Production of bacterial cellulose tubes for biomedical applications: Analysis of the effect of fermentation time on selected properties.

Biosynthesis of bacterial cellulose (BC) in cylindrical oxygen permeable molds allows the production of hollow tubular structures of increasing interest for biomedical applications (artificial blood vessels, ureters, urethra, trachea, esophagus, etc.). In the current contribution a simple set-up is used to obtain BC tubes of predefined dimensions; and the effects of fermentation time on the water holding capacity, nanofibrils network architecture, specific surface area, chemical purity, thermal stability, mechanical properties, and cell adhesion, proliferation and migration of BC tubes are systematically analysed for the first time. The results reported highlight the role of culture time on key properties of the BC tubes produced, with significant differences arising from the denser and more compact fibril arrangements generated at longer fermentation intervals.

Modeling of post-traumatic epilepsy and experimental research aimed at its prevention

Research on the prevention of post-traumatic epilepsy (PTE) has seen remarkable advances regarding its physiopathology in recent years. From the search for biomarkers that might be used to indicate individual susceptibility to the development of new animal models and the investigation of new drugs, a great deal of knowledge has been amassed. Various groups have concentrated efforts in generating new animal models of traumatic brain injury (TBI) in an attempt to provide the means to further produce knowledge on the subject. Here we forward the hypothesis that restricting the search of biomarkers and of new drugs to prevent PTE by using only a limited set of TBI models might hamper the understanding of this relevant and yet not preventable medical condition.

Modeling of post-traumatic epilepsy and experimental research aimed at its prevention.

Research on the prevention of post-traumatic epilepsy (PTE) has seen remarkable advances regarding its physiopathology in recent years. From the search for biomarkers that might be used to indicate individual susceptibility to the development of new animal models and the investigation of new drugs, a great deal of knowledge has been amassed. Various groups have concentrated efforts in generating new animal models of traumatic brain injury (TBI) in an attempt to provide the means to further produce knowledge on the subject. Here we forward the hypothesis that restricting the search of biomarkers and of new drugs to prevent PTE by using only a limited set of TBI models might hamper the understanding of this relevant and yet not preventable medical condition.

Applications of bacterial cellulose as precursor of carbon and composites with metal oxide, metal sulfide and metal nanoparticles: A review of recent advances.

This mini review is limited to very recent studies (last 5-10 years) on two major issues, concerning: the production and physical/chemical modification of bacterial cellulose (BC), and its transformation into carbon and integrated synthesis of metal oxides (TiO2, ZnO, Fe3O4, etc.), metal sulfide (ZnS, CdS, etc.) and metal nanoparticles (Au, Ag, Pt, Pd, etc.) within bacterial cellulose nanoribbons network. We believe that the crossover of these two domains could be of considerable interest in the view of improving the performance of materials prepared with bacterial cellulose. The diversity of these nanomaterials allows targeting of many very different properties/applications: electrochemical devices, catalysis and photocatalysis, sensors, etc. After an introduction to the most important chemical and physical characteristics of BC, production parameters, and its physical and chemical modifications, we review the use of BC as a precursor of inorganic materials like carbon and composites with metal or inorganic nanoparticles.

Organocatalytic route for the synthesis of propionylated starch.

In recent years acetylated, propionylated and butyrylated starches have received special attention due to their capacity to deliver specific short chain fatty acids (SCFAs) to the colon in a sustained and predictable manner, and thus contribute to maintaining the normal physiologic function of the large bowel and preventing specific diseases. In the current contribution a non-conventional organocatalytic solventless route for the eco-friendly propionylation of corn starch is proposed. The catalyst used in the acylation is a naturally occurring α-hydroxy acid (l-tartaric acid). Propionylated starches with degree of substitution (DS) in the 0.05-1.59 interval were obtained and characterized in terms of chemical structure, morphology, crystallinity, thermal stability and hydrophilicity. Results showed that by the proposed methodology propionylated starch with the DS required for clinical use (i.e. 0.2-0.3) could be obtained within 2-3h of reaction. Characterization results evidenced the progressive loss of crystallinity of starch granules as higher substitution levels were conferred.

Facile synthesis of cobalt ferrite nanotubes using bacterial nanocellulose as template.

