1,2-Dihydro-1-hydroxy-2,3,1-benzodiazaborine Bearing an Acridine Moiety as a Circular Dichroism Probe for Determination of Absolute Configuration of Mono-Alcohols

A new chiral probe molecule for mono-alcohols is developed by using 1,2-dihydro-1-hydroxy-2,3,1-benzodiazaborine (DAB) bearing an acridine moiety 1 . In the presence of mono-alcohols, DAB 1 forms borate 2 by boronic ester formation, followed by coordination of the acridine moiety to the boron atom. Borate 2 has a chiral center on the boron atom and works as a stereodynamic circular dichroism (CD) probe molecule for chiral mono-alcohols based on the π–π interaction between the acridine moiety and the carbon–carbon unsaturated moiety on mono-alcohols.     

Highly sensitive perylene tetra-(alkoxycarbonyl) based colorimetric and ratiometric probes for fluorine detection

Fluoride anion (F^?) affects environmental, biological, and chemical processes significantly. Therefore, its detection has received increasing attention, and sensitive, effective, and convenient probes for F^? detection need to be developed urgently. In this work, two perylene tetra-(alkoxycarbonyl) (PTAC) based colorimetric and ratiometric probes, P1 and P2, were developed for the detection of F^?. The interactions between F^? and these two probes were investigated by absorption, electrochemistry, ¹H NMR, and density functional methods. Both the two probes were complexed with F^? with a ratio of 1:1. The detection limits of P1 and P2 were 0.22 μM and 0.87 μM, respectively. It was worth noting that the absorption peak of P1 showed a 190 nm red shift when sensing F^?, and P1 is the largest red shift value reported in F^? probes based on PTAC derivatives. This phenomenon was resulted from the unique configuration and deprotonation of P1 that can promote the intramolecular charge transfer (ICT). This strategy provides an example for the development of other ion probes based on D-A type ICT mechanism.     

Probing molecular environments with a fictitious isotopic dipole

A HD-like (HD: mono-deuterated hydrogen molecule) isotopic dipole moment is proposed as a sensible probe for molecular environments, in particular for electrostatic fields and polarizable (reactive) sites of molecules. Fictitious nuclear masses are chosen in order to yield a rigid dipole with a small appropriate magnitude. Upon subtracting the Born-Oppenheimer energy, the interaction is reduced to field-dipole-like and dipole-polarizability-like terms, the last one being particularly informative since connected to potentially reactive sites. Possible asymmetries of this term appear as signatures of charged sites in the molecule. The field strength and orientation are easily obtained by identifying the minimum field-dipole energy configuration and flipping the dipole from it. Tests with hydrogen, water, benzene, and chlorobenzene molecules confirm the good performance of the method. In an application to test the present models for hydrogen activation by a frustrated Lewis pair, the full potential of the method is assessed.     

Fluorescent macrocyclic chemosensor for Zn(II) detection at alkaline pH values

ABSTRACT

The new macrocyclic ligand L (28,29-dimethoxy-27-oxa-8,11,14,17,25,26-hexaazatetracyclo[22.2.1.1(2,6).1(19,23)]nonacosa-2,4,6(28),19,21,23(29),24,26(1)-octaene) has been synthesised. It contains a tetramine chain and the 2,5-bis(2-methoxy-3-metyl-phenyl)-1,3,4-oxadiazole (PPD-OMe) chromophore, acting as coordinating and sensing units, respectively.

The fluorescent emission of L depends on the pH being highly fluorescent at pH = 2 and not emitting from pH >10. The studies highlighted that L is a PET mediated emitting chemosensor, being the PET effect regulated by the degree of the tetraamine protonation.

L coordinates metal ions (Cu(II), Zn(II) and Cd(II)) in water giving rise to an OFF-ON fluorescent response for the presence of Zn(II) ion thus signalling its presence in the medium. This response is particularly notable at pH = 9 allowing to extend the Zn(II) sensing also in the alkaline pH field.     

Tween 20-stabilized gold nanoparticles combined with adenosine triphosphate-BODIPY conjugates for the fluorescence detection of adenosine with more than 1000-fold selectivity

This study describes the development of a simple, enzyme-free, label-free, sensitive, and selective system for detecting adenosine based on the use of Tween 20-stabilized gold nanoparticles (Tween 20-AuNPs) as an efficient fluorescence quencher for boron dipyrromethene-conjugated adenosine 5′-triphosphate (BODIPY-ATP) and as a recognition element for adenosine. BODIPY-ATP can interact with Tween 20-AuNPs through the coordination between the adenine group of BODIPY-ATP and Au atoms on the NP surface, thereby causing the fluorescence quenching of BODIPY-ATP through the nanometal surface energy transfer (NSET) effect. When adenosine attaches to the NP surface, the attached adenosine exhibits additional electrostatic attraction to BODIPY-ATP. As a result, the presence of adenosine enhances the efficiency of AuNPs in fluorescence quenching of BODIPY-ATP. The AuNP-induced fluorescence quenching of BODIPY-ATP progressively increased with an increase in the concentration of adenosine; the detection limit at a signal-to-noise ratio of 3 for adenosine was determined to be 60 nM. The selectivity of the proposed system was more than 1000-fold for adenosine over any adenosine analogs and other nucleotides. The proposed system combined with a phenylboronic acid-containing column was successfully applied to the determination of adenosine in urine.     

