An Atomically Precise Au10Ag2 Nanocluster with Red–Near‐IR Dual Emission

A red–near‐IR dual‐emissive nanocluster with the composition [Au₁₀Ag₂(2‐py?C≡C)₃(dppy)₆](BF₄)₅ ( 1 ; 2‐py?C≡C is 2‐pyridylethynyl, dppy=2‐pyridyldiphenylphosphine) has been synthesized. Single‐crystal X‐ray structural analysis reveals that 1 has a trigonal bipyramidal Au₁₀Ag₂ core that contains a planar Au₄(2‐py?C≡C)₃ unit sandwiched by two Au₃Ag(dppy)₃ motifs. Cluster 1 shows intense red–NIR dual emission in solution. The visible emission originates from metal‐to‐ligand charge transfer (MLCT) from silver atoms to phosphine ligands in the Au₃Ag(dppy)₃ motifs, and the intense NIR emission is associated with the participation of 2‐pyridylethynyl in the frontier orbitals of the cluster, which is confirmed by a time‐dependent density functional theory (TD‐DFT) calculation.     

An immersed smoothed point interpolation method (IS‐PIM) for fluid‐structure interaction problems

An immersed smoothed point interpolation method using 3‐node triangular background cells is proposed to solve 2D fluid‐structure interaction problems for solids with large deformation/displacement placed in incompressible viscous fluid. In the framework of immersed‐type method, the governing equations can be decomposed into 3 parts on the basis of the fictitious fluid assumption. The incompressible Navier‐Stokes equations are solved using the semi‐implicit characteristic‐based split scheme, and solids are simulated using the newly developed edge‐based smoothed point interpolation method. The fictitious fluid domain can be used to calculate the coupling force. The numerical results show that immersed smoothed point interpolation method can avoid remeshing for moving solid based on immersed operation and simulate the contact phenomenon without an additional treatment between the solid and the fluid boundary. The influence from information transfer between solid domain and fluid domain on fluid‐structure interaction problems has been investigated. The numerical results show that the proposed interpolation schemes will generally improve the accuracy for simulating both fluid flows and solid structures.     

Identification of reducing and nonreducing neutral carbohydrates by laser‐enhanced in‐source decay (LEISD) MALDI MS

In this work, laser‐enhanced in‐source decay (LEISD) technique of matrix‐assisted laser desorption/ionization Fourier transform ion cyclotron resonance mass spectrometry (MALDI‐FT‐ICR‐MS) was used to distinguish reducing and nonreducing carbohydrates. Interestingly, easier cleavage of (1 → 2)‐linked glycosidic bonds for nonreducing carbohydrates containing D‐fructofuranosyl units was observed in MALDI‐FT‐ICR‐MS, which was in agreement with the result of theoretical calculation by the software package Gaussian 09. Importantly, no cross‐ring cleavage of fructofuranosyl residues was detected in the LEISD spectra of nonreducing carbohydrates. LEISD method therefore offers an attractive alternative for fast and efficient differentiation of reducing and nonreducing carbohydrates, and the positions of nonreducing monosaccharide residues in a carbohydrate chain could be easily speculated. Copyright © 2013 John Wiley & Sons, Ltd.     

Sterically congested macrobicycles with heteroatomic bridgehead functionality

A series of cyclophanes composed of two triarylelement caps linked by two-atom bridges has been synthesized. The bridgehead functional groups include phosphines in combination with amines, hydrosilanes, methylsilanes, and ethoxysilanes. Computational studies accurately predicted that when the bridgehead substituents are small (lone pairs or protons), an in_,in bridgehead stereochemistry is strongly favored, but larger bridgehead substituents favor the formations of in_,out stereoisomers. The X-ray structures, spectra, and reactivity of these compounds are discussed, as well as the resolution of one of the cyclophanes into pure enantiomers.     

Effect of Demulsifiers on Dilatational Properties of Crude Oil–Water Interfaces

The dilatational properties of polyether demulsifiers PEA, PEB, PEC, PED, PEF, and PEG at the decane-water interface were investigated. Meanwhile, the effect of demulsifiers with different structures on interfacial dilatational modulus of diluted crude oil also was explored. The properties of demulsifiers are compared and analyzed in combine with the dilatational parameters at decane-water interface and at 5% crude oil-water interface. The results show that interfacial dilatational viscoelasticity could characterize the interfacial behavior of demulsifiers. The demulsifiers, which have different kinds or structures, have different effects on destroying the interfacial film of crude oil with increasing bulk concentration. Therefore, the dosage of demulsifier is a very important role in controlling nature of crude oil film.     

A wide range optical pH sensor for living cells using Au@Ag nanoparticles functionalized carbon nanotubes based on SERS signals

p-Aminothiophenol (pATP) functionalized multi-walled carbon nanotubes (MWCNTs) have been demonstrated as an efficient pH sensor for living cells. The proposed sensor employs gold/silver core-shell nanoparticles (Au@Ag NPs) functionalized MWCNTs hybrid structure as the surface-enhanced Raman scattering (SERS) substrate and pATP molecules as the SERS reporters, which possess a pH-dependent SERS performance. By using MWCNTs as the substrate to be in a state of aggregation, the pH sensing range could be extended to pH 3.0～14.0, which is much wider than that using unaggregated Au@Ag NPs without MWCNTs. Furthermore, the pH-sensitive performance was well retained in living cells with a low cytotoxicity. The developed SERS-active MWCNTs-based nanocomposite is expected to be an efficient intracellular pH sensor for bio-applications.