Synthesis and use of a stable aminal derived from TsDPEN in asymmetric organocatalysis

A stable aminal formed stereoselectively from (R,R)-N-tosyl-1,2-diphenyl-1,2-ethylenediamine (TsDPEN) is capable of asymmetric organocatalysis of Diels-Alder and alpha-amination reactions of aldehydes

Surface amination of poly(acrylonitrile)

The surface amination of poly (acrylonitrile) by ammonia plasma treatment has been studied. Furthermore, two other surface modification techniques have been investigated, the plasma chemical decomposition of an amino group containing chemical (tris-(2-aminoethyl)amine) onto the polymer surface and the surface reduction by lithium aluminium hydride. The three different methods are compared with respect to the adhesion improvement of the coatings onto the modified surfaces

Synthesis, Characterization, and Utilization of a Lignin-Based Adsorbent for Effective Removal of Azo Dye from Aqueous Solution

How to effectively remove toxic dyes from the industrial wastewater using a green low-cost lignocellulose-based adsorbent, such as lignin, has become a topic of great interest but remains quite challenging. In this study, cosolvent-enhanced lignocellulosic fractionation (CELF) pretreatment and Mannich reaction were combined to generate an aminated CELF lignin which is subsequently applied for removal of methylene blue and direct blue (DB) 1 dye from aqueous solution. 31P NMR was used to track the degree of amination, and an orthogonal design was applied to determine the relationship between the extent of amination and reaction parameters. The physicochemical, morphological, and thermal properties of the aminated CELF lignin were characterized to confirm the successful grafting of diethylenetriamine onto the lignin. The aminated CELF lignin proved to be an effective azo dye-adsorbent, demonstrating considerably enhanced dye decolorization, especially toward DB 1 dye (>90%). It had a maximum adsorption capacity of DB 1 dye of 502.7 mg/g, and the kinetic study suggested the adsorption process conformed to a pseudo-second-order kinetic model. The isotherm results also showed that the modified lignin-based adsorbent exhibited monolayer adsorption. The adsorbent properties were mainly attributed to the incorporated amine functionalities as well as the increased specific surface area of the aminated CELF lignin

Aminated TiO2 nanotube as a Photoelectrochemical Water Splitting photoanode

The present work reports on the enhancement of TiO2 nanotubes photoelectrochemical water splitting rate by decorating the nanostructure with an amine layer in a hydrothermal process using diethylenetriamine (DETA). The aminate coated TiO2 tubes show a stable improvement of the photoresponse in both UV and visible light spectrum and under hydrothermal conditions, 4-fold increase of the photoelectrochemical water splitting rate is observed. From intensity modulated photocurrent spectroscopy (IMPS) measurements significantly faster electron transport times are observed indicating a surface passivating effect of the N-decoration.Comment: In Catalysis Today, Available online 21 July 201

Simplified immobilisation method for histidine-tagged enzymes in poly(methyl methacrylate) microfluidic devices

Article in press. Kulsharova, G., New BIOTECHNOLOGY (2017), https://doi.org/10.1016/j.nbt.2017.12.004Poly(methyl methacrylate) (PMMA) microfluidic devices have become promising platforms for a wide range of applications. Here we report a simple method for immobilising histidine-tagged enzymes suitable for PMMA microfluidic devices. The 1-step-immobilisation described is based on the affinity of the His-tag/Ni-NTA interaction and does not require prior amination of the PMMA surface, unlike many existing protocols. We compared it with a 3-step immobilisation protocol involving amination of PMMA and linking NTA via a glutaraldehyde cross-linker. These methods were applied to immobilise transketolase (TK) in PMMA microfluidic devices. Binding efficiency studies showed that about 15% of the supplied TK was bound using the 1-step method and about 26% of the enzyme was bound by the 3-step method. However, the TK-catalysed reaction producing l-erythrulose performed in microfluidic devices showed that specific activity of TK in the device utilising the 1-step immobilisation method was approximately 30% higher than that of its counterpart. Reusability of the microfluidic device produced via the 1-step method was tested for three cycles of enzymatic reaction and at least 85% of the initial productivity was maintained. The device could be operated for up to 40 h in a continuous flow and on average 70% of the initial productivity was maintained. The simplified immobilisation method required fewer chemicals and less time for preparation of the immobilised microfluidic device compared to the 3-step method while achieving higher specific enzyme activity. The method represents a promising approach for the development of immobilised enzymatic microfluidic devices and could potentially be applied to combine protein purification with immobilisation.Peer reviewe

Trispyrazolylborate Ligands Supported on Vinyl Addition Polynorbornenes and Their Copper Derivatives as Recyclable Catalysts

Polynorbornenes prepared by vinyl addition poly- merization and bearing pendant alkenyl groups serve as skeletons to support trispyrazolylborate ligands (Tpx) built at those alkenyl sites. Reaction with CuI in acetonitrile led to VA-PNB–TpxCu(NCMe) (VA-PBN = vinyl addition polynorbor- nene) with a 0.8–1.4 mmol incorporation of Cu per gram of polymer. The presence of tetracoordinated copper(I) ions was been assessed by FTIR studies on the corresponding VA-PNB-TpxCu(CO) adducts, in agreement with those on discrete TpxCu(CO). The new materials were employed as heteroge- neous catalysts in several carbene- and nitrene-transfer reac- tions, showing a behavior similar to that of the homogene- ous counterparts but also being recycled several times main- taining a high degree of activity and selectivity. This is the first example of supported Tpx ligands onto polymeric sup- ports with catalytic applications.MINECO (CTQ2017-82893-C2-1-R, CTQ2016-80913-P and Red Intecat CTQ2016-81923-REDC)Junta de Castilla y León (VA051P17, VA062G18)European Union (CHAOS COST ACTION CA-15106)

The conversion of citrulline to arginine in kidney

Glycocyamine is formed in the kidney by the transfer of the amidine group of arginine to the nitrogen atom of glycine. In the study of this reaction it was observed that glycocyamine was also formed from citrulline and glycine. No other donor or precursor of the amidine group was found (1)