Highly Efficient Ru-Based Catalysts for Lactic Acid Conversion to Alanine.

The primary objective of this research was to develop efficient solid catalysts that can directly convert the lactic acid (LA) obtained from lignocellulosic biomass into alanine (AL) through a reductive amination process. To achieve this, various catalysts based on ruthenium were synthesized using different carriers such as multi-walled carbon nanotubes (MWCNTs), beta-zeolite, and magnetic nanoparticles (MNPs). Among these catalysts, Ru/MNP demonstrated a remarkable yield of 74.0% for alanine at a temperature of 200 °C. This yield was found to be superior not only to the Ru/CNT (55.7%) and Ru/BEA (6.6%) catalysts but also to most of the previously reported catalysts. The characterization of the catalysts and their catalytic results revealed that metallic ruthenium nanoparticles, which were highly dispersed on the external surface of the magnetic carrier, significantly enhanced the catalyst's ability for dehydrogenation. Additionally, the -NH2 basic sites on the catalyst further facilitated the formation of alanine by promoting the adsorption of acidic reactants. Furthermore, the catalyst could be easily separated using an external magnetic field and exhibited the potential for multiple reuses without any significant loss in its catalytic performance. These practical advantages further enhance its appeal for applications in the reductive amination of lactic acid to alanine.

Fish Scale Gelatin Nanofibers with Helichrysum italicum and Lavandula latifolia Essential Oils for Bioactive Wound-Healing Dressings.

Essential oils are valuable alternatives to synthetic antibiotics that have the potential to avoid the pathogen resistance side effects generated by leather. Helichrysum italicum and Lavandula latifolia essential oils combined with fish scale gelatin were electrospun using a coaxial technique to design new bioactive materials for skin wound dressings fabrication. Fish scale gelatins were extracted from carp fish scales using two variants of the same method, with and without ethylenediaminetetraacetic acid (EDTA). Both variants showed very good electrospinning properties when dissolved in acetic acid solvent. Fish scale gelatin nanofibers with Helichrysum italicum and Lavandula latifolia essential oil emulsions ensured low microbial load (under 100 CFU/g of total number of aerobic microorganisms and total number of yeasts and filamentous fungi) and the absence of Staphylococcus aureus ATCC 6538, Escherichia coli ATCC 10536, and Candida albicans ATCC 1023 as compared to fish scale gelatin without essential oils, which recommends them for pharmaceutical or topical applications. A scratch-test performed on human dermal fibroblasts proved that the biomaterials contributing to the wound healing process included fish scale gelatin nanofibers without EDTA (0.5% and 1%), fish scale gelatin nanofibers without EDTA and Lavandula latifolia essential oil emulsion (1%), fish scale gelatin nanofibers with EDTA (0.6%), and fish scale gelatin nanofibers with EDTA with Helichrysum italicum essential oil emulsion (1% and 2%).

New MgFeAl-LDH Catalysts for Claisen-Schmidt Condensation.

A rapid, cheap and feasible new approach was used to synthesize the Mg0.375Fe0.375Al0.25-LDH in the presence of tetramethylammonium hydroxide (TMAH), as a nontraditional hydrolysis agent, applying both mechano-chemical (MC) and co-precipitation methods (CP). For comparison, these catalysts were also synthesized using traditional inorganic alkalis. The mechano-chemical method brings several advantages since the number of steps and the energy involved are smaller than in the co-precipitation method, while the use of organic alkalis eliminates the possibility of contaminating the final solid with alkaline cations. The memory effect was also investigated. XRD studies showed Fe3O4 as stable phase in all solids. Regardless of the alkalis and synthesis methods used, the basicity of catalysts followed the trend: mixed oxides > parent LDH > hydrated LDH. The catalytic activity of the catalysts in the Claisen−Schmidt condensation between benzaldehyde and cyclohexanone showed a linear dependence to the basicity values. After 2 h, the calcined sample cLDH-CO32−/OH−-CP provided a conversion value of 93% with a total selectivity toward 2,6-dibenzylidenecyclohexanone. The presence of these catalysts in the reaction media inhibited the oxidation of benzaldehyde to benzoic acid. Meanwhile, for the self-condensation of cyclohexanone, the conversions to mono- and di-condensed compounds did not exceed 3.8%.

DES-Based Biocatalysis as a Green Alternative for the l-menthyl Ester Production Based on l-menthol Acylation.

