A Highly Oxidizing and Isolable Oxoruthenium(V) Complex [RuV(N4O)(O)]2+: Electronic Structure,Redox Properties,and Oxidation Reactions Investigated by DFT Calculations

The electronic structure and redox properties of the highly oxidizing, isolable Ru^V?O complex [Ru^V(N₄O)(O)]²⁺, its oxidation reactions with saturated alkanes (cyclohexane and methane) and inorganic substrates (hydrochloric acid and water), and its intermolecular coupling reaction have been examined by DFT calculations. The oxidation reactions with cyclohexane and methane proceed through hydrogen atom transfer in a transition state with a calculated free energy barrier of 10.8 and 23.8 kcal mol^?1, respectively. The overall free energy activation barrier (ΔG^≠=25.5 kcal mol^?1) of oxidation of hydrochloric acid can be decomposed into two parts: the formation of [Ru^III(N₄O)(HOCl)]²⁺ (ΔG=15.0 kcal mol^?1) and the substitution of HOCl by a water molecule (ΔG^≠=10.5 kcal mol^?1). For water oxidation, nucleophilic attack on Ru^V?O by water, leading to O? O bond formation, has a free energy barrier of 24.0 kcal mol^?1, the major component of which comes from the cleavage of the H? OH bond of water. Intermolecular self‐coupling of two molecules of [Ru^V(N₄O)(O)]²⁺ leads to the [(N₄O)Ru^IV? O₂? Ru^III(N₄O)]⁴⁺ complex with a calculated free energy barrier of 12.0 kcal mol^?1.     

Development of a rapid method for the simultaneous separation and determination of 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol and its N- and O-glucuronides in human urine by liquid chromatography–tandem mass spectrometry

Determination of the tobacco-specific nitrosamine metabolite 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol (NNAL) and its N- and O-glucuronides (NNAL-N-Gluc and NNAL-O-Gluc) is important for toxicology analysis of tobacco smoke induced carcinogenicity and the understanding of detoxification mechanisms of the carcinogenic nitrosamine in humans. But previously reported indirect measurement methods involving enzymolysis and base treatment steps were tedious and time-consuming. In this work, a direct measurement method for simultaneous determination of urinary NNAL, NNAL-N-Gluc and NNAL-O-Gluc by liquid chromatography–tandem mass spectrometry (LC–MS/MS) in a single run was developed for the first time without the need to perform enzymatic or base hydrolysis. Urine samples were purified using dichloromethane and further extracted by solid-phase extraction. Then they were analyzed by LC–MS/MS operated in electrospray positive ionization mode. Chromatographic separation was achieved on a Phenomenex Kinetex PFP column within 6 min. The proposed method was validated and the results demonstrated that the method can produce satisfactory recoveries and reproducibility for the analytes. The applicability of this newly developed method was investigated for the simultaneous analysis of the three metabolites in smokers’ urine and the obtained results were comparable to those detected using the conventional enzymolysis method.     

Enhancement of sensitivity of paper-based sensor array for the identification of heavy-metal ions

Paper-based microfluidic devices have been widely investigated in recent years. Among various detection techniques, colorimetric method plays a very important role in paper-based microfluidic devices. The limitation, however, is also clear: they generally require highly sensitive indicators. In this work, we have developed a novel enrichment-based paper test for the discrimination of heavy-metal ions. Comparing to regular paper-based microfluidic devices, enrichment-based technique showed largely improved sensitivity. Combining with eight pyridylazo compounds and array technologies-based pattern-recognition, we have obtained the discrimination capability of eight different heavy-metal ions at same concentration as low as 50 μM using our enrichment-based pyridylazo compounds array paper. Identification of the heavy-metal ions was readily achieved using a standard chemometric approach. This method can be, of course, used for other analytes as well.     

Experimental Evidence for Ion Accumulation Time Affecting Qualitative and Quantitative Analysis of Ophiopogons in Ophiopogon Extract by Hybrid Ion Trap Time-of-Flight Mass Spectrometry

The qualitative and quantitative capability of the ion trap mass analyzer could be greatly affected by the accumulation time. However, the importance of the accumulation time has not so far been thoroughly explored. Here, the influence of ion accumulation time on qualitative and quantitative analysis of complicated components was systematically investigated based on the case study of 40 ophiopogonins in Ophiopogon extract by hybrid ion trap time-of-flight mass spectrometry (LCMS-IT-TOF). In this process, the accumulation time was set at 10, 25, 50, 100, and 200 ms, respectively. The effect of accumulation time on qualitative analysis of ophiopogonins was studied by comparing the total ion current (TIC) of MS¹, TIC of MS², and the number and signal of fragmental ions. The results demonstrated that the signal could be greatly influenced by varying the accumulation time. The number and signal of the fragmental ions were increased significantly with a longer accumulation time in the range of 10–100 ms. Also, the effect of accumulation time on quantitative analysis of ophiopogonins was investigated by comparing the linearity, accuracy, and precision measured on LCMS-IT-TOF. Importantly, quantitative parameters could all be significantly improved by choosing an appropriate accumulation time.

