Synthesis of Calix[4]arene Derivatives Containing a Nucleobase and their Interaction with Complementary Nucleosides at the Air–Water Interface

Amphiphilic calix[4]arene derivatives with a nucleobase on the lower rim have been synthesized in good yields by the condensation of calix[4]arenediamine {5,11,17,23-tetra-tert-butyl-25,27-bis(2-aminoethoxy)-26,28-dihydroxycalix[4]arene} with uracilo-N-acetic acid, thymino-N-acetic acid and adenino-N-propionic acid in the presence of CDI in DMF. Monolayers of the amphiphilic calix[4]arene-nucleobase derivatives on the surface of pure water, the aqueous subphases containing complementary nucleosides, were studied by film balance measurement and relaxation experiments. LB films deposited from all subphases were investigated by UV spectra and FT-IR spectroscopy. All the results indicate that the interaction between the nucleobases in the headgroup of amphiphilic p-tert-butylcalix[4]arene derivatives and the complementary nucleosides in the subphase takes place through multiple hydrogen bonding and the nucleosides can be transferred to solid substrates along with their monolayers.     

Easy One‐Pot Synthesis of 1‐Monosubstituted Aliphatic 1,2,3‐Triazoles from Aliphatic Halides,Sodium Azide and Propiolic Acid by a Click Cycloaddition/Decarboxylation Process

1‐Monosubstituted aliphatic 1,2,3‐triazoles were synthesized by a one‐pot reaction from aliphatic halides (Cl and Br), sodium azide and propiolic acid. The yields ranged from moderate to good. The reaction was easily carried out in DMF with Cs₂CO₃ at 100°C by copper‐catalyzed click cycloaddition/decarboxylation.     

Discrimination and simultaneous determination of hydroquinone and catechol by tunable polymerization of imidazolium-based ionic liquid on multi-walled carbon nanotube surfaces

Tunable polymerization of ionic liquid on the surfaces of multi-walled carbon nanotubes (MWCNTs) was achieved by a mild thermal-initiation-free radical reaction of 3-ethy-1-vinylimidazolium tetrafluoroborate in the presence of MWCNTs. Successful modification of polymeric ionic liquid (PIL) on MWCNTs surfaces (PIL-MWCNTs) was demonstrated by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis and X-ray photoelectron spectroscopy. The resulting PIL-MWCNTs possessed unique features of high dispersity in aqueous solution and tunable thickness of PIL layer, due to positive imidazole groups along PIL chains and controllable ionic liquid polymerization by tuning the ratio of precursor. Based on cation-π interaction between the positive imidazole groups on PIL-MWCNTs surface and hydroquinone (HQ) or catechol (CC), excellent discrimination ability toward HQ and CC and improved simultaneous detection performance were achieved. The linear range for HQ and CC were 1.0 × 10⁻⁶ to 5.0 × 10⁻⁴ M and 1.0 × 10⁻⁶ to 4.0 × 10⁻⁴ M, respectively. The detection limit for HQ was 4.0 × 10⁻⁷ M and for CC 1.7 × 10⁻⁷ M (S/N = 3), correspondingly.     

Synthesis and Characterization of Iron Nanowires

The iron nanowires can be fabricated via the process in which sodium borohydride reduces iron salts in external magnetic field. The iron nanowires are found to be covered by passivated layers of iron oxide which prevent the oxidation of iron nanowires. In this process, the boron will include in iron nanowires. The average length and diameter of iron nanowires is around 1.2 micrometers and 60 nanometers, respectively. According to ICP results, the contents of B and Fe are about 1.98 wt% and 87.04 wt%, respectively, in iron nanowires. A wide variety of equipment is used to investigate the morphological, microchemical, and structural characteristics of the newly synthesized iron nanowires ––– e.g., XRD, FE‐SEM, HR‐TEM, VSM and XANES. XANES analysis indicates the boron in iron nanowires exists in the form of B₂O₃. The saturation magnetization and the coercive force of iron nanowires are 157.93 emu/g and 9.74 Oe, respectively. In‐situ images of synthesized iron nanowires during reduction process in magnetic field are observed by NSRRC transmission X‐ray microscope. Thus, this study develop a novel process to produce iron nanowires with large quantitates and can control its length and diameter by various the concentration of precursors for various applications.     

