d-d Orbital coupling induced by crystal-phase engineering assists acetonitrile electroreduction to ethylamine

The d-d orbital coupling induced by crystal-phase engineering can effectively adjust the electronic structure of electrocatalysts,thus showing significant catalytic performance,while it has been rarely explored in electrochemical acetonitrile reduction reaction(ARR)to date.Herein,we successfully realize the structural transformation of Pd Cu metallic aerogels(MAs)from face-centered cubic(FCC)to body-centered cubic(BCC)through annealing treatment.Specifically,the BCC Pd Cu MAs exhibit excellent ARR performance with high ethylamine selectivity of 90.91%,Faradaic efficiency of 88.60%,yield rate of 316.0 mmol h^(-1)g^(-1)_(Pd+Cu)and long-term stability for consecutive electrolysis within 20 h at-0.55 V vs.reversible hydrogen electrode,outperforming than those of FCC Pd Cu MAs.Under the membrane electrode assembly system,BCC Pd Cu MAs also demonstrate excellent ethylamine yield rate of 389.5 mmol h^(-1)g^(-1)_(Pd+Cu).Density functional theory calculation reveals that the d-d orbital coupling in BCC Pd Cu MAs results in an evident correlation effect for the interaction of Pd and Cu sites,which boosts up the Cu sites electronic activities to enhance ARR performance.Our work opens a new route to develop efficient ARR electrocatalysts from the perspective of crystalline structure transformation.

Enhancement of Selectivity in Capillary Zone Electrophoresis by Adding Ethanolamines or Ethylamines in the Running Buffer

Mono-, di-, tri-ethanolamines and di-, tri-ethylamines were used to prepare phosphate buffer at pH 2.5 and shown to be capable of enhancing the separation selectivity of chiral drug pinacidil and melittin in bee venom in capillary zone electrophoresis. The reason is due to the reduction of the average apparent mobilities of the analytes.

Cu(OAc)_(2)-Mediated Synthesis of Fullerodihydropyridine-3-ones via the Reaction of[60]Fullerene with β-Substituted Ethylamines in the Absence or Presence of Arylacetaldehydes

A series of unreported fullerodihydropyridine-3-ones were synthesized as a new family of fullerene derivatives in moderate to good yields by a simple one-step reaction of[60]fullerene with cheap and readily available β-substituted ethylamines in the absence or presence of arylacetaldehydes under the assistance of Cu(OAc)_(2).The in situ generation of arylacetaldehydes by the C—N bond cleavage of arylethylamines avoided their complex synthesis in advance and realized the preparation of fullerodihydropyridine-3-ones with structural and functional diversities,which may have promising applications in perovskite solar cells to improve the performance of photovoltaic devices due to the existence of a largeπ-conjugated system on the dihydropyridine-3-one ring.

Fast ethylamine gas sensing based on intermolecular charge-transfer complexation

We have investigated the fast ethylamine gas sensing of 2-chloro-3,5-dinitrobenzotrifluoride（CDBF） loaded poly（acrylonitrile） nanofiber based on an intermolecular charge-transfer complexation.Reversible response and recovery were achieved using alternating gas exposure.This system shows a fast ethylamine gas sensing within 0.4 s.

Liquid-phase oxidation of ethylamine to acetaldehyde oximes over tungsten-doped zeolites

The liquid-phase oxidation of ethylamine with hydrogen peroxide was studied over tungsten-doped zeolites to develop a clean and simple route for producing acetaldehyde oxime. The investigations were firstly performed over W/MOR, where the coordinated state as well as the acidity of the W species were characterized. The reaction parameters, including H_2O_2 amount, solvent,temperature, tungsten content as well as catalyst amount, governed the activity and oxime selectivity. Under optimized reaction conditions, W/MOR showed an ethylamine conversion and corresponding oxime selectivity of 18.3% and 88.9%. W/MOR showed a superior performance in comparison to other tungsten-containing zeolites of W/Beta, W/MWW and W/Y. Although W/MOR exhibited lower amine conversion than titanosilicates of TS-1 and Ti-MWW, it gave higher selectivity to the main product of oxime. Moreover, W/MOR proved to be a robust catalyst, exhibiting a stable catalytic performance after being reused at least for 5 times.

Pocket Modification of x-Amine Transaminase AtATA for Overcoming the Trade-Off Between Activity and Stability Toward 1-Acetonaphthone

Amine transaminases(ATAs)catalyze the asymmetric amination of prochiral ketones or aldehydes to their corresponding chiral amines.However,the trade-off between activity and stability in enzyme engineering represents a major obstacle to the practical application of ATAs.Overcoming this trade-off is important for developing robustly engineered enzymes and a universal approach for ATAs.Herein,we modified the binding pocket of co-ATA from Aspergillus terreus(AtATA)to identify the key amino acid residues controlling the activity and stability of AtATA toward 1-acetonaphthone.We discovered a structural switch comprising four key amino acid sites(R128,V149,L182,and L187),as well as the"best"mutant(AtATAD224K/V149A/L182 F/L187F;termed M4).Compared to the parent enzyme AtATAD224K(AtATAPa),M4 increased the catalytic efficiency(k_(cat)/K_(m)^(1-acetonaphthone),where kcatis the constant of catalytic activities and is 10.1 min^(-1),K_(m)^(1-acetonaphthoneis) Michaelis-Menten constant and is 1.7 mmol·L^(-1))and half-life(t1/2)by 59-fold to 5.9 L·min^(-1)·mmol-1and by 1.6-fold to 46.9 min,respectively.Moreover,using M4 as the biocatalyst,we converted a 20 mmol·L^(-1)aliquot of 1-acetonaphthone in a 50 mL scaled-up system to the desired product,(R)-(+)-1(1-naphthyl)ethylamine((R)-NEA),with 78%yield and high enantiomeric purity(R>99.5%)within 10 h.M4 also displayed significantly enhanced activity toward various 1-acetonaphthone analogs.The related structural properties derived by analyzing structure and sequence information of robust ATAs illustrated their enhanced activity and thermostability.Strengthening of intramolecular interactions and expansion of the angle between the substratebinding pocket and the pyridoxal 5’-phosphate(PLP)-binding pocket contributed to synchronous enhancement of ATA thermostability and activity.Moreover,this pocket engineering strategy successfully transferred enhanced activity and thermostability to three other ATAs,which exhibited 8%-22%sequence similarity with AtATA.This research has important implications for overcoming the trade-off between ATA activity and thermostability.

Zinc and Silver Salts-Containing Lamellar Titanium Phosphate: A Multifunctional Filler

Zinc and silver compounds have been studied because they have ultraviolet light barrier properties and bactericidal action, respectively. Materials with multifunctional characteristics have been sought to produce polymeric nanocomposites. In this work, the chemical modification of titanium phosphate (TiP) was carried out through a route with successive intercalations. TiP was synthesized and consecutively pre-expanded with ethylamine and pyromellitic acid. Then it was modified with zinc acetate and silver nitrate. The final product was characterized by Fourier transform infrared spectroscopy, differential scanning calorimetry, wide-angle X-ray diffractometry, field emission scanning electron microscopy coupled with energy dispersive X-ray spectroscopy and thermogravimetry. Infrared revealed dislocation and appearance of bands according to the intercalating agent. Inorganic salts interfered in the crystallization and melting processes of pyromellitic acid. Vanishing of the TiP hkl plane and variation and appearance of new crystallographic planes at low diffraction angles induced intercalation. SEM showed agglomerated structures. New thermal degradation events at higher temperatures endorsed the formation of zinc and silver carboxylate salts. We concluded that a new miscellaneous and multifunctional matter was achieved.