     

Multiple discrete energy levels and the bistable state of weak anchoring NLC cells

The weak anchoring nematic liquid crystal (NLC) cell is investigated with regard to energy. Because the Gibbs free energy of liquid crystal system used in theory does not include temperature and entropy, and because the equations and boundary conditions for δG=0 are also the mechanical equilibrium conditions of the continuum, the Gibbs free energy G is equivalent to the energy E of the liquid crystal continuum. There are multiple solutions which satisfy these equations and boundary conditions, each solution corresponding to a certain energy value. We call these discrete energy values and energy levels. Adopting a simple liquid crystal cell model, the energy levels are calculated in detail by means of analytical and numerical methods. The results show that there are three energy levels (or more in certain cases). The values and sequence of the energy levels are related to the external field and anchoring parameters. The relationships between the energy level structure and the bistable. Fréedericksz transition are disussed, together with their influence on the response time. The physical condition for the existence of more than three energy levels is also given.     

Preparation and properties of highly birefringent liquid crystalline materials: styrene monomers with acetylenes,naphthyl, and isothiocyanate groups

Two new series of styrene monomers with different alkyl chain length were successfully synthesised. The chemical structures of synthetic intermediates and monomers were confirmed by Fourier transform infrared spectroscopy, ¹H nuclear magnetic resonance spectroscopy, mass spectrometry and elemental analysis. Their thermal stability, transition temperatures and phase sequences were investigated by polarised light microscopy, thermogravimetric analysis, differential scanning calorimetry and one-dimensional wide-angle X-ray diffraction. The birefringent and photoelectric properties, UV–vis and fluorescence spectroscopy were also measured using Abbe refractometer and fluorescent apparatus. The results indicated that all the monomers exhibited a liquid crystalline phase at higher temperature, high birefringence values between 0.4 and 0.7, and good photoluminescence properties. Optical anisotropy of homologous molecules was reduced with the increase of alkyl chain length due to the decrease of molecular polarisation. Moreover, a significant effect of the chemical structure on the photoluminescence properties was also found and discussed according to the length of π-conjugation.     

Expression of Cholera Toxin B–Lumbrokinase Fusion Protein in Pichia pastoris—The Use of Transmucosal Carriers in the Delivery of Therapeutic Proteins to Protect Rats Against Thrombosis

Cholera toxin B-subunit (CTB) has been widely used to facilitate antigen delivery by serving as an effective mucosal carrier molecule for the induction of oral tolerance. However, whether CTB can be used as a transmucosal carrier in the delivery of not only vaccines but also therapeutic proteins has not been widely studied. Thus, we investigate here the concept of receptor-mediated oral delivery of lumbrokinase (LK) proteins which is an important fibrinolytic enzyme derived from earthworm. CTB and LK, separated by a furin cleavage site, was expressed via Pichia pastoris. The activity and proper folding of recombinant protein in yeast were confirmed by Western blot analysis, fibrin plate assays, and G_M1-ganglioside ELISA. Following oral administration of recombinant protein, the thrombosis model of rats and mice revealed that the oral treatment of rCTB–LK has a more significant anti-thrombotic effect on animals compared with rLK. It is possible to conclude that CTB can successfully enhance its fusion protein LK to be absorbed. The use of CTB as a transmucosal carrier in the delivery of not only vaccines but also therapeutic proteins was supported.     

Graphene Oxide Protected Nucleic Acid Probes for Bioanalysis and Biomedicine

Recently, the binding ability of DNA on GO and resulting nuclease resistance have attracted increasing attention, leading to new applications both in vivo and in vitro. In vivo, nucleic acids absorbed on GO can be effectively protected from enzymatic degradation and biological interference in complicated samples, making it useful for targeted delivery, gene regulation, intracellular detection and imaging with high uptake efficiencies, high intracellular stability, and very low toxicity. In vitro, the adsorption of ssDNA on GO surface and desorption of dsDNA or well‐folded ssDNA from GO surface result in the protection and deprotection of DNA from nucleic digestion, respectively, which has led to target‐triggered cyclic enzymatic amplification methods (CEAM) for amplified detection of analytes with sensitivity 2–3 orders of magnitude higher than that of 1:1 binding strategies. This Concept article explores some of the latest developments in this field.     

Novel Tripod Amphiphiles for Membrane Protein Analysis

Integral membrane proteins play central roles in controlling the flow of information and molecules across membranes. Our understanding of membrane protein structures and functions, however, is seriously limited, mainly due to difficulties in handling and analysing these proteins in aqueous solution. The use of a detergent or other amphipathic agents is required to overcome the intrinsic incompatibility between the large lipophilic surfaces displayed by the membrane proteins in their native forms and the polar solvent molecules. Here, we introduce new tripod amphiphiles displaying favourable behaviours toward several membrane protein systems, leading to an enhanced protein solubilisation and stabilisation compared to both conventional detergents and previously described tripod amphiphiles.     

Formation and Properties of Self‐Assembly‐Driven Fluorescent Nanoparticle Sensors

Fluorescent nanoparticles (FNPs) are obtained in water by self‐assembly from a polymeric ionic liquid, fluorescent carboxylate moiety, and a surfactant through two main supramolecular interactions, that is, ionic bonds and hydrophobic/hydrophilic interactions. The hydrophobicity of the surfactant is tunable and a highly hydrophobic surfactant increases the fluorescence intensity and stability of the FNPs. The fluorescence of the FNPs is sensitive to a quenching effect by various ions with high selectivity, and consequently, they may be used as sensors. The self‐assembly approach used to generate the FNPs is considerably simpler than other methods based on more challenging synthetic methods and the flexibility of the approach should allow a wide and diverse range of FNPs to be prepared with specific sensor applications.