifiers, and biomodulators. These systems may be designed for disease tissue disposition and cell recognition/penetration. Cyclodextrins, for example, have been functionalized with polyethylene glycol and folic acid to produce tumor-targeted drug carriers. Interesting results have been obtained with this novel class of drug delivery systems. In addition, responsive polymers have been conjugated to gold nanoparticles to endow a new colloidal platform with triggerable cell disposition properties, which can be exploited either in biomedicine or diagnosis.     

Bona Fide Tumor Suppressor Genes Hypermethylated in Melanoma: A Narrative Review

Loss-of-function events in tumor suppressor genes (TSGs) contribute to the development and progression of cutaneous malignant melanoma (CMM). Epigenetic alterations are the major mechanisms of TSG inactivation, in particular, silencing by promoter CpG-island hypermethylation. TSGs are valuable tools in diagnosis and prognosis and, possibly, in future targeted therapy. The aim of this narrative review is to outline bona fide TSGs affected by promoter CpG-island hypermethylation and their functional role in the progression of CMM. We conducted a systematic literature review to identify studies providing evidence of bona fide TSGs by cell line or animal experiments. We performed a broad first search and a gene-specific second search, supplemented by reference checking. We included studies describing bona fide TSGs in CMM with promoter CpG-island hypermethylation in which inactivating mechanisms were reported. We extracted data about protein role, pathway, experiments conducted to meet the bona fide criteria and hallmarks of cancer acquired by TSG inactivation. A total of 24 studies were included, describing 24 bona fide TSGs silenced by promoter CpG-island hypermethylation in CMM. Their effect on cell proliferation, apoptosis, growth, senescence, angiogenesis, migration, invasion or metastasis is also described. These data give further insight into the role of TSGs in the progression of CMM.