Magnetic Fe2O3-polystyrene/PPy core/shell particles: bioreactivity and self-assembly

This paper describes the synthesis of new magnetic, reactive polystyrene/polypyrrole core/shell latex particles. The core consists of a polystyrene microsphere containing gamma-Fe2O3 superparamagnetic nanoparticles (PSmag), and the shell is made of reactive N-carboxylic acid-functionalized polypyrrole (PPyCOOH). These PSmag-PPyCOOH latex particles, average diameter 220 nm, were prepared by copolymerization of pyrrole (Py) and the active carboxyl-functionalized pyrrole (PyCOOH) in the presence of PSmag particles. PNVP was used as a steric stabilizer. The functionalized polypyrrole-coated PSmag particles were characterized in terms of their particle size, surface morphology, chemical composition, and electrochemical and magnetic properties using transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry, and SQUID magnetometry. Activation of the particle surface carboxyl groups was achieved using 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide (EDC) and N-hydroxysuccinimide (NHS), which helps transform the carboxyl groups into activated ester groups (NSE). The activated particles, PSmag-PPyNSE, were further evaluated as bioadsorbents of biotin used as a model biomolecule. It was shown that biotin was immobilized at the surface of the PSmag-PPyNSE particles by forming interfacial amide groups. The assemblies of PSmag-PPyCOOH particles on glass plates were further investigated. When no magnetic field is applied, the particles assemble into 3D colloidal crystals. In contrast, under a magnetic field, one-particle-thick chains gathered in hedgehog-like architectures are obtained. Furthermore, PSmag-PPyCOOH coated ITO electrodes were shown to be electroactive and electrochemically stable, thus offering potentialities for creating novel high-specific-area materials for biosensing devices where the conducting polymer component would act as the transducer through its conductive properties.     

Antioxidant compounds of propolis determined by capillary electrophoresis-mass spectrometry

Propolis is a resinous hive product rich in antioxidant compounds. Capillary electrophoresis coupled to mass spectrometric detection can provide selective information about the analytes present in complex extracts of propolis and has turned out to be an attractive alternative to HPLC methods. Therefore, a CE-ESI-MS method has been developed for the analysis of antioxidant compounds obtained from propolis. For this purpose, different electrophoretic parameters such as the nature, pH, and concentration of the separation buffer, as well as electrospray parameters (dry gas temperature and flow, nebulising gas pressure, and make-up flow) have been carefully optimised. Different phenolic compounds (e.g. pinobanksin 3-acetate, naringenin, pinocembrin, chrysin, daidzein, quercetin 3',7-dimethyl ether, apigenin, and kaempferid) could be detected. To confirm the identity of the phenolic compounds in propolis extracts, accurate mass data of the molecular ions were obtained by TOF MS. Limits of detection ranging from 6 mg/100 g of raw propolis for chrysin to 58 mg/ 100 g of raw propolis for luteolin, were obtained.     

Invertase production is related to the nitrogen source in Hansenula anomala

Differences in invertase accumulation of Hansenula anomala cultivated in ammonium and nitrate are reported. Media supplemented with sucrose and ammonium sulfateas the solecarbon and nitrogen source, respectively, show strong media acidification (pH 3.0 or lower), and vigorous cell growth. Invertase activity was not detected under such conditions. A cell-free imitation experiment suggests that, under such low pH, extensive chemical break-down of sucrose (>22%) occurs. Thus, H. anomala is able togrow under strong acidic conditions that permit sucrose metabolism by the uptake of monosaccharides generated from chemical hydrolysis. In addition, invertase activity is not present in cells grown in nitrate as nitrogen source at pH 5.0, but at pH 7.0 activity is detected. If ammonium is supplied instead of nitrate, cells grown at pH 5.0 show invertase activity and at pH 7.0 high levels of activity are detected. These results indicate a specific physiological response of the sucrose metabolism to the presence of alternate nitrogen source.     

Intermediates trapped during nitrogenase reduction of N triple bond N, CH3-N=NH, and H2N-NH2

A high population intermediate has been trapped on the nitrogenase active site FeMo cofactor during reduction of N2. In addition, intermediates have been trapped during reduction of CH3-N=NH by the alpha-195Gln variant and during reduction of H2N-NH2 by the alpha-70Ala/alpha-195Gln variant. Each of these trapped states shows an EPR signal arising from an S = 1/2 state of the FeMo cofactor. 15N ENDOR shows that each intermediate has a nitrogenous species bound to the FeMo cofactor, with a single type of N seen for each bound intermediate. The g tensors are unique to each intermediate, g(e) = [2.084, 1.993, 1.969], g(m) = [2.083, 2.021, 1.993], g(l) = [2.082, 2.015, 1.987], as are the 15N hyperfine couplings at g1, which suggests that three distinct stages of NN reduction may have been trapped. The 1H ENDOR spectra show that the N2 intermediate is at a distinct and earlier stage of reduction from the other two, so at least two stages of NN reduction have been trapped. Some possible structures of the hydrazine intermediate are presented.     

