An electrochemical chiral sensor based on electrochemically modified electrode for the enantioselective discrimination of D-/L-tryptophan

Journal of Solid State Electrochemistry - Chirality is a universal characteristic of natural systems and discrimination of enantiomers of a chiral molecule plays a major role particularly in...     

Chloro-Modified Magnetic Fe3O4@MCM-41 Core–Shell Nanoparticles for L-Asparaginase Immobilization with Improved Catalytic Activity,Reusability, and Storage Stability

This paper describes a new support that permits to efficient immobilization of L-asparaginase (L-ASNase). For this purpose, Fe₃O₄ magnetic nanoparticles were synthesized and coated by MCM-41. 3-chloropropyltrimethoxysilane (CPTMS) was used as a surface modifying agent for covalent immobilization of L-ASNase on the magnetic nanoparticles. The chemical structure; thermal, morphological, and magnetic properties; chemical composition; and zeta potential value of Fe₃O₄@MCM-41-Cl were characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), differential thermal analysis (DTA), differential scanning calorimetry (DSC), vibrating sample magnetometer (VSM), scanning electron microscope (SEM), energy dispersive X-ray (EDX), X-ray diffraction patterns (XRD), and zeta-potential measurement. The immobilization efficiency onto Fe₃O₄@MCM-41-Cl was detected as 63%. The reusability, storage, pH, and thermal stabilities of the immobilized L-ASNase were investigated and compared to that of soluble one. The immobilized enzyme maintained 42.2% of its original activity after 18 cycles of reuse. Furthermore, it was more stable towards pH and temperature compared with soluble enzyme. The Michaelis–Menten kinetic properties of immobilized L-ASNase showed a lower V_max and a similar K_m compared to soluble L-ASNase. Immobilized enzyme had around 47 and 32.5% residual activity upon storage a period of 28 days at 4 and 25 °C, respectively. In conclusion, the Fe₃O₄@MCM-41-Cl@L-ASNase core–shell nanoparticles could successfully be used in industrial and medical applications.

     

Optimization of the finned double-pipe heat exchanger using nanofluids as working fluids

Journal of Thermal Analysis and Calorimetry - The heat exchanger pipe diameter has a significant effect on the flow characteristics as well as on the initial investment, operation and overall cost....     

Direct and Fast Electrochemical Determination of Catechin in Tea Extracts using SWCNT‐Subphthalocyanine Hybrid Material

In this study, single walled carbon nanotubes (SWCNTs) were covalently functionalized by terminal ethynyl bearing subphthalocyanine (SubPc) to obtain a new hybrid material, viz. SWCNT‐SubPc (CS), via “click” reaction for the first time. The structural characterization and study of the electrochemical sensor properties of the CS hybrid material to catechin were carried out. A convenient and fast analytical method was offered for the determination of catechin. It was shown that the deposition of CS on the surface of a glassy carbon electrode (GCE) led to a 2.2 and 8‐fold increase in the differential pulse voltammetry (DPV) responses to catechin in Britton‐Robinson (BR) buffer solution (a pH of 3) in comparison with SWCNT‐modified and bare GCE, respectively. The dynamic range, detection and quantification limits of catechin were determined to be 0.1–1.5 μM, 13 nM and 43 nM, respectively. Selectivity of the suggested CS/GCE sensor was investigated on addition of a number of interfering metal ions, antioxidants and biomolecules. The applicability of the modified electrode for the detection of catechin in real tea samples such as green, rosehip fruit, Turkish and Indian black tea was demonstrated with the standard addition method. Along with the ease in fabrication and low prices, the proposed CS/GCE sensor was reproducible, selective, stable and sensitive to catechin in major types of tea samples.     

Photopolymerization of enzymatically synthesized methacrylated poly(caprolactone) with poly(ethylene glycol) macromonomer

Polycaprolactone (PCL) based α,ω-methacrylated macromonomer (DMPCL) was synthesized via enzymatic ring-opening polymerization (eROP) by using Novozyme 435 as the enzyme immobilized catalyst. DMPCL was further photopolymerized with monofunctional poly(ethylene glycol) methyl ether methacrylate (PEGMA-950) macromonomer and trimethylolpropane triacrylate (TMPTA) as tri-functionalized crosslinking agent in glass vials when CHCl₃ was the solvent and Irgacure 819 was the photoinitiator. Ultraviolet (UV) Light Emitting Diode (LED) bulbs enabled photoinduced reactions at room temperature with low heat generation and high reaction efficiency. The obtained gels were characterized with Fourier Transform Infrared Spectroscopy (FT-IR) and Differential Scanning Calorimetry (DSC). DMPCL participated as an effective crosslinking agent in the photopolymerization of PEGMA-950. Combined usage of DMPCL and PEGMA-950 resulted in significantly more effective polymerization than the separate photopolymerizations of these macromonomers.     

