A reusable zirconium(IV) Schiff base complex catalyzes highly efficient synthesis of quinoxalines under mild conditions

A zirconium(IV) complex of a bidentate Schiff base (ZrL₂Cl₂) has been synthesized by the reaction of (z)-N-benzylidene-2-hydroxypropane-1-amine (HL) and ZrCl₄. Spectroscopic data and elemental analyses are consistent with a monomeric complex with a ligand:Zr ratio of 2:1. The catalytic activity of ZrL₂Cl₂ has been investigated for the efficient synthesis of a wide variety of quinoxaline derivatives under mild conditions. The employment of ethanol as an environmentally benign solvent in this high yield method, along with high turnover numbers and reusability of the catalyst providing ready scalability, makes it appropriate for practical applications.     

Synthesis and radioiodination of new dipeptide coupled with biologically active pyridine moiety

The adsorption of uranium (VI), cesium and strontium ions from aqueous solutions onto a commercial activated carbon obtained by physical activation of coconut shell has been studied in batch systems. In particular the adsorption of uranium, studied as a function of contact time and metal ion concentration, followed pseudo-first-order kinetics. Equilibrium adsorption data were fitted by Langmuir and Freundlich isotherm models and the maximum adsorption capacity of the activated carbon resulted to be 55.32 mg/g. The study showed that the considered activated carbon could be successfully used for uranium adsorption from aqueous solutions. Feasibility of cesium and strontium adsorption onto the same activated carbon has been also investigated. Results showed that no affinities with both of these ions exist.     

On-line simultaneous and rapid separation of anions and cations from a single sample using dual-capillary sequential injection-capillary electrophoresis

A novel capillary electrophoresis (CE) approach has been developed for the simultaneous rapid separation and identification of common environmental inorganic anions and cations from a single sample injection. The method utilised a sequential injection-capillary electrophoresis instrument (SI-CE) with capacitively-coupled contactless conductivity detection (C⁴D) constructed in-house from commercial-off-the-shelf components. Oppositely charged analytes from a single sample plug were simultaneously injected electrokinetically onto two separate capillaries for independent separation and detection. Injection was automated and may occur from a syringe or be directly coupled to an external source in a continuous manner. Software control enabled high sample throughput (17 runs per hour for the target analyte set) and the inclusion of an isolation valve allowed the separation capillaries to be flushed, increasing throughput by removing slow migrating species as well as improving repeatability. Various environmental and industrial samples (subjected only to filtering) were analysed in the laboratory with a 3 min analysis time which allowed the separation of 23 inorganic and small organic anions and cations. Finally, the system was applied to an extended automated analysis of Hobart Southern Water tap water for a period of 48 h. The overall repeatability of the migration times of a 14 analyte standard sample was less than 0.74% under laboratory conditions. LODs ranged from 5 to 61 μg L⁻¹. The combination of automation, high confidence of peak identification, and low limits of detection make this a useful system for the simultaneous identification of a range of common inorganic anions and cations for discrete or continuous monitoring applications.     

Ion-exchange and hydrophobic interactions affecting selectivity for neutral and charged solutes on three structurally similar agglomerated ion-exchange and mixed-mode stationary phases

The nature and extent of mixed-mode retention mechanisms evident for three structurally related, agglomerated, particle-based stationary phases were evaluated. These three agglomerated phases were Thermo Fisher ScientificIon PacAS11-HC – strong anion exchange, Thermo Fisher Scientific IonPac CS10 – strong cation-exchange PS-DVB, and the Thermo Fisher Scientific Acclaim Trinity P1silica-based substrate, which is commercially marketed as a mixed-mode stationary phase. All studied phases can exhibit zwitterionic and hydrophobic properties, which contribute to the retention of charged organic analytes. A systematic approach was devised to investigate the relative ion-exchange capacities and hydrophobicities for each of the three phases, together with the effect of eluent pH upon selectivity, using a specifically selected range of anionic, cationic and neutral aromatic compounds. Investigation of the strong anion-exchange column and the Trinity P1 mixed-mode substrate, in relation to ion-exchange capacity and pH effects, demonstrated similar retention behaviour for both the anionic and ampholytic solutes, as expected from the structurally related phases. Further evaluation revealed that the ion-exchange selectivity of the mixed-mode phase exhibited properties similar to that of the strong anion-exchange column, with secondary cation-exchange selectivity, albeit with medium to high anion-exchange and cation-exchange capacities, allowing selective retention for each of the anionic, cationic and ampholytic solutes. Observed mixed-mode retention upon the examined phases was found to be a sum of anion- and cation-exchange interactions, secondary ion-exchange and hydrophobic interactions, with possible additional hydrogen bonding. Hydrophobic evaluation of the three phases revealed log P values of 0.38–0.48, suggesting low to medium hydrophobicity. These stationary phases were also benchmarked against traditional reversed-phase substrates namely, octadecylsilica YMC-Pac Pro C18 and neutral μPS-DVB resin IonPac NS1-5u, yielding log P values of 0.57 and 0.52, respectively.     