Iron uptake and toxicity in Caco-2 cells

The differences between the in vitro effects of iron attributed to valence, chelation, and complexation are known in terms of markers of oxidative stress. Few studies, however, describe the effects of iron on general markers of toxicity used in the testing of cell cultures. The aim of the present study was to determine the toxicity and uptake of different salts and iron complexes in the human intestinal cell line, Caco-2.Cells were incubated with 1.5 mM of different species of iron [FeCl₃/nitrilotriacetic acid (NTA) (1:2), FeCl₃/citric acid (1:2), FeCl₃ and FeSO₄] for 22–24 h. Thereafter, toxicological and uptake experiments were performed.The iron uptake, viability (via MTT assay), and membrane stability (via LDH release) of Caco-2 cells incubated with various iron forms differed significantly from untreated controls which showed no detrimental effects on cells and less iron uptake. The lowest signal for cell viability (MTT assay) was found after the incubation of the cells with FeCl₃/citric acid, being significantly different to treatment with FeCl₃, where the highest MTT signal was detected (p=0.002). No differences between the tested iron species could be found regarding cell proliferation (via serial cell counting) and viability using the trypan blue exclusion test. The lowest membrane damage (via LDH release) was registered in cells treated with FeCl₃/citric acid (1:2), whereas the highest LDH release could be found in cells incubated with FeCl₃/NTA (1:2). The highest intracellular iron concentration (measured via GFAAS) was detected after the treatment of Caco-2 cells with FeCl₃ and FeCl₃/NTA (1:2).This study substantiates the importance of the choice of complexes, as NTA seemed to enhance the toxicity of iron, while citric acid inhibited iron uptake and toxicity.     

The preparation of silica entrapped homogeneous hydrogenation catalysts by conventional and ionic liquid mediated sol-gel routes

[RhCl(PPh₃)₃] has been entrapped inside silica matrices by two methods: a conventional sol-gel synthesis in ethanol/water and a new route performed in an ionic liquid. The activity of these heterogenised catalysts has been tested for the hydrogenation of styrene. The catalyst prepared in an ionic liquid was found to be more active and have low Rh leaching.     

Effect of Emulsifier Type on the Characterization of O/W Emulsions Using a Spectroscopy Technique

The droplet size distribution (DSD) of emulsions is the result of two competitive effects that take place during emulsification process, i.e., drop breakup and drop coalescence, and it is influenced by the formulation and composition variables, i.e., nature and amount of emulsifier, mixing characteristics, and emulsion preparation, all of which affect the emulsion stability. The aim of this study is to characterize oil-in-water (O/W) emulsions (droplet size and stability) in terms of surfactant concentration and surfactant composition (sodium dodecyl benzene sulphonate (SDBS)/Tween 80 mixture). Ultraviolet-visible (UV-vis) transmission spectroscopy has been applied to obtain droplet size and stability of the emulsions and the verification of emulsion stability with the relative cleared volume technique (time required for a certain amount of emulsion to separate as a cleared phase). It is demonstrated that the DSD of the emulsions is a function of the oil concentration and the surfactant composition with higher stability for emulsions prepared with higher SDBS ratio and lower relative cleared volume with the time. Results also show that smaller oil droplets are generated with increasing Tween 80 ratio and emulsifier concentration.     

Diffuse Reflectance Spectroscopy Versus Mexameter® MX18 Measurements of Melanin and Erythema in an African Population

Melanin provides protection against excess exposure to solar ultraviolet radiation (UVR) and related adverse health effects. Diffuse reflectance spectroscopy (DRS) can be used to calculate cutaneous melanin and erythema, but this is complex and has been mostly used for light‐to‐medium pigmented skin. Handheld reflectance spectrophotometers, such as the Mexameter^® MX18, can also be used. We compared DRS‐calculated melanin and erythema values with Mexameter melanin and erythema index values to understand how these techniques/measurements correlate in an African population of predominantly deeply pigmented skin. Five hundred and three participants comprised 68.5% self‐identified Black African, 9.9% Indian/Asian, 18.4% White and 2.9% Colored. The majority of Black African (45%), Indian/Asian (34%) and Colored (53%) participants self‐identified their skin as being “brown.” Measured melanin levels increased with darker self‐reported skin color. DRS‐calculated and Mexameter melanin values demonstrated a positive correlation (Spearman rho = 0.87, P < 0.001). The results from both instruments showed erythema values were strongly correlated with their own melanin values. This finding is considered spurious and may result from the complexity of separating brown and red pigment when using narrowband reflectance techniques. Further work is needed to understand melanin, erythema and color in Black skin given sun‐related health risks in vulnerable groups in Africa.