Insights into Pore Size Control in Cellulose Nanopapers Through Modeling and Experiments.

An easy way of controlling pore sizes during the preparation of cellulose nanopapers using nanofibrillated cellulose and different solvents, such as water, ethanol and acetone, was applied in this study. A possible mathematical model is also presented, that describes the occuring processes, which model is based on simple probability theory computations taking the number of possible hydrogen bonds into consideration. This model allows the better understanding of the solvent dependence of pore formation on a molecular level. For the comparison of the effects of solvents two different series of cellulose nanopapers were prepared. In the cases of both series, an aqueous nanofibrillated cellulose suspension was used for the fabrication of nanopapers, and different solvents were used for their modification. Based on scanning electron microscopy images and mercury intrusion porosimetry data it has been concluded, that using different solvents was a crucial point in controlling pore sizes. A theory about the swelling effects, as well as the formation and decomposition of nanofibrillated cellulose aggregates based on the hydrogen bonding abilities of the solvents, was proposed and proven in this paper. As-prepared nanocellulose papers can be excellent candidates for further applications as support materials (e.g., virus filtration).

Electrospun TiO(2) fiber composite photoelectrodes for water splitting.

This work has focused on the development of electrospun TiO2 fiber composite photoelectrodes for hydrogen production by water splitting. For comparison, similar photoelectrodes were also developed using commercial TiO2 (Aeroxide P25) nanoparticles (NPs). Dispersions of either fibers or P25 NPs were used to make homogenous TiO2 films on fluorine-doped SnO2 (FTO) glass substrates by a doctor blade (DB) technique. Scanning electron microscopy (SEM) analysis revealed a much lower packing density of the DB fibers, with respect to DB-P25 TiO2 NPs; this was also directly reflected by the higher photocurrent measured for the NPs when irradiating the photoelectrodes at a light intensity of 1.5AM (1 sun, 1000 W/m(2)). For a better comparison of fibers vs. NPs, composite photoelectrodes by dip-coating (onto FTO) TiO2 sol-gel (SG) matrixes containing an equal amount (5 or 20 wt %) of either fibers or P25 NPs were also investigated. It emerged that the photoactivity of the fibers was significantly higher. For composites containing 5 wt % TiO2 fibers, a photocurrent of 0.5 mA/cm(2) (at 0.23 V vs Ag/AgCl) was measured, whereas 5 wt % P25 NPs only provided 0.2 mA/cm(2). When increasing to 20 wt % fibers or NPs, the photocurrent decreased, because of the formation of microcracks in the photoelectrodes, because of the shrinkage of the sol-gel. The high photoactivity of the fiber-based electrodes could be confirmed by incident photon to current efficiency (IPCE) measurements. Remarkably, the IPCE of composites containing 5 wt % fibers was between 35% and 40% in the region of 380-320 nm, and when accounting for transmission/reflection losses, the absorbed photon to current efficiency (APCE) was consistently over 60% between 380 nm and 320 nm. The superior photoactivity is attributed to the enhanced electron transport in the electrospun fibers, with respect to P25 NPs. According to this study, it is clear that the electronic connectivity ensured by the sol-gel also contributes positively to the enhanced photocurrent.

Phototransformation of ibuprofen and ketoprofen in aqueous solutions.

The UV (254 nm) and UV/VUV (254/185 nm) photolysis of two anti-inflammatory drugs, ibuprofen and ketoprofen, have been studied in aqueous solutions as a possible process for the removal of non-biodegradable compounds. We have examined the effects of dissolved oxygen and initial target concentration. Upon irradiation at 254 nm, the decomposition rate of ketoprofen is almost forty times higher as it of ibuprofen whilst VUV irradiation only increased the ibuprofen decomposition rate. The presence of dissolved oxygen accelerated the photodegradation of ibuprofen, whereas no effect was observed on the degradation of ketoprofen. The maximum quantum yield for the phototransformation was 0.2. The rate of mineralization in both cases was ∼60%, even after 1h of treatment and this suggests the formation of stable by-products which were identified using GC-MS and HPLC-MS, respectively.

Solution equilibrium characterization of insulin-mimetic Zn(II) complexes.

Solution speciation (stoichiometry and stability constants) of the insulin mimetic Zn(II) complexes of several bidentate ligands with (O,O), (N,O) or (S,O) coordination modes have been determined by pH-metry at 25 degrees Celsius and I=0.2M (KCl). All ligands were found to coordinate in a bidentate way forming mono, bis and tris complexes, besides a mixed hydroxo bis complex ZnL(2)(OH) detected in the slightly basic pH range together with the tris complex. Relationships between the stability data, lipophilicity of the complexes and earlier biological data are evaluated. The validity of the linear free energy relationships (LFER) between the proton and Zn(II) complexes and also between the VO(IV) and Zn(II) complexes is tested.

[Preparation and spectroscopic studies of diorganotin(IV) complexes with adenosine and related compounds]. / Az adenozin és rokonvegyületei di-n-butilón(IV) komplexeinek elóállítása és spektroszkópiás vizsgálata.

Nine complexes of adenosine and related compounds (adenosine-5'-monophosphate, adenosine-5'-triphosphate, 1-methyl-adenosine, pyridoxal-5-phosphate and beta-nicotinamide-adenine-dinucleotide-phosphoric acid) with di-n-butyltin(IV) oxide and/or di-n-butytin(IV) dichloride were prepared in the solid state. The compositions of the complexes were determined by standard analytical methods. It was found that the complexes contain organotin(IV) moiety and the ligand in a ratio of 1:1 or 2:1. The FTIR spectra demonstrated that di-n-butyltin(IV) oxide reacts with the D-ribose moiety of the ligands, while di-n-butyltin(IV) dichloride is co-ordinated to the deprotonated phosphate group. The basic part of the ligands does not participate directly in complex formation. Comparison of the experimental Mössbauer delta E values with those calculated on the basis of the PQS concept revealed that the organotin(IV) moiety has trigonal-bipyramidal, octahedral and in some cases tetrahedral geometry also. Some of the complexes contain the organotin(IV) cation in two different surroundings.