Construction of a (NNN)Ru-Incorporated Porous Organic Polymer with High Catalytic Activity for β-Alkylation of Secondary Alcohols with Primary Alcohols

Solid supports functionalized with molecular metal catalysts combine many of the advantages of heterogeneous and homogeneous catalysis. A (NNN)Ru-incorporated porous organic polymer (POP-bp/bbpRuCl3) exhibited high catalytic efficiency and broad functional group tolerance in the C–C cross-coupling of secondary and primary alcohols to give β-alkylated secondary alcohols. This catalyst demonstrated excellent durability during successive recycling without leaching of Ru which is ascribed to the strong binding of the pincer ligands to the metal ions.

NMR relaxation time measurements of solvent effects in an organocatalysed asymmetric aldol reaction over silica SBA-15 supported proline

Immobilisation of organocatalysts onto solid supports represents a very promising solution to tackle their low productivity by enabling their reuse. Herein, the use of NMR relaxation measurements, coupled with reaction...

Cross-Linked Enzyme Aggregates and Their Application in Enzymatic Pretreatment of Microalgae: Comparison Between CLEAs and Combi-CLEAs

Carrier-free immobilization is a key process to develop efficient biocatalysts able to catalyze the cell wall degradation in microalgae where the traditional solid supports cannot penetrate. Thus, the insolubilization of commercial Celluclast®, Alcalase®, and Viscozyme® enzymes by carrier-free immobilization and their application in microalgae pretreatment was investigated. In this study, different precipitants at different ratios (ethanol, acetone, and polyethylene glycol 4000) were tested in the first part of the method, to establish the precipitation conditions. The screening of the best precipitant is needed as it depends on the nature of the enzyme. The best results were studied in terms of immobilization yield, thermal stability, and residual activity and were analyzed using scanning electron microscopy. Moreover, a novel strategy was intended including the three enzymes (combi-CLEAs) to catalyze the enzymatic degradation of Nannochloropsis gaditana microalgal cell wall in one pot. The carrier-free immobilized derivatives were 10 times more stable compared to soluble enzymes under the same. At the best conditions showed its usefulness in the pretreatment of microalgae combined with ultrasounds, facilitating the cell disruption and lipid recovery. The results obtained suggested the powerful application of these robust biocatalysts with great catalytic properties on novel and sustainable biomass such as microalgae to achieve cost-effective and green process to extract valuable bioactive compounds.

Development of New Efficient Adsorbent by Functionalization of Mg3Al-LDH with Methyl Trialkyl Ammonium Chloride Ionic Liquid

The present paper describes a new way of obtaining an efficient adsorbent material by functionalization of Mg3Al layered double hydroxides (LDH) with methyl trialkyl ammonium chloride-ionic liquid (IL) using two methods: ultrasound and cosynthesis. Layered double hydroxides are good solid support for the functionalization with ionic liquids due to their well-ordered structure. The immobilization of the ILs in suitable solid supports combine the advantages of the ILs with the properties of the solid supports bringing more benefits such as use of lower quantity of ILs and avoiding of ILs loss in the aqua phase which overall decrease the treatment costs. In case of ultrasound method of functionalization is assured a uniform distribution of IL on the solid surface, but through immobilization by cosynthesis due to the tunable properties of LDH, is assured an intercalation of the ILs between the LDH layers. This fact was highlighted by the X-ray diffraction (RXD), scanning electron microscopy (SEM) analyses and Fourier-transform infrared (FTIR) spectroscopy of the obtained adsorbent. The added value brought by the functionalization of Mg3Al with the studied IL was underlined by the adsorption studies conducted in the treatment process of water with diclofenac content. Kinetic, thermodynamic, and equilibrium studies were performed. DCF adsorption onto the studied materials correspond to a chemisorption, the pseudo-second-order kinetic model describing the most accurately the experimental data. DCF adsorption onto the studied materials occurs as a heterogeneous process, with the experimental data fitting best with the SIPS isotherm. The sample obtained through cosynthesis developed a maximum adsorption capacity of 648 mg/g.

