Hybrid materials with nanoscopic anion-binding pockets for the colorimetric sensing of phosphate in water using displacement assays

Mesoporous amino-functionalised solids containing certain dyes have been used as suitable anion hosts in displacement assays for the colorimetric signalling of phosphate in water.     

Fluorescent probes for sensing processes in polymers

Fluorescence spectroscopy is an important analytical technique that has been widely used in a variety of applications, such as biomedicine, biology, and science of materials, because it presents some properties which makes it unique, that is, extraordinary sensitivity and selectivity, short delay time (<10(-9) s), and it is neither invasive nor destructive, so it can be used for in situ measurements. Generally, intrinsic fluorescence of many materials, like polymers, is unspecific so it is not useful to analyse their properties or to be correlated to changes in their microenvironment. The incorporation of additives with fluorescent groups would be necessary. When the fluorescence emission of these molecules is sensitive to changes of properties, such as polarity, fluidity, order, molecular mobility, pH, or electric potential, they can be used for detecting such changes in their microenvironment, and they are called fluorescent probes. As long as these probes can follow processes of practical interest, they can be employed as sensors, if the information given by the measure of fluorescence adequately reflects the changes in the system. In addition, a sensor must fulfil some other requirements in order to make them of practical use, the most important being that the material support in which the sensor molecule is inserted. This support should permit a rapid detection of the process and should allow easy processing in a variety of forms. Polymers are well-known systems in which estimation of local parameters are possible by means of fluorimetric techniques. It allows the study of dynamic processes of interest, such as polymerization kinetics and mechanisms, thermal transitions, photodegradation, swelling morphology changes, and so forth.     

A novel fluorescent sensor for hydrophobic amines in aqueous solution

A novel fluorescent tweezer was designed and synthesised to sense hydrophobic amines in aqueous solution. Association of the guest was driven by both hydrophobic effect and electrostatic interactions, with the hydrophobic interactions being dominant. The affinity and selectivity of the sensor for amine-based stimulants are reported.     

A kinetic model explaining the enhanced rates of hydrogen evolution on anodically polarized magnesium in aqueous environments

A model to explain the increasing rates associated with hydrogen evolution (HE) originating at the dissolving regions of Mg under anodic polarization is presented. The actively dissolving anodes have been shown experimentally to be the primary source of anomalous evolution of hydrogen. In this model, standard electrochemical laws are used to account for this phenomenon. The fractional coverage of active Mg sites is introduced to localize the cathodic contribution of HE during anodic polarization. A kinetic equation is derived showing that the rate of HE will increase with increasing potential if the charge transfer coefficient associated with the Mg oxidation reaction is greater than the charge transfer coefficient for the HE reaction. Experimental data obtained on high purity Mg galvanodynamically polarized at potentials above and below its E_corr in 0.1 M NaCl solution are presented to validate the model.     

Fluorescence probes for thiol-containing amino acids and peptides in aqueous solution

A new fluorescence probe is described using the "chemosensing ensemble" method. The probe shows high selectivity and sensitivity for thiol-containing amino acids and peptides, and can detect cysteine and homocysteine from healthy to abnormal levels under physiologically-relevant conditions.     

Crosslinked nanofibrillated cellulose: poly(acrylic acid) nanocomposite films; enhanced mechanical performance in aqueous environments

Nanofibrillated cellulose (NFC) was compounded with poly(acrylic acid) (PAA) via solvent casting. Nanocomposite films were thermally-crosslinked to allow the formation of ester bonds between NFC and PAA, as confirmed by ¹³CNMR and infrared spectroscopy. The network morphology of the cellulose nanofibrils was left intact by the introduction of PAA and crosslinking. Water absorption and swelling was diminished by the introduction of crosslinking, due to the reduced number of vacant hydroxyl and carboxyl groups available to interact with water molecules. Crosslinking with PAA increased the activation energy required for thermal degradation. PAA effectively reinforced NFC, increasing Young’s modulus, tensile strength and glass transition temperature. Crosslinking imparted restraints on segmental motion of polymer chains, further enhancing the thermomechanical properties and retaining elasticity. Wet-strength properties were enhanced due to the reduced hydrophilicity of crosslinked nanocomposite films.     

A cyclometalated palladium-azo complex as a differential chromogenic probe for amino acids in aqueous solution

Solutions of a cyclometalated palladium-azo complex exhibited differential UV-Vis absorption spectra in the presence of alpha-amino acids with different side chain groups.     

Ratiometric probes for hydrogencarbonate analysis in intracellular or extracellular environments using europium luminescence

A series of six, cationic, zwitterionic and anionic Eu complexes has been examined for the analysis of hydrogencarbonate concentration in the intracellular and extracellular ranges; an anionic complex incorporating three glutarate residues and a sensitising acridone chromophore (lambda exc = 410 nm) exhibits a 69% change in the intensity ratio of the 618/588 nm Eu emission bands between 5 and 15 mM HCO3- in a cell lysate medium.     