Self‐assembly of Carbon Particles as a Heat Sink Coating to Promote Radiative Cooling

Novel composite carbon particles are developed that can self‐assemble as a coating on a substrate without a binder. These carbon particles were used as a coating to enhance thermal dissipation and their thermal conductivity, surface emissivity and cooling performance were measured. Carbon particles with both thiol and epoxy functional groups self‐assembled to form a coating on the surface of a heat sink without a binder, which greatly improved the thermal conductivity of the coating. Coating a heat sink with the carbon particles yielded a higher thermal conductivity and emissivity than could be obtained with the addition of binder in the conventional approach, and significantly enhanced the cooling performance. In addition, the cooling performance of the carbon nanotube outperformed all other particles when coated on a substrate, because it had the highest thermal conductivity and good radiation emissivity. We developed an equation to describe the various parameters affecting the cooling performance of the thermally dissipative coating. This equation was confirmed by the experimental data.     

Decontamination of radionuclides on construction materials

A wide variety of materials can become contaminated by radionuclides, either from a terrorist attack or an industrial or nuclear accident. The final disposition of these materials depends, in large part, on the effectiveness of decontamination measures. This study reports on investigations into the decontamination of a selection of building materials. The aim has been to find an effective, easy-to-use and inexpensive decontamination system for radionuclides of cesium and cobalt, considering both the chemical and physical nature of these potential contaminants. The basic method investigated was surface washing, due to its ease and simplicity. In the present study, a basic decontamination formulation was modified by adding isotope-specific sequestering agents, to enhance the removal of cesium(I) and cobalt(II) from such construction materials as concrete, marble, aluminum and painted steel. Spiking solutions contained ¹³⁴Cs or ⁶⁰Co, which were prepared by neutron activation in the SLOWPOKE-2 nuclear reactor facility at the Royal Military College of Canada. Gamma spectroscopy was used to determine the decontamination efficiency. The results showed that the addition of sequestering agents generally improved the radiological decontamination. Although the washing of both cesium and cobalt from non-porous materials, such as aluminum and painted steel, achieved a 90–95 % removal, the decontamination of concrete and marble was more challenging, due to the porous nature of the materials. Nevertheless, the removal efficiency from 6-year-old concrete increased from 10 % to approximately 50 % for cobalt(II), and from 18 to 55 % for cesium(I), with the use of isotope binding agents, as opposed to a simple water wash.     

An ionic liquid-based sorbent for solid phase extraction of trace iron(Ш) from biological and natural water samples

A new ionic liquid modified silica gel sorbent was prepared from the reaction of active silica gel with N-3-(-3-triethoxysilylepropyl)-3-methylimidazolium chloride ([(TESP)MIm]Cl). This sorbent was exploited as solid phase extractant for separation and preconcentration of metal ions prior to their determination by inductively coupled plasma atomic emission spectrometry (ICP-AES). It was found that it can selectively adsorb Fe(Ш). Identification of the surface modification was performed on the basis of FT-IR. Experimental conditions for effective adsorption of trace Fe(Ш) were optimised using both batch and column procedures. At pH 3, Fe(Ш) could be quantitatively adsorbed and completely eluted by using 2?mL of 0.1?mol?L^?1 of HCl. 150?mL of sample solution was adopted as the maximum sample volume and a high enrichment factor of 75 was obtained. Most common coexisting ions did not interfere with the separation and preconcentration of Fe(Ш) at optimal conditions. The maximum static adsorption capacity of the sorbent was 37.0?mg?g^?1. The detection limit of the present method was 0.48?µg?L^?1, and the relative standard deviation (R. S. D.) was lower than 1.7%. The method was successfully applied to the preconcentration of trace Fe(Ш) in biological and natural water samples with satisfactory results.     