Development of Amino Acids Functionalized SBA-15 for the Improvement of Protein Adsorption

Ordered mesoporous materials and their modification with multiple functional groups are of wide scientific interest for many applications involving interaction with biological systems and biomolecules (e.g., catalysis, separation, sensor design, nano-science or drug delivery). In particular, the immobilization of enzymes onto solid supports is highly attractive for industry and synthetic chemistry, as it allows the development of stable and cheap biocatalysts. In this context, we developed novel silylated amino acid derivatives (Si-AA-NH2) that have been immobilized onto SBA-15 materials in biocompatible conditions avoiding the use of toxic catalyst, solvents or reagents. The resulting amino acid-functionalized materials (SBA-15@AA) were characterized by XRD, TGA, EA, Zeta potential, nitrogen sorption and FT-IR. Differences of the physical properties (e.g., charges) were observed while the structural ones remained unchanged. The adsorption of the enzyme lysozyme (Lyz) onto the resulting functionalized SBA-15@AA materials was evaluated at different pHs. The presence of different functional groups compared with bare SBA-15 showed better adsorption results, for example, 79.6 nmol of Lyz adsorbed per m2 of SBA-15@Tyr compared with the 44.9 nmol/m2 of the bare SBA-15.

Palladium and Copper: Advantageous Nanocatalysts for Multi-Step Transformations

Metal nanoparticles have been deeply studied in the last few decades due to their attractive physical and chemical properties, finding a wide range of applications in several fields. Among them, well-defined nano-structures can combine the main advantages of heterogeneous and homogenous catalysts. Especially, catalyzed multi-step processes for the production of added-value chemicals represent straightforward synthetic methodologies, including tandem and sequential reactions that avoid the purification of intermediate compounds. In particular, palladium- and copper-based nanocatalysts are often applied, becoming a current strategy in the sustainable synthesis of fine chemicals. The rational tailoring of nanosized materials involving both those immobilized on solid supports and liquid phases and their applications in organic synthesis are herein reviewed.

Smart Sensing for Antibiotic Monitoring in Mineral and Surface Water: Development of an Electronic Tongue Device

Sensors are considered the future monitoring tools, since, compared to traditional sampling and analysis techniques, they provide fast response on the output data in a timely, continuous, safe, and cost-effective fashion. Antibiotics are important pharmaceuticals with a large variety of applications. However, the overconsumption of these drugs is under the spotlight, since traces of antibiotics are being found in aquatic ecosystems and may lead to the development of antibiotic resistance. Thus, in this work, sensors consisting of ceramic or glass BK7 solid supports with interdigitated gold electrodes coated with five bilayers of polyethyleneimine (PEI) and poly(sodium 4-styrenesulfonate) (PSS) thin films were developed and able to distinguish clarithromycin concentrations between 10−15 M and 10−5 M in mineral and surface water matrices. In mineral water, the ceramic support sensors have shown high reproducibility, whereas glass support sensors are not reproducible for this matrix. For the surface water matrix, both types of sensors proved to be reproducible. The surface water’s principal component analysis, obtained for an electronic tongue composed of the aforementioned sensors, demonstrated the concept’s ability to discriminate between different concentrations of the target compound, although no significant pattern of trend was achieved.

Applied Voltage Effect in Lbl Sensors While Detecting 17α-Ethinylestradiol in Water Samples

The effect of the applied voltage on impedance spectra, measured on sensors based on solid supports with interdigitated electrodes (IDE) that are either covered or not with a layer-by-layer film prepared with polyethylenimine and poly (sodium 4-styrenesulfonate), was analyzed to detect 17α-ethinylestradiol(EE2) in mineral water and tap water. The results show that the sensor response is strongly affected by the applied voltage, the presence of film, and the water matrix, meaning that electrochemical reactions develop near the IDE. However, for low values of applied voltage, the sensor response is reproducible with negligible electrochemical reactions, allowing us to conclude that 25 mV is the appropriate voltage.

Immobilized Fluorescent Probes for Simultaneous Multiple Protease Detection

A new concept for simultaneous detection of two model proteases based on immobilized fluorescently labelled peptides was developed and evaluated. Each probe was composed of a carrier modified by poly(ethylene glycol) (PEG) chains, a specifically cleavable linker, and a fluorescent dye incorporated in the peptide tail. Based on a single excitation–double emission fluorescence response of liberated fluorophores caused by enzymatic cleavage, the presence of a single or both proteases in a mixture was unambiguously determined in an experimentally established concentration range. Among the tested solid supports, Rink Amide PEGA resin was recognized as the most suitable choice from the perspective of on-resin enzyme assays.