Anthroneamine based chromofluorogenic probes for Hg2+ detection in aqueous solution

Anthroneamine derivatives 1–3 (H₂O:DMSO; 9:1, HEPES buffer, pH 7.0 ± 0.1) undergo highly selective fluorescence quenching with Hg²⁺. The observed linear fluorescence intensity change allows the quantitative detection of Hg²⁺ between 200 nM/40 ppb—12 μM/2.4 ppm even in the presence of interfering metal ions viz. Na⁺, K⁺, Mg²⁺, Ca²⁺, Ba²⁺, Cr³⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Ag⁺, Cd²⁺, Pb²⁺. Probes 1–3 and their Hg²⁺ complexes also show the broad pH resistance for their practical applicability.     

A redox-mediator pathway for enhanced multi-colour electrochemiluminescence in aqueous solution

The classic and most widely used co-reactant electrochemiluminescence (ECL) reaction of tris(2,2′-bipyridine)ruthenium(ii) ([Ru(bpy)₃]²⁺) and tri-n-propylamine is enhanced by an order of magnitude by fac-[Ir(sppy)₃]³⁻ (where sppy = 5′-sulfo-2-phenylpyridinato-C²,N), through a novel ‘redox mediator’ pathway. Moreover, the concomitant green emission of [Ir(sppy)₃]³⁻* enables internal standardisation of the co-reactant ECL of [Ru(bpy)₃]²⁺. This can be applied using a digital camera as the photodetector by exploiting the ratio of R and B values of the RGB colour data, providing superior sensitivity and precision for the development of low-cost, portable ECL-based analytical devices.

A water-soluble Ir(iii) complex is shown to enhance the ‘remote’ mechanism of the most widely used co-reactant ECL reaction of tris(2,2′-bipyridine)ruthenium(ii) with tripropylamine.     

A fluorescein-based fluorogenic and chromogenic chemodosimeter for the sensitive detection of sulfide anion in aqueous solution

A highly sensitive chromo- and fluorogenic chemodosimeter for sulfide anion was developed based on its nucleophilicity. 2,4-Dinitrobenzenesulfonyl-fluorescein (I) is a weakly fluorescent compound. Upon mixing with sulfide anion in aqueous acetone solution, the 2,4-dinitrobenzenesulfonyl group of I was efficiently removed and highly fluorescent fluorescein was released, hence leading to the dramatic increases in both fluorescence and absorbance of the reaction solution. The fluorescence increment is linear with sulfide anion concentration in the range 50-1000 nmol L⁻¹ with a detection limit of 4.3 nmol L⁻¹ (3σ). The proposed chemodosimeter showed excellent selectivity toward sulfide anion and was successfully applied to the determination of sulfide anion in synthetic wastewater samples.     

Study of complexation of an ionic liquid inside into crown ethers in aqueous environments by physicochemical techniques

Inclusion complexation between crown ethers (CEs) (viz., 15-crown-5, 18-crown-6) and an ionic liquid (IL) (viz., 1-ethyl-3-methylimidazolium tosylate) in aqueous medium have been demonstrated by conductivity, surface tension and ¹Proton Nuclear Magnetic Resonance (H NMR) study. The results show the formation of 1:1 complexes between CEs and the IL through electron-deficient imidazolium cation and electron pairs of oxygen atoms of the CEs. Hydrogen bonding is the key factor responsible for complexation, while, the ion–dipole interactions also contribute towards the complex formation. The formation constants have been derived from conductivity study and the complexes have been analysed by ¹H NMR study.     

Bisindole anchored mesoporous silica nanoparticles for cyanide sensing in aqueous media

For CN(-) recognition, a series of bisindolyl compounds 1-3 were prepared, and their chromodosimetric color changes toward anions were investigated. Nucleophilic addition of the cyanide ion to the meso position of the bisindolyl group gave rise to breaking of the double bond conjugation, thereby inducing spectroscopic changes in the compound. Mesoporous silica nanoparticles 3 also gave color changes from deep orange to yellow in response to the cyanide ion.     

Fluorescent amphiphilic cellulose nanoaggregates for sensing trace explosives in aqueous solution

A novel fluorescent amphiphilic cellulose nanoaggregates sensing system is designed and applied in detecting explosives in aqueous solution. Due to the maximized interaction between sensing material and analyte within the cellulose-based nanoaggregates, significantly enhanced sensitivity with 50-fold higher quenching efficiency is obtained.     