The deep eutectic solvent (DES)-based biocatalysis of l-menthol acylation was designed for the production of fatty acid l-menthyl ester (FME) using fatty acid methyl ester (FAME). The biocatalytic reaction was assisted by a lipase enzyme in the DES reaction medium. ւՒ-menthol and fatty acids (e.g., CA-caprylic acid; OA-oleic acid; LiA-linoleic acid; and LnA-linolenic acid) were combined in the binary mixture of DES. In this way, the DES provided a nonpolar environment for requested homogeneity of a biocatalytic system with reduced impact on the environment. The screening of lipase enzyme demonstrated better performance of immobilized lipase compared with powdered lipase. The performance of the biocatalytic system was evaluated for different DES compositions (type and concentration of the acid component). l-menthol:CA = 73:27 molar ratio allowed it to reach a maximum conversion of 95% methyl lauric ester (MLE) using a NV (Candida antarctica lipase B immobilized on acrylic resin) lipase biocatalyst. The recyclability of biocatalysts under optimum conditions of the system was also evaluated (more than 80% recovered biocatalytic activity was achieved for the tested biocatalysts after five reaction cycles). DES mixtures were characterized based on differential scanning calorimetry (DSC) and refractive index analysis.

Biocatalytic Strategy for Grafting Natural Lignin with Aniline.

This paper presents an enzyme biocatalytic method for grafting lignin (grafting bioprocess) with aniline, leading to an amino-derivatized polymeric product with modified properties (e.g., conductivity, acidity/basicity, thermostability and amino-functionalization). Peroxidase enzyme was used as a biocatalyst and H2O2 was used as an oxidation reagent, while the oxidative insertion of aniline into the lignin structure followed a radical mechanism specific for the peroxidase enzyme. The grafting bioprocess was tested in different configurations by varying the source of peroxidase, enzyme concentration and type of lignin. Its performance was evaluated in terms of aniline conversion calculated based on UV-vis analysis. The insertion of amine groups was checked by 1H-NMR technique, where NH protons were detected in the range of 5.01-4.99 ppm. The FTIR spectra, collected before and after the grafting bioprocess, gave evidence for the lignin modification. Finally, the abundance of grafted amine groups was correlated with the decrease of the free -OH groups (from 0.030 to 0.009 -OH groups/L for initial and grafted lignin, respectively). Additionally, the grafted lignin was characterized using conductivity measurements, gel permeation chromatography (GPC), thermogravimetric analysis (TGA), temperature-programmed desorption (TPD-NH3/CO2) and scanning electron microscopy (SEM) analyses. The investigated properties of the developed lignopolymer demonstrated its disposability for specific industrial applications of derivatized lignin.

Optimized Nb-Based Zeolites as Catalysts for the Synthesis of Succinic Acid and FDCA.

Nb(0.05 moles%)-zeolites prepared via a post synthesis methodology (BEA, Y, ZSM-5), or a direct sol-gel method (Silicalite-1) were investigated in the hydroxymethylfurfural (HMF) oxidation by both molecular oxygen, in aqueous phase, and organic peroxides, in acetonitrile. The catalysts prepared through the post synthesis methodology (i.e., Nb-Y5, Nb-ZSM25, Nb-Y30, Nb-BEA12, and Nb-BEA18) displayed a mono-modal mesoporosity and contain residual framework Al-acid sites, extra framework isolated Nb(V)O-H and Nb2O5 pore-encapsulated clusters, while Nb-Sil-1, prepared through a direct synthesis procedure, displayed a bimodal micro-mesoporosity and contains only -Nb=O species. These modified zeolites behave as efficient catalysts in both HMF/glucose wet oxidation to succinic acid (SA) and HMF oxidation with organic peroxides to the 2,5-furandicarboxylic acid (FDCA). The catalytic behavior of these catalysts, in terms of conversion and especially the selectivity, mainly depended on the base/acid sites ratio. Thus, the HMF/glucose wet oxidation occurred with a total conversion and a selectivity to SA of 37.7% (from HMF) or 69.1% (from glucose) on the Nb-Y5 catalyst, i.e., the one with the lowest base/acid sites ratio. On the contrary, the catalysts with the highest base/acid sites ratio, i.e., Nb-ZSM25 and Nb-Sil-1, afforded a high catalytic efficiency in HMF oxidation with organic peroxides, in which FDCA was produced with selectivities of 61.3-63.8% for an HMF conversion of 96.7-99.0%.

New Nanofibers Based on Protein By-Products with Bioactive Potential for Tissue Engineering.