Preparation of Unconventional Dendrimers that Contain Rigid NH?Triazine Linkages and Peripheral tert‐Butyl Moieties for CO2‐Selective Adsorption

Three unconventional dendrimers that contained rigid NH? triazine linkages and peripheral tert‐butyl moieties were prepared by using a convergent approach and characterized by ¹H and ¹³C NMR spectroscopy, mass spectrometry, and elemental analysis. Based on a thermogravimetric analysis study, these dendrimers were observed to display thermal stability at about 300 °C. The NH? triazine moiety, which possessed protonated and proton‐free nitrogen sites (like the imidazole unit), displayed the capture of polarizable CO₂ molecules through hydrogen‐bond and/or dipole–quadrupole interactions. In addition, the adsorption of various amounts of CO₂ and N₂ at different pressures suggests that the dendritic pores, which arise from the stacking of the middle co‐planar and rim protuberant dendrimers, G _n ‐N～N‐G _n (n=1–3), either swell or shrink at high pressure, thus indicating that these dendrimers may have a breathing ability.     

Bioconjugation of Proteins with a Paramagnetic NMR and Fluorescent Tag

Site‐specific labeling of proteins with lanthanide ions offers great opportunities for investigating the structure, function, and dynamics of proteins by virtue of the unique properties of lanthanides. Lanthanide‐tagged proteins can be studied by NMR, X‐ray, fluorescence, and EPR spectroscopy. However, the rigidity of a lanthanide tag in labeling of proteins plays a key role in the determination of protein structures and interactions. Pseudocontact shift (PCS) and paramagnetic relaxation enhancement (PRE) are valuable long‐range structure restraints in structural‐biology NMR spectroscopy. Generation of these paramagnetic restraints generally relies on site‐specific tagging of the target proteins with paramagnetic species. To avoid nonspecific interaction between the target protein and paramagnetic tag and achieve reliable paramagnetic effects, the rigidity, stability, and size of lanthanide tag is highly important in paramagnetic labeling of proteins. Here 4′‐mercapto‐2,2′: 6′,2′′‐terpyridine‐6,6′′‐dicarboxylic acid (4MTDA) is introduced as a a rigid paramagnetic and fluorescent tag which can be site‐specifically attached to a protein by formation of a disulfide bond. 4MTDA can be readily immobilized by coordination of the protein side chain to the lanthanide ion. Large PCSs and RDCs were observed for 4MTDA‐tagged proteins in complexes with paramagnetic lanthanide ions. At an excitation wavelength of 340 nm, the complex formed by protein–4MTDA and Tb³⁺ produces high fluorescence with the main emission at 545 nm. These interesting features of 4MTDA make it a very promising tag that can be exploited in NMR, fluorescence, and EPR spectroscopic studies on protein structure, interaction, and dynamics.     

Facile Self‐Assembly Synthesis of PdPt Bimetallic Nanotubes with Good Performance for Ethanol Oxidation in an Alkaline Medium

PdPt bimetallic nanotubes were prepared by the self‐assembly of Pt and Pd on Te nanowires at room temperature. The morphologies of the as‐prepared PdPt nanotubes were investigated by scanning electron microscopy and transmission electron microscopy, and the results display a large amount of PdPt bimetallic nanotubes with a diameter of 10–20 nm and a length of several micrometers. The composition and structure of the nanotubes were characterized by X‐ray diffraction, high‐resolution transmission electron microscopy, scanning transmission electron microscopy, and energy spectrum analysis, and the results display uniform compositional distributions of both elements (Pd and Pt). The mechanism of the formation of the nanotube structure was supposed. The electrocatalytic performance of PdPt nanotubes were studied by cyclic voltammetry and chronoamperometry. Electrochemical results show that the as‐prepared PdPt nanotube catalysts have not only high activity but also good stability for ethanol oxidation in alkaline medium.