Study on the influence of ageing on chemical and mechanical properties of N,N′-dimethyl-N,N′-diphenylcarbamide stabilized propellants

Double-base propellants undergo chemical, physical and mechanical changes upon ageing, leading to changes in ballistic performance and presenting explosive hazards. This report studies the variation of chemical and mechanical properties of aged N,N′-dimethyl-N,N′-diphenylcarbamide (methyl centralite) stabilized propellants in order to simulate and evaluate the natural ageing throughout the artificial one. Therefore, a comparative study of stabilizer depletion, plasticizers content, heat of combustion and mechanical properties such as storage modulus, loss modulus and damping of naturally and artificially aged propellants has been carried out by the following techniques: high-performance liquid chromatography (HPLC), thermogravimetric analyzer (TG), calorimeter of combustion and dynamic mechanical analyzer (DMA), respectively. The results obtained show that all properties are closely connected. In addition, the determination of stabilizer depletion, plasticizers evaporation, decrease of heat of combustion and mechanical properties are very useful for a better understanding of the decomposition and ageing behaviour of propellants. The HPLC investigation of stabilizer has shown good stability of the propellants. The results obtained for DMA have shown that some considerable changes of the mechanical and viscoelastic properties of the propellants occurred during ageing. These results confirm the results obtained by TG for the reduction of the nitroglycerine amount and the decrease of the heat of combustion.     

Electrochemical impedance spectroscopy as a highly sensitive tool for a dynamic interaction study between heparin and antithrombin: a novel antithrombin sensor

Specific recognition between two biological partners is widely exploited in biosensors nowadays. To explore this avenue, a novel biosensor for antithrombin (AT) detection was constructed. Heparin was used as the affinity ligand.A well-known acrylic monomer (butyl methacrylate) was polymerized and grafted onto the heparin polysaccharide by the use of ceric ammonium nitrate as a redox initiator in aqueous nitric acid medium. Polymers were deposited as a thin layer onto surface of stainless steel electrode (SS316L).The obtained polymers were studied by Fourier transform infrared spectroscopy (FTIR) and analyzed by differential scanning calorimetry (DSC).Moreover, the films were characterized by electrochemical impedance spectroscopy (EIS), contact-angle measurements and AFM.EIS was used to study the biosensor affinity to AT and the relationship between functionalization growth of modified electrode and the response of the sensor.The proposed approach appears to be simple, sensitive and correlated with methods that analyse the detection of antithrombin.     

Retention behavior and selectivity of a latex nanoparticle pseudostationary phase for electrokinetic chromatography

The retention characteristics and separation selectivity of a novel latex nanoparticle (NP) pseudostationary phase (PSP) for electrokinetic chromatography have been characterized. The anionic NPs have very low or no affinity for cationic solutes, but show significant interactions and retention based on hydrophobic interactions. Retention factors of alkyl-phenyl ketones increase linearly with the concentration of the NPs and have zero or near zero y-intercepts as expected for electrokinetic chromatography with non-micellar PSPs. The retention factors of these solutes and representative pharmaceuticals decrease logarithmically with increases in the concentration of ACN in the background electrolyte, as expected for reversed-phase retention. Linear solvation energy relationship analysis indicates that the NPs are less cohesive than would be expected for polymeric PSPs with similar structure but that the overall separation selectivity can be expected to be similar to polymer PSPs with similar backbone chemistry. The results indicate that the hydrophobic core of the NPs is non-cohesive and is highly accessible to solutes, whereas the ionic head groups are not as accessible and do not contribute substantially to retention or selectivity.     

The nonclassical noncovalent interactions control: A case study of the crystal structure of 3,5-dibromo-2-amino-4,6-dimethylpyridinium tetrahalocuprate [3,5-DBr-2-A-4,6-DMPH]2CuX4 (X = Cl, and Br)

The compound [3,5-dibromo-2-amino-4,6-dimethylpyridinium]₂CuCl₄, (1), was prepared from acidic hydrochloric acetonitrilic medium containing CuCl₂ and 3,5-dibromo-2-amino-4,6-dimethylpyridinium bromide while [3,5-dibromo-2-amino-4,6-dimethylpyridinium]₂CuBr₄, (2), from acidic HBr/Br₂ ethanolic medium containing 4,6-dimethylpyridine and CuBr₂. The ring got dibrominated at 3 and 5 positions in situ. Single-crystal X-ray diffraction proved the compounds to be isomorphous in P − 1. A systematic study of the crystallographic parameters in dibrominated and nonbrominated 2-amino-4,6-dimethylpyridine salts will explain the role of nonclassical noncovalent interaction between aryl bromine and ionic metal bromide in the control of structure.     

Ultrafast x-ray phase-contrast imaging of the initial coalescence phase of two water droplets

We report an ultrafast x-ray phase-contrast imaging study of the early merging dynamics of two water drops in air. Owing to the edge-enhancement capability, the high penetrability, and the unprecedented temporal and spatial resolutions offered by this new x-ray technique, the coalescence singularity of two water drops was revisited. A finite initial contact radius was identified and the evolvement of the trapped toroidal air bubble was studied for the first time. Despite the existence of this finite initial contact radius, the subsequent meniscus radius followed power laws which agree with theoretical predictions for the inviscid regime.     

Enhancing Chaos Complexity of a Plasma Model through Power Input with Desirable Random Features

The present work introduces an analysis framework to comprehend the dynamics of a 3D plasma model, which has been proposed to describe the pellet injection in tokamaks. The analysis of the system reveals the existence of a complex transition from transient chaos to steady periodic behavior. Additionally, without adding any kind of forcing term or controllers, we demonstrate that the system can be changed to become a multi-stable model by injecting more power input. In this regard, we observe that increasing the power input can fluctuate the numerical solution of the system from coexisting symmetric chaotic attractors to the coexistence of infinitely many quasi-periodic attractors. Besides that, complexity analyses based on Sample entropy are conducted, and they show that boosting power input spreads the trajectory to occupy a larger range in the phase space, thus enhancing the time series to be more complex and random. Therefore, our analysis could be important to further understand the dynamics of such models, and it can demonstrate the possibility of applying this system for generating pseudorandom sequences.