Concentrated collagen hydrolysate (HC10CC), rabbit collagen glue (RCG), and keratin hydrolysate (KH) were investigated in terms of their extraction from mammalian by-products and processing by electrospinning. The electrospun nanofibers were characterized by scanning electron microscopy coupled with the energy dispersive X-ray spectroscopy (SEM/EDS), attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), differential scanning calorimetry (DSC), and indentation tests. The cytotoxicity of the electrospun nanofibers was conducted on L929 fibroblast cells using MTT and LDH assays and cell morphology observations. The electrospun RCG and KH nanofibers morphology showed an average size of nanofibers ranging between 44 and 410 nm, while the electrospun HC10CC nanofibers exhibited higher sizes. The ATR-FTIR spectra performed both on extracted proteins and electrospun nanofibers showed that the triple helix structure of collagen is partially preserved. The results were in agreement with the circular dichroism analysis for protein extracts. Furthermore, the viscoelastic properties of electrospun KH nanofibers were superior to those of electrospun RCG nanofibers. Based on both in vitro quantitative and qualitative analysis, the electrospun nanofibers were not cytotoxic, inducing a healthy cellular response. The results of new electrospun protein-based nanofibers may be useful for further research on bioactive properties of these nanofibers for tissue engineering.

One-Pot Enzymatic Production of Lignin-Composites.

A novel and efficient one-pot system for green production of artificial lignin bio-composites has been developed. Monolignols such as sinapyl (SA) and coniferyl (CA) alcohols were linked together with caffeic acid (CafAc) affording a polymeric network similar with natural lignin. The interaction of the dissolved SA/CA with CafAc already bound on a solid support (SC2/SC6-CafAc) allowed the attachment of the polymeric product direct on the support surface (SC2/SC6-CafAc-L1 and SC2/SC6-CafAc-L2, from CA and SA, respectively). Accordingly, this procedure offers the advantage of a simultaneous polymer production and deposition. Chemically, oxi-copolymerization of phenolic derivatives (SA/CA and CAfAc) was performed with H2O2 as oxidation reagent using peroxidase enzyme (2-1B mutant of versatile peroxidase from Pleurotus eryngii) as catalyst. The system performance reached a maximum of conversion for SA and CA of 71.1 and 49.8%, respectively. The conversion is affected by the system polarity as resulted from the addition of a co-solvent (e.g., MeOH, EtOH, or THF). The chemical structure, morphology, and properties of the bio-composites surface were investigated using different techniques, e.g., FTIR, TPD-NH3, TGA, contact angle, and SEM. Thus, it was demonstrated that the SA monolignol favored bio-composites with a dense polymeric surface, high acidity, and low hydrophobicity, while CA allowed the production of thinner polymeric layers with high hydrophobicity.

Graphene oxide as a catalyst for the diastereoselective transfer hydrogenation in the synthesis of prostaglandin derivatives.

Modification of GO by organic molecules changes its catalytic activity in the hydrogen transfer from i-propanol to enones, affecting the selectivity to allyl alcohol and diastereoselectivity to the resulting stereoisomers. It is noteworthy the system does not contain metals and is recyclable.

Bifunctional carbohydrate biopolymers entrapped lipase as catalyst for the two consecutive conversions of α-pinene to oxy-derivatives.

Bifunctional catalysts designed as carbohydrate biopolymers entrapping lipase have been investigated for the biotransformation of a natural compound (α-pinene) to oxy-derivatives. Lipases assisted the epoxidation of α-pinene using H2O2 as oxidation reagent and ethyl acetate as both acetate-supplier and solvent affording α-pinene oxide as the main product. Further, the biopolymer promoted the isomerization of α-pinene oxide to campholenic aldehyde and trans-carenol. In this case, the biopolymers played double roles of the support and also active part of the bifunctional catalyst. Screening of enzymes and their entrapping in a biopolymeric matrix (e.g. Ca-alginate and κ-carrageenan) indicated the lipase extracted from Aspergillus niger as the most efficient. In addition, the presence of biopolymers enhanced the catalytic activity of the immobilized lipase (i.e. 13.39×10(3), 19.76×10(3)and 26.46×10(3) for the free lipase, lipase-carrageenan and lipase-alginate, respectively). The catalysts stability and reusability were confirmed in eight consecutively reaction runs.

Direct synthesis of sorbitol and glycerol from cellulose over ionic Ru/magnetite nanoparticles in the absence of external hydrogen.

A sweet catalyst: A catalyst formed of Ru/functionalized silica-coated magnetite nanoparticles is highly efficient in the one-pot production of sorbitol and glycerol, starting from cellulose and in the absence of an external hydrogen source. The ease of recoverability of the catalyst from the solid residues, and its reuse without loss of activity or selectivity for several runs, is an important green element of the process.

Sensitive Aflatoxin B1 Determination Using a Magnetic Particles-Based Enzyme-Linked Immunosorbent Assay.

