TDDFT Study on Different Sensing Mechanisms of Similar Cyanide Sensors Based on Michael Addition Reaction

The solvents and substituents of two similar fluorescent sensors for cyanide, 7-diethylamino- 3-formylcoumarin （sensor a） and 7-diethylamino-3-（2-nitrovinyl）coumarin （sensor b）, are proposed to account for their distinct sensing mechanisms and experimental phenomena. The time-dependent density functional theory has been applied to investigate the ground states and the first singlet excited electronic states of the sensor as well as their possible Michael reaction products with cyanide, with a view to monitoring their geometries and photophysieal properties. The theoretical study indicates that the protic water solvent could lead to final Michael addition product of sensor a in the ground state, while the aprotic acetonitrile solvent could lead to carbanion as the final product of sensor b. Furthermore, the Michael reaction product of sensor a has been proved to have a torsion structure in its first singlet excited state. Correspondingly, sensor b also has a torsion structure around the nitrovinyl moiety in its first singlet excited state, while not in its carbanion structure. This could explain the observed strong fluorescence for sensor a and the quenching fluorescence for the sensor b upon the addition of the cyanide anions in the relevant sensing mechanisms.

Guanidinium Lactate Ionic Liquid: An Efficient and Recycling Catalyst for Michael Addition Reaction

A facile and efficient 1, 4-conjungate addition（Michael addition） reaction of active methylene compounds to aft-unsaturated compounds, catalyzed by guanidinium lactate ionic liquid（IL9）, has been developed. A range of chalcones and nitroalkenes together with active methylene compounds have been converted smoothly to the corresponding products in high yields.

Modification of Nano-alumina Surface by Michael Addition Reaction

A general method for modification of nano-alumina surface is investigated using Michael addition reaction with α,β-unsaturated carbonyl compounds.

Tetramethylguanidium Lactate Ionic Liquid: Catalyst-free Medium for Michael Addition Reaction

A catalyst-free, facile and efficient Michael addition reaction of active methylene compounds as well as nitromethane with chalcones catalyzed by guanidinium lactate ionic liquid was done. A series of chalcones, nitromethane, and active methylene compounds were converted smoothly to the corresponding products in high yields. The simple procedure, very mild conditions, high yields, and reuse of the IL without any loss of catalytic activity make this protocol considerably attractive for academic researches and practical applications.

Organophosphine bearing multiple hydrogen-bond donors for asymmetric Michael addition reaction of 1-oxoindane-2-carboxylic acid ester via dual-reagent catalysis

Multiple hydrogen bonds containing nucleophilic phosphines derived from dipeptide dual-reagents catalyzed asymmetric Michael addition reactions between indene esters and activated olefins in high yields and good to excellent enantioselectivities under mild reaction conditions.The success of current highly selective reactions should provide inspiration for expansion to other reactions and would open up new paradigms for the synthesis of indanone derivatives bearing chiral quaternary carbon centers.

Michael Addition Reaction of Fluorinated Nitro Compounds

The Michael addition reactions of fluorinated nitro compounds with electron deficient olefins to give γ-fiuoro-γ-nitro-esters, nitriles and ketones which bear a fluorinated quaternary carbon center were reported. The reactions were promoted by TMG, affording the desired adducts in acceptable to good yields.

Theoretical Study on the Addition Reactions of Benzaldoximes with Propene

The Michael addition reactions of Z and E benzaldoximes with propene were investigated theoretically by DFT method at B3LYP/6-31G^＊ level. The calculation results show that both addition reactions are concerted processes accompanied by the migration of hydrogen from the atom oxygen to carbon. Both products Z and E nitrones have dipolar charge distributions and activities. Z isomer is more favorable in the reaction due to the barrier is lower.

The Preparation and Properties of Starch Based Shape Memory Hydrogel

In this work,the–catechol and–thiol modified starch was prepared by the esterification and amino condensation reaction,then a fully starch based hydrogel was prepared via the thiol-catechol Michael addition reaction.The starch hydrogel gained shape memory behaviors by coordinate with Fe^(3+)ions at alkaline condition.1H-NMR had been used to character the structure of the starch derivatives and its character peaks.The hydrogel’s modulus had also been measured before and after coordinating with Fe^(3+)ions in linear area and the result showed that both the hydrogel’s storage modulus and loss modulus kept constant in linear area from 0.1 rad/s to 100 rad/s,which demonstrated a good network was formed inside the hydrogel.Furthermore,the shape memory behaviors had been tested by changing the pH value in solution.The result showed that the hydrogel can keep its temporary shape in high pH condition and recover to its original state after the shaped hydrogel immersed into acidic solution.This hydrogel might have great application prospects in the field of biomedical and engineering.

Synthesis of trifluoromethyl-/cyclopropyl-substituted 2-isoxazolines by DBU-promoted domino reaction

NTrifluoromethyl and cyclopropyl substituted 2-isoxazolines were synthesized via a DBU-promoted domino reaction of β-trifluoromethyl-/β-cyclopropyl-substituted enones with hydroxylamine. The domino reaction consists of a Michael addition and the followed cyclization. A wide range of 3-substituted 5-cyclopropyl-5-trifluoromethyl-2-isoxazolines were obtained in good to excellent yields under mild reaction conditions. The method could also apply to other trifluoromethyl-substituted enones.

One-step preparation of branched PEG functionalized AIE-active luminescent polymeric nanoprobes

The synthesis of amphiphilic aggregation-induced emission （ALE） dyes based organic nanoparticles has recently attracted in- creasing attention in the biomedical fields. These AlE dyes based nanoparticles could effectively overcome the aggregation caused quenching effect of conventional organic dyes, making them promising candidates for fabrication of ultrabright organic luminescent nanomaterials. In this work, AIE-active luminescent polymeric nanoparticles （4-NH2-PEG-TPE-E LPNs） were facilely fabricated through Michael addition reaction between tetraphenylethene acrylate （TPE-E） and 4-arm-poly（ethylene glycol）-amine （4-NH2-PEG） in rather mild ambient. The 4-NH2-PEG can not only endow these AlE-active LPNs good water dispersibility, but also provide functional groups for further conjugation reaction. The size, morphology and luminescent prop- erties of 4-NH2-PEG-TPE-E LPNs were characterized by a series of techniques in detail. Results suggested that these AlE-active LPNs showed spherical morphology with diameter about 100-200 nm. The obtained 4-NH2-PEG-TPE-E LPNs display high water dispersibility and strong fluorescence intensity because of their self assembly and AlE properties of TPE-E. Biological evaluation results demonstrated that 4-NH2-PEG-TPE-E LPNs showed negative toxicity toward cancer cells and good fluorescent imaging performance. All of these features make 4-NHz-PEG-TPE-E LPNs promising candidates for biolog- ical imaging and therapeutic applications.