Amorphous Aggregation of Amyloid Beta 1‐40 Peptide in Confined Space

The amorphous aggregation of Aβ1‐40 peptide is addressed by using micromolding in capillaries. Both the morphology and the size of the aggregates are modulated by changing the contact angle of the sub‐micrometric channel walls. Upon decreasing the hydrophilicity of the channels, the aggregates change their morphology from small aligned drops to discontinuous lines, thereby keeping their amorphous structure. Aβ1‐40 fibrils are observed at high contact angles.     

Fabrication and luminescent properties of Eu(BMPPA)3BPy complex and its functionalized silica nanocomposites

Luminescent silica nanocomposites functionalized with a Eu-complex have been prepared and characterized.The europium complex is composed of 2,2'-bipyridyl(BPy) and 2-(4-bromomethyI)-phenylpropionic acid(BMPPA),which contains highly active benzyl bromide substituents and can covalently bind with poly(4-vinylpyridine)(P4VP)-modified silica nanoparticles(nanoSiO_2P4VP) to form nanoSiO_2P4VPEuBPy composites.Microscopic images revealed that the nanoSiO_2P4VPEuBPy composites easily formed aggregates,due to an inter-particle binding caused by the benzyl bromide among the composites.The as-prepared nanocomposites showed the typical emissions of Eu(III) ions at the wavelengths from 580 nm to 750 nm designated to the ~5D_0→~7F_n transitions.Time-resolved fluorescence decay measurements revealed that the emission lifetime was approximately 0.204 ms and 0.576 ms for the nanoSiO_2EuBPy composites,a little shorter than that in the Eu(BMPPA)_3BPy complex.     

Direct Estimation of the Surface Location of Immobilized Functional Groups for Concerted Catalysis Using a Probe Molecule

The location of active sites during concerted catalysis by a metal complex and tertiary amine on a SiO₂ surface is discussed based on the interaction between the functionalized SiO₂ surface and a probe molecule, p‐formyl phenylboronic acid. The interactions of the probe molecule with the surface functionalities, diamine ligand, and tertiary amine, were analyzed by FT‐IR and solid‐state ¹³C and ¹¹B MAS NMR. For the catalyst exhibiting high 1,4‐addition activity, the diamine ligand and tertiary amine base exist in closer proximity than in the catalyst with low activity.     

Imaging and tracking an electrostatic charge micro-domain by Kelvin force microscopy as evidence of water adsorption on mica surface

Muscovite mica is a widely accepted substrate for scanning probe microscopy (SPM) investigations. However, mica has intrinsic properties that alter samples and obstruct their analysis due to free charges build-up, ionic exchange and water adsorption taking place at the surface. In addition to interfacial phenomena, there is a growing interest in electrostatic charges on insulators as they are crucial in diverse applications. Despite the high demand for studies of this nature, experimental set-ups capable of resolving charge build-up at the micro-scale are still scarce and technically limited. Here, we report the imaging of surface charge dissipation on freshly cleaved mica by Kelvin-probe Force Microscopy (KPFM). A local electrostatic charge micro-domain was generated by friction between an atomic force microscope (AFM) tip and mica, and its decay was tracked by two-dimensional mapping using KPFM. We found time-dependent charge dissipation, which is attributed to the adsorption of water molecules on mica surface.     

Determination of cobalt ion based on polyethyleneimine modified silver nanoclustersEI北大核心CSCD

PolyethyleneiminePEImodified silver nanoclustersAg NCswere synthesized through chemical reduction method by using PEI as stabilizerAgNO3 as silve source and ascorbic acid as reducing agentand it was applied to the detection of cobalt ions. It was found that the fluorescence of the silver nanoclusters was quenched by Co2+ for the aggregation of PEI-Ag NCs caused by the coordination between cobalt ion and amino group on polyethyleneimine. Under the optimized experimental conditionsthe fluorescence quenching degree of PEI-Ag NCs was piecewise linear with the concentration of cobalt ion in the range of 8.30×10-7-4.17×10-4 mol/L and the detection limit was 0.41 μµmol/L. © 2022, Youke Publishing Co.,Ltd. All rights reserved.