A facile method for the preparation of cobalt ferrite nanotubes by use of bacterial cellulose nanoribbons as a template is described. The proposed method relays on a simple coprecipitation operation, which is a technique extensively used for the synthesis of nanoparticles (either isolated or as aggregates) but not for the synthesis of nanotubes. The precursors employed in the synthesis are chlorides, and the procedure is carried out at low temperature (90 °C). By the method proposed a homogeneous distribution of cobalt ferrite nanotubes with an average diameter of 217 nm in the bacterial nanocellulose (BC) aerogel (3%) was obtained. The obtained nanotubes are formed by 26-102 nm cobalt ferrite clusters of cobalt ferrite nanoparticles with diameters in the 9-13 nm interval. The nanoparticles that form the nanotubes showed to have a certain crystalline disorder, which could be attributed in a greater extent to the small crystallite size, and, in a lesser extent, to microstrains existing in the crystalline lattice. The BC-templated-CoFe2O4 nanotubes exhibited magnetic behavior at room temperature. The magnetic properties showed to be influenced by a fraction of nanoparticles in superparamagnetic state.

Selective electrodesorption based atomic layer deposition (SEBALD): a novel electrochemical route to deposit metal clusters on Ag(111).

The possibility of synergic effects of some metals on the catalytic activity of silver led us to study the way to perform controlled deposition on silver. In fact, many metals of technological interest such as Co, Ni, and Fe cannot be deposited at underpotential on silver, and any attempt to control the deposition at overpotential, even at potentials slightly negative of the Nernst value, did not allow an effective control. However, due to the favorable energy gain involved in the formation of the corresponding sulfides, these metals can be deposited at underpotential on sulfur covered silver. The deposition is surface limited and the successive electrodesorption of sulfur leaves confined clusters of metals. The method can also be used to obtain metal clusters of different size. In fact, the alternate underpotential deposition of elements that form a compound is the basis of the electrochemical atomic layer epitaxy (ECALE), and the reiteration of the basic cycle allows us to obtain sulfide deposits whose thickness increases with the number of cycles. Therefore, the successive selective desorption of sulfur leaves increasing amounts of metals.

In situ scanning tunneling microscopy investigation of sulfur oxidative underpotential deposition on Ag(100) and Ag(110).

Underpotential (UPD) deposition of sulfur from Na(2)S solution in 0.1 M NaOH was studied on Ag(100) and Ag(110) using in situ scanning tunneling microscopy (STM). The cyclic voltammogram on Ag(100) presents two broad peaks, whereas three partial overlapping peaks and a sharper one are observed on Ag(110). STM measurements carried out during the whole UPD process show that progressively more compact structures are formed as the applied potential is scanned toward more positive potentials. More precisely, p(2×2), c(2×6), and c(2×2) were found on Ag(100) at E = -1.25, -1.0, and -0.9 V, respectively. Less definite conclusions can be drawn for the structures of S overlayers on Ag(110). However, the experimental findings are consistent with an incomplete p(2×1) at potentials preceding the sharp peak, and with a c(2×2) structure at E = -0.9 V vs Ag/AgCl, KCl(sat). The coverage values calculated on the basis of the hypothesized structures have been compared with the values obtained from chronocoulometric measurements at the most positive potentials investigated. Thus, the experimental coverage θ = 0.5 coincides with the coverage calculated for the c(2×2) structure found on Ag(110) at E = -0.9 V by STM, whereas the experimental coverage θ = 0.42 suggests that a mixture of structures c(2×6) and c(2×2) is formed on Ag(100).

Confined electrodeposition of CdS in the holes left by the selective desorption of 3-mercapto-1-propionic acid from a binary self-assembled monolayer formed with 1-octanethiol.

Confined electrodeposition can be achieved through the use of suitable templates, by which the electrodeposition occurs in natural or artificial holes of an insulating layer on a conducting substrate. Here, we present the electrodeposition of CdS on the holes left by the selective desorption of 3-mercaptopropionic acid (MPA) from a binary self-assembled monolayer (SAM) formed on Ag(111) with 1-octanethiol (OT). The electrodeposition of a compound is quite demanding, since it requires the right stoichiometry. In addition, the surface underpotential deposition phenomena exploited by electrochemical atomic layer epitaxy (ECALE) technique ensures that the surface available for electrodeposition after the selective desorption is still Ag(111). Parallel electrochemical experiments show that the amount of compound electrodeposited is consistent with this free Ag(111) surface, and the morphological analysis performed both by atomic force microscopy (AFM) and by lateral force microscopy (LFM) confirm the electrochemical data.