Characterisation of α-chitin extracted from a lichenised fungus species Xanthoria parietina

Lichens are symbiotic associations formed mainly by ascomycete fungi and green algae or cyanobacteria. The presence of chitin in the fungal cell wall has been revealed by previous studies. Considering the presence of fungi in the lichens, this work determines the presence of chitin in a cosmopolitan lichen species Xanthoria parietina. In this study, chitin was derived from a lichen species for the first time and its physicochemical properties were determined by Fourier transform infrared spectroscopy, thermogravimetric analysis, X-ray diffraction, scanning electron microscopy and elemental analysis. The dry weight chitin content of X. parietina was 4.23%, and this chitin was in the α-form. The crystalline index value of the lichen chitin was calculated as 70.1%. The chitin from X. parietina had a smooth surface.     

Novel silver(I)N-heterocyclic carbene complexes bearing 2-(4-hydroxyphenyl)ethyl group: Synthesis,characterization, and enzyme inhibition properties

Herein, novel silver-based N-heterocyclic carbene (NHC) complexes bearing 2-(4-hydroxyphenyl)ethyl group were synthesized. Novel Ag(I)NHC complexes were synthesized from the 2-(4-hydroxyphenyl)ethyl-substituted benzimidazolium salts and silver oxide via in situ deprotonation method. The successful formation of all Ag(I)NHC complexes was proved by using ¹H NMR, ¹³C NMR, FTIR spectroscopy, and elemental analysis techniques. In addition, their inhibitory effects have been investigated of these substances on acetylcholinesterase (AChE), α-glycosidase (α-Gly), human carbonic anhydrase I (hCA I), and human carbonic anhydrase II (hCA II) enzymes. It has been seen that all compounds have a better ability to inhibit compared with existing tried inhibitors. Among these, the best inhibitor against AChE enzyme is 1g (K_i : 9.54 ± 0.98 μM and IC₅₀ : 17.40), and against α-Gly, 1c showed the highest effect (K_i 3.09 ± 0.36 μM and IC₅₀ 7.91). The best inhibitor against hCA I and hCA II enzymes are 1c and 1g compounds. For hCA I and hCA II, IC₅₀ values were calculated as 17.85 and 9.06 μM and K_i values were measured as 5.45 ± 2.02 and 8.99 ± 2.02 μM, respectively.     

Fundamental Characterization,Photophysics and Photocatalysis of a Base Metal Iron(II)-Cobalt(III) Dyad

A new base metal iron-cobalt dyad has been obtained by connection between a heteroleptic tetra-NHC iron(II) photosensitizer combining a 2,6-bis[3-(2,6-diisopropylphenyl)imidazol-2-ylidene]pyridine with 2,6-bis(3-methyl-imidazol-2-ylidene)-4,4′-bipyridine ligand, and a cobaloxime catalyst. This novel iron(II)-cobalt(III) assembly has been extensively characterized by ground- and excited-state methods like X-ray crystallography, X-ray absorption spectroscopy, (spectro-)electrochemistry, and steady-state and time-resolved optical absorption spectroscopy, with a particular focus on the stability of the molecular assembly in solution and determination of the excited-state landscape. NMR and UV/Vis spectroscopy reveal dissociation of the dyad in acetonitrile at concentrations below 1 mM and high photostability. Transient absorption spectroscopy after excitation into the metal-to-ligand charge transfer absorption band suggests a relaxation cascade originating from hot singlet and triplet MLCT states, leading to the population of the ³MLCT state that exhibits the longest lifetime. Finally, decay into the ground state involves a ³MC state. Attachment of cobaloxime to the iron photosensitizer increases the ³MLCT lifetime at the iron centre. Together with the directing effect of the linker, this potentially makes the dyad more active in photocatalytic proton reduction experiments than the analogous two-component system, consisting of the iron photosensitizer and Co(dmgH)₂(py)Cl. This work thus sheds new light on the functionality of base metal dyads, which are important for more efficient and sustainable future proton reduction systems.