Sensing Abilities of Crown Ether Functionalized Polythiophenes

Tuning sensing abilities! The affinity of three different [15]crown‐5 ether functionalized polythiophenes for alkali ions has been explored (see figure). Ab initio and DFT quantum mechanical calculations show that the binding energy between neutral conducting polymers and metallic ions, which interact attractively, decreases as the size of the ion increases. Oxidation of these polythiophene derivatives significantly reduces their affinity towards alkali ions, becoming low or even nonexistent.

     

Red‐ and Green‐Emitting Iridium(III) Complexes for a Dual Barometric and Temperature‐Sensitive Paint

A new dual luminescent sensitive paint for barometric pressure and temperature (T) is presented. The green‐emitting iridium(III) complex [Ir(ppy)₂(carbac)] (ppy=2‐phenylpyridine; carbac=1‐(9H‐carbazol‐9‐yl)‐5,5‐dimethylhexane‐2,4‐dione) was applied as a novel probe for T along with the red‐emitting complex [Ir(btpy)₃], (btpy=2‐(benzo[b]thiophene‐2‐yl)pyridine) which functions as a barometric (in fact oxygen‐sensitive) probe. Both iridium complexes were dissolved in different polymer materials to achieve optimal responses. The probe [Ir(ppy)₂(carbac)] was dispersed in gas‐blocking poly(acrylonitrile) microparticles in order to suppress any quenching of its luminescence by oxygen. The barometric probe [Ir(btpy)₃], in turn, was incorporated in a cellulose acetate butyrate film which exhibits good permeability for oxygen. The effects of temperature on the response of the oxygen probe can be corrected by simultaneous optical determination of T, as the poly(acrylonitrile) microparticles containing the temperature indicator are incorporated into the film. The phosphorescent signals of the probes for T and barometric pressure, respectively, can be separated by optical filters due to the ≈75 nm difference in their emission maxima. The dual sensor is applicable to luminescence lifetime imaging of T and barometric pressure. It is the first luminescent dual sensor material for barometric pressure/T based exclusively on the use of Ir^III complexes in combination with luminescence lifetime imaging.     

基于柔性硫醚与Cu2Br2单元二维配位聚合物的合成、结构和荧光性质

A complex [Cu₂Br₂(L)₂]_n(1) (L=bis(2-pyrimidinylthio)methane) has been synthesized and structurally characterized. Complex 1 contains dinuclear Cu₂Br₂ units, which are linked by ditopic L to form a 2D layer structure with a 36-membered macrometallocycle. The adjacent layers are further connected through interpyrimidyl rings C-H…N and π-π interactions to give rise to a three-dimensional supramolecular structure. Complex 1 also displays strong green solid-state photoluminescence, due to metal-to-ligand charge-transfer (MLCT) at room temperature. CCDC: 711434.     

Recent developments in electrochemical flow detections—A review: Part I. Flow analysis and capillary electrophoresis

Recent years have provided numerous new examples of applying flow-through electrochemical detectors in chemical analysis. This review, based on about 250 original research papers cited from the current analytical literature, presents their application in flow analysis and capillary electrophoretic methods. Example applications are also given for arrays of electrochemical sensors in flow analysis and electrochemical detection in microfluidic systems. Potentiometric detection with ion-selective electrodes predominates in flow analysis carried out mostly in a flow-injection system, while amperometric and conductivity detections are most commonly employed in capillary electrophoresis.     

A novel electromagnetism‐assisted imprinting technology to replicate microstructures onto a large‐area curved surface using a flexible magnetic mold

Replication of microstructures from a mold onto a curved surface is difficult. The conformal contact between the mold and the substrate has to be ensured. The present study proposes an innovative mechanism, which employs an electromagnetic disk to provide magnetic force and a PDMS flexible mold with a layer compounded magnetic powder. This mechanism provides not only the gradual contact from center to edge to avoid air entrapment but also conformal contact between the mold and the substrate during the imprinting operation. A system based on this electromagnetic soft imprinting technology has been implemented, and imprinting to replicate microstructures from the mold onto a curved surface has been carried out. The results reveal that the PDMS magnetic mold and the electromagnetic disk‐controlled magnetic force can successfully perform the imprinting and accurately replicate the microstructures onto the large‐area, curved surface glass. The PDMS flexible magnetic mold incorporated with the magnetic disk can be employed to achieve the conformal contact between the mold and the substrate. In addition, due to the low surface free energy of the PDMS, the de‐molding without sticking can be easily accomplished. Copyright © 2008 John Wiley & Sons, Ltd.     

Ratiometric Single‐Nanoparticle Oxygen Sensors for Biological Imaging

It makes sense : Conjugated polymer nanoparticles doped with a platinum porphyrin dye exhibit bright phosphorescence that is highly sensitive to the concentration of molecular oxygen. The small size, extraordinary brightness, excellent sensitivity, and ratiometric emission, together with the demonstration of single‐particle sensing and cellular uptake, indicate the potential of the nanoparticle sensors for quantitative mapping of local molecular oxygen concentration.

     

Development of a Fluorescent Pb2+ Sensor

A real turn‐on : The emission intensity of heterocycle 1 increases upon binding to Pb²⁺. Thus, 1 acts as a small‐molecule “turn‐on” fluorescent sensor for lead. The sensor is highly selective and is functional over a wide range of pH values.

     

Sulfonium Boranes for the Selective Capture of Cyanide Ions in Water

Going fishing ! The sulfonium borane [ 1 ]⁺ complexes cyanide in pure water at the maximum allowable concentration of 50 ppb recommended by the European Union. The high cyanide ion affinity displayed by this compound arises from favorable Coulombic effects augmented by a direct bonding interaction between the cyano and sulfonio groups.

     

An extremely stable host-guest complex that functions as a fluorescence probe for calcium ions

Herein, we report a crown ether based molecular cage that forms extremely stable supramolecular complexes with dimethyldiazapyrenium (DMDAP) ions in CD(3)CN through the collaboration of multiple weak C-HO hydrogen bonds. The very strong binding affinity in this host-guest system allows the molecular cage to bleach the fluorescence signal of DMDAP substantially in equimolar solutions at concentrations as low as 1 x 10(-5) M. Remarkably, a 1x10(-5) M equimolar solution of the molecular cage and DMDAP is highly selective toward Ca(2+) ions-relative to other biologically important Li(+), Na(+), K(+), and Mg(2+) ions-and causes a substantial increase in the fluorescence intensity of the solution. As a result, this molecular cage/DMDAP complex behaves as a supramolecular fluorescence probe for the detection of Ca(2+) ions in solution.     

Designed boronate ligands for glucose-selective holographic sensors

In this study, 2-acrylamidophenylboronate (2-APB) was synthesised and its ability to bind with glucose was investigated both in solution and when integrated into a holographic sensor. Multiple forms of 2-APB, resulting from the neighbouring effect of the amido group with the boronic acid through an intramolecular B--O-coordinated interaction, were shown to exist in solution by using multinuclear NMR spectrometry. It was found that 2-APB predominantly adopts a zwitterionic tetrahedral form at physiological pH values. The complex formation of 2-APB with glucose and lactate was investigated in DMSO; 2-APB favours binding with glucose rather than lactate and generates a five-membered-ring complex. Furthermore, a 2-APB-based holographic sensor displayed a significant response to glucose with little interference from lactate, and with no dependence on pH in the physiological pH range. These features suggest that the new ligand 2-APB is a potential candidate for the development of glucose-selective sensors.