Selective adsorption of plant cysteine peptidases onto TiO2.

A crude extract rich in plant cysteine peptidases was obtained from the latex of the fruits of Araujia hortorum, a South American climbing plant. The highly concentrated extract was immobilized onto titanium dioxide to produce biocatalysts through a simple adsorption procedure. Absorbance measurement at 280 nm and Bradford's method for protein quantification revealed that the protein content of the crude extract was selectively adsorbed onto the titanium dioxide surface at a very high rate. In 5 min of contact with the support all protein present in the crude extract was selectively withdrawn from the solution, leading to an immobilized biocatalyst with a high protein concentration. Caseinolytic assays indicated that, except for the catalyst obtained with the highest crude amount contacted with the support, all the proteolytic activity present in the crude extract was adsorbed onto TiO(2). The amidasic activity of the immobilized catalysts (Ah/TiO(2)) was tested in the hydrolysis of a synthetic chromogenic substrate (PFLNA) showing partial deactivation with respect to the native enzyme. In amidasic activity assays the ionic strength of the buffer medium showed to be a key feature to consider in order to avoid protease desorption from the support, indicating the importance of electrostatic interactions between the enzymes and TiO(2). Reuse of the produced biocatalysts with PFLNA as substrate revealed that after five successive uses Ah/TiO(2) retained more than 20% of its initial activity.

Ternary CdSxSe 1-x deposited on Ag(111) by ECALE: synthesis and characterization.

Morphology and electronic properties of CdS, CdSe, and the ternary compounds of formula CdSxSe(1-x) deposited on Ag(111) by ECALE have been characterized as a function of the composition. The number of the attainable x values is limited by the necessity of using well-defined CdS/CdSe deposition sequences. However, the quantitative analysis carried out by XPS and electrochemical stripping experiments indicates that the ECALE method has a good control on composition. The AFM images together with the electrochemical characterization indicate both two-dimensional and three-dimensional growth contributions. The photospectra recorded at CdS film electrodes in liquid junction with an alkaline (poly)sulfide electrolyte show good efficiency of photoconversion and band gap typical of the single crystal. Lower photoconversion efficiency and the presence of subband gap response are observed for CdSe; a possible reason is some crystalline disorder due to lower control of the layer-by-layer deposition in the case of Se. The dependence of band gap on composition of ternary CdSxSe(1-x) ECALE films is monotonic and in agreement with literature data reported for bulk materials.

Frequent analytical/experimental problems in lipase-mediated synthesis in solvent-free systems and how to avoid them.

Compared with chemical catalysis, enzymatic catalysis is a relatively new topic. Experimental work involving lipases deserves careful attention and accurate procedures still need to be implemented. A rapid but careful survey of published data immediately demonstrates that experiments performed under similar conditions with similar reagents have led to very different results. The aim of this work is to point out the importance of accurate and systematic procedures in order to ensure the reproducibility of experimental data. We strongly believe that different results found by different labs are due to problems detected in the procedures used. Quantification of the immobilisation efficiency of lipase on several supports through UV/visible methods and sampling methods used to obtain correct enzymatic activity values are specifically analysed. After a brief review which demonstrates the big discrepancies found in the literature, original data from Candida rugosa lipase adsorption on polypropylene powder and its use in the solvent-free synthesis of ethyl oleate are introduced in order to exemplify the difficulties found in these kinds of systems. Several procedures described in the literature are assayed and the accuracy of the results obtained is carefully analysed. The aim of the whole analysis performed is that it would be useful for any powdered solid to be used as a support for a lipase in a solvent-free system for any synthesis reaction, especially for those involving a volatile reagent. Throughout this contribution, special emphasis is placed on how catalytic reaction results using enzymes (free and immobilised) are reported so as to allow comparison between published data, something which is usually difficult since very different units are used and often complementary data are not included.