A magnetic particle-based enzyme-liked immunosorbent assay (mp-ELISA) has been developed as new an alternative immunoassay for Aflatoxin B1 determination. The method is based on conventional competitive ELISA whereby the anti-Aflatoxin B1 antibody is immobilized on the magnetic particles' surface. The influence of the antibody type as well as antibody immobilization on the magnetic beads surface was investigated in detail. Also, optimum values for the general parameters of the method (e.g. tracer concentration, type of antibody, and incubation time) were established. Finally, a sensitive immunoassay method (mp-ELISA) was performed for Aflatoxin B1 determination at ppt level (LOD = 1 ppt Aflatoxin B1).

Biosensors based on screen-printing technology, and their applications in environmental and food analysis.

This review summarizes scientific research activity on biosensors, especially screen-printed, electrode-based biosensors. The basic configurations of biosensors based on screen-printing technology are discussed and different procedures for immobilization of the biorecognition component are reviewed. Theoretical aspects are exemplified by practical environmental and food-analysis applications of screen-printed, electrode-based biosensors.

Evaluation of progesterone content in saliva using magnetic particle-based immuno supported liquid membrane assay (m-ISLMA).

Progesterone in saliva was monitored using a new method called magnetic particle-based immuno supported liquid membrane assay (m-ISLMA) in a sequential injection (SI) setup, allowing automatic sample cleanup, analyte enrichment, and detection in a single analysis unit. Progesterone (Ag) diffuses from a continuous flowing sample - the donor - into a supported organic liquid membrane (SLM), based on analyte partitioning (solubility) between the aqueous donor and the organic phase. The Ag is re-extracted from the SLM into a second stagnant aqueous acceptor, containing antibodies (Ab) immobilized on magnetic beads, held at the bottom of the acceptor by a magnet. Due to the formation of strong Ag-Ab-bead complexes and a large excess of Ab-beads, the Ag is accumulated and selectively enriched in the acceptor. The extracted progesterone was quantified by injecting into the acceptor a horseradish peroxidase (HRP) labeled analyte tracer, the substrate (luminol, H(2)O(2), and p-iodophenol), and finally detection of the generated chemiluminescence by a photomultiplier tube. After optimization of experimental parameters (e.g., sample flow rate, extraction time, type of organic solvent and antibody-bead concentration in the acceptor), a detection limit of 8.50+/-0.17 fgL(-1) and a dynamic range between 35 fgL(-1) and 10 pgL(-1) was reached. The progesterone level of saliva for three subjects (women in different period of ovarian cycle) was investigated, and the corresponding progesterone concentrations detected with m-ISLMA coincided well with the expected values.

A micro-immuno supported liquid membrane assay (mu-ISLMA).

A chemiluminescent (CL) based micro-immuno supported liquid membrane assay (mu-ISLMA) has been developed that enables clean up, enrichment and detection of simazine in a single miniaturised cartridge system. The mu-ISLM cartridge contains a supported liquid membrane (SLM) sandwiched between a donor and an acceptor plate (channel volumes 1.65 microL), the latter being covered by a thin layer of gold on to which anti-simazine antibodies were covalently immobilised via a self assembled monolayer (SAM) of either dithiobis(11-aminoundecane, hydrochloride) (DTAU) or beta-mercaptoethylamine (beta-MEA). The mu-ISLMA based on DTAU was characterised by both a high apparent extraction efficiency (E(app) = 136%) and high apparent enrichment factor (E(e)(app) = 544), which resulted in a very high sensitivity for simazine (LOD = 0.1 ng L(-1)). The paper discusses the influence of the different SAMs and three different anti-simazine-antibody preparations (polyclonal, affinity purified polyclonal and monoclonal) on the extraction parameters and assay sensitivity. The influence of the sample matrix (e.g. mineral water, orange juice and milk) on the simazine mu-ISLMA was also investigated.

Ultrasensitive magnetic particle-based immunosupported liquid membrane assay.