Chlamydomonas reinhardtii genetic variants as probes for fluorescence sensing system in detection of pollutants

The unicellular green alga Chlamydomonas reinhardtii is employed here for the setup of a biosensor demonstrator based on multibiomediators for the detection of herbicides. The detection is based on the activity of photosystem II, the multienzymatic chlorophyll–protein complex located in the thylakoid membrane that catalyzes the light-dependent photosynthetic primary charge separation and the electron transfer chain in cyanobacteria, algae, and higher plants. Several C. reinhardtii mutants modified on the D1 photosystem II protein are generated by site-directed mutagenesis and experimentally tested for the development of a biosensor revealing the modification of the fluorescence parameter (1 − V _J) in the presence of herbicides. The A250R, A250L, A251C, and I163N mutants are highly sensitive to the urea and triazine herbicide classes; the newly generated F255N mutant is shown to be especially resistant to the class of urea. It follows that the response of the multibiomediators is associated to a particular herbicide subclass and can be useful to monitor several species of pollutants.     

Gold nanocluster-based fluorescent probes for near-infrared and turn-on sensing of glutathione in living cells

In this study, a novel Au nanocluster (NC)-based fluorescent sensor has been designed for near-infrared (NIR) and turn-on sensing of glutathione (GSH) in both living cells and human blood samples. The large Stokes-shifted (140 nm) fluorescent Au NCs with NIR emission and long-wavelength excitation have been rapidly synthesized for 2 h by means of a microwave-assisted method in aqueous solution. The addition of Hg(II) leads to an almost complete emission quenching (98%) of Au NCs because of the interaction of Hg(II) and Au(I) on the surface of Au NCs. After introducing GSH to the Au NC-Hg(II) system, a more than 20 times fluorescent enhancement is obtained because of the preferable affinity of GSH with Hg(II). Under optimum conditions, the fluorescence recovery is linearly proportional to the concentration of GSH between 0.04 and 16.0 μM and the detection limit is as low as 7.0 nM. This Au NC-based sensor with high sensitivity and low spectral interference has been proven to facilitate biosensing applications.     

Recent advances in development of devices and probes for sensing and imaging in the brain

As the most important part of the central nervous system, the brain is extremely complex in structure and function. In vivo analysis of chemical signals is an essential way to investigate brain activity and function. Although functional magnetic resonance imaging(fMRI) or electrophysiology can be used to record brain activity, they are usually limited by low spatiotemporal fidelity or the difficulty of distinguishing the contributions of various neurochemicals. In addition, the development of in vivo biosensors with high selectivity and accuracy is essential to understand the roles that neurochemicals play in the brain. In this review, we focus on the development of instruments and devices for recording chemical signals in the live brain. Meanwhile,the strategies for development of electrochemical and fluorescent probes with high selectivity, high accuracy and good stability are also summarized. In particular, this review highlighted the contributions of our research group to this field. The development of techniques and probes enable us to understand the brain structure and function, and the mechanism of brain diseases, providing the solution for preventing and treating brain diseases.     

Salicylaldehyde hydrazones as fluorescent probes for zinc ion in aqueous solution of physiological pH

Salicylaldehyde hydrazones of 1 and 2 were synthesized and their potential as fluorescent probes for zinc ion was investigated in this paper. Both of the probes were found to show fluorescence change upon binding with Zn²⁺ in aqueous solutions, with good selectivity to Zn²⁺ over other metal ions such as alkali/alkali earth metal ions and heavy metal ions of Pb²⁺, Cd²⁺ and Hg²⁺. They showed 1:2 metal-to-ligand ratio when their Zn²⁺ complex was formed. By introducing pyrene as fluorophore, 2 showed interesting ratiometric response to Zn²⁺. Under optimal condition, 2 exhibited a linear range of 0-5.0 μM and detection limit of 0.08 μM Zn²⁺ in aqueous buffer, respectively. The detection of Zn²⁺ in drinking water samples using 2 as fluorescent probe was successful.     

A composite thin film optical sensor for dissolved oxygen in contaminated aqueous environments

A robust optical composite thin film dissolved oxygen sensor was fabricated by ionically trapping the dye ruthenium(II) tris(4,7-diphenyl-1,10-phenanthroline) dichloride in a blended fluoropolymer matrix consisting of Nafion^® and Aflas^®. Strong phosphorescence, which was strongly quenched by dissolved oxygen (DO), was observed when the sensor was immersed in water. The sensor was robust, optically transparent, with good mechanical properties. Fast response, of a few seconds, coupled with sensitivity of about 0.1 mg L⁻¹ (DO) over the range 0-30 mg L⁻¹ and resistance to leaching, were also exhibited by this system. The Stern-Volmer (SV) plot exhibited slight downward turning at all oxygen concentrations. A linear plot was obtained when the SV equation was modified to account for the varying sensitivity of dye molecules in the matrix to the quencher. Good long term stability was observed.