A magnetic particle-based immuno-supported liquid membrane assay (m-ISLMA) based on chemiluminescence detection of a horseradish peroxidase-labeled hapten tracer that allows sample cleanup, analyte enrichment, and detection in a single analysis unit has been developed. Antibodies were immobilized on magnetic beads, and their position in the acceptor was controlled by two alternating opposing electromagnetic fields generated by a voltage applied to either of two electromagnets placed below and above the acceptor channel of the supported liquid membrane unit. The influence of antibody bead dilution in the acceptor was investigated and found to follow the ISLM theory, that is improved enrichment and sensitivity with increasing antibody concentration. Two different extraction procedures were investigated: procedure 1 (m-ISLMA-P1), which keeps the antibody beads trapped at the bottom of the acceptor during the entire analysis process; and procedure 2 (m-ISLMA-P2), which keeps the antibody beads dispersed and in motion in the acceptor phase during the extraction process. m-ISLMA-P2 resulted in 2000 times improved enrichment of simazine and a more than 3 orders of magnitude better limit of detection (LOD(10%)) (1.29 x 10(-5) microg L(-1)) than for m-ISLMA-P1 (2.00 x 10(-2) microg L(-1)) and corresponding microtiter plate magnetic particle-based ELISA (m-ELISA, LOD(10%) 1.30 x 10(-1) microg L(-1)). m-ISLMA-P2 and m-ELISA were further applied for the extraction and analysis of simazine-spiked surface water and fruit juice, finding no evidence for matrix influence for the former method; however, indications that trace amounts (nanograms per liter) of simazine or specific cross-reactants were present in both samples.

A chemiluminescence flow immunosensor based on a porous monolithic metacrylate and polyethylene composite disc modified with protein G.

A generic, fast, sensitive and new type of flow immunosensor has been developed. The basis is a monolithic porous poly(glycidyl methacrylate-co-trimethylolpropane trimethacrylate) polymer disc modified with protein G, placed in a fountain type flow cell compartment, in close proximity to a photomultiplier tube (PMT). Analyte and HRP labelled analyte derivative (tracer) compete for anti-analyte antibody binding sites. The mixture is then injected into the flow immunosensor system where the formed analyte- and tracer-antibody complexes are trapped by the monolithic protein G disc. The amount of bound tracer, inversely related to the concentration of analyte in the sample, is determined in a second step by injection of luminol, p-iodophenol and H2O2, generating enhanced chemiluminescence (CL) with horseradish peroxidase (HRP). A third and final step is need for regeneration of the protein G disc so that a new analysis cycle can take place. The performance of the disc immunosensor system was compared with a one step continuous flow injection immunoassay (FIIA) system, using the same reagents and a protein G column, in terms of assay sensitivity and influence of matrix effects from various water samples (millipore-, tap- and surface water). The detection limit for the analyte atrazine in PBS and surface water (SW) was 0.208 +/- 0.004 microg l(-1) (PBS) and 0.59 +/- 0.120 microg l(-1) (SW) for the FIIA and 0.033 +/- 0.003 microg l(-1) (PBS) and 0.038+/-0.003 microg l(-1) (SW) for the disc immunosensor. Statistical comparison of the two systems shows that the disc immunosensor results were significantly less influenced by the sample matrix, which is explained by the fact that the sample in the FIIA arrives simultaneously with the matrix to the detector, whereas these are separated in time in the disc immunosensor system.

Immuno-SLM-a combined sample handling and analytical technique.

Immuno-supported liquid membrane (immuno-SLM) extraction is a new technique that makes use of antibody (Ab)-antigen interactions as the "extraction force" to drive the mass transfer in a selective way. In immuno-SLM, anti-analyte (Ag) Abs are introduced into the acceptor phase of the SLM unit to trap the Ag that passes from the flowing donor through the SLM into the stagnant acceptor. The amount of immuno-extracted analyte (AbAg) is quantified by connecting the immuno-SLM unit on-line with a non-competitive heterogeneous fluorescence flow immunoassay (FFIA) that makes use of a fluorescein-labeled analyte tracer that titrates the residual excess of Ab present in the acceptor. A restricted access (RA) column is used for the separation of the two tracer fractions (Ag* and AbAg*) formed, and the eluted AbAg* fraction is measured downstream by a fluorescence detector. Factors influencing the optimum immuno-SLM extraction parameters, i.e., donor flow rate, extraction time and type of Ab, were investigated for immuno extraction of the model analyte atrazine. Immuno-SLM coupled to FFIA (immuno-SLM-FFIA) and FFIA alone were compared in terms of the assay sensitivities obtained and the sample matrix influence. The concentration at the mid-point of the calibration curve (IC(50)) was 16.0+/-1.4 and 36+/-16 microg/l, the limit of detection (LOD) was 2.0+/-1.1 and 20+/-10 microg/l, and the dynamic range was 2-100 and 20-500 microg/l atrazine for immuno-SLM-FFIA and FFIA, respectively. The matrix influence on the FFIA was significant in orange juice and surface water, whereas the influence was minor for immuno-SLM-FFIA with recoveries between 104% and 115% for 5 microg/l atrazine in tap water, orange juice and river water.