A Ru(II)-Based Nanoassembly Exhibiting Theranostic PACT Activity in NIR Region

Photoactivated chemotherapy (PACT) has appealing merits over traditional chemotherapy as well as photodynamic therapy (PDT) by virtue of its spatial and temporal control on drug activity and oxygen-independent mechanisms of action. However, the short photoactivation wavelengths, e.g., visible light–activated Ru(II)-based PACT agents, limit the clinical application severely. In this work, a facile construction of supramolecular nanoparticles from a poly(ethylene glycol) (PEG)-modified [Ru(dip)₂(py-SO₃)]⁺ (abbreviated as Ru-PEG, dip = 4,7-diphenyl-1,10-phenanthroline, py-SO₃ = pyridine-2-sulfonate) and 1,3-phenylenebis(pyren-1-ylmethanone) (BP) is shown. While Ru-PEG may undergo photoinduced ligand dissociation and release anticancer species of [Ru(dip)₂(H₂O)₂]²⁺, BP has extremely large two-photon absorption cross sections (δ₂) in the NIR region and intense fluorescence over the wavelengths where Ru-PEG has strong absorption. Thus, two-photon excitation of BP followed by an efficient Förster resonance energy transfer (FRET) from BP to Ru-PEG may lead to a potent inactivation against cisplatin-resistant cancer cells and 3D multicellular tumor spheroids (MCTSs). The residue fluorescence of BP also allows the cellular uptake of the particles to be visualized. This work provides a universal and convenient strategy to realize theranostic PACT in the ideal phototherapeutic window of 650–900 nm.     

New protonic solid electrolyte with tetragonal tungsten bronze structure obtained through ionic exchange

Proton exchange reactions have been performed on tetragonal tungsten bronze-like NaNbWO₆ by using nitric acid as an exchanging agent. The characterization of the exchange reaction products has been made by means of chemical analysis, X-ray diffraction, thermal analysis, and IR spectroscopy. The exchange reaction takes place topotactically and the following formula is proposed for the obtained phase of variable composition: Na_1−xH_xNbWO₆·yH₂O (0<x?0.46 and 0?y?0.12). Impedance spectroscopy on the present proton exchanged samples indicated that these samples behaved as solid electrolytes under high humidity. As an example, the compound with the composition Na_0.68H_0.32NbWO₆·0.1 H₂O exhibits ionic conductivity of 8×10⁻³ and 1×10⁻² S cm⁻¹ at 70°C and 90°C, respectively.     

A highly selective solid phase extraction sorbent for pre-concentration of sameridine made by molecular imprinting

Summary A novel approach to solid phase extraction, based on the use of a highly selective molecularly imprinted polymer, is presented. The versatility of this type of sorbent for solid phase extraction was demonstrated in a model batch-wise pre-concentration of sameridine prior to gas chromatography. Problems associated with leakage of remaining imprint molecules during the desorption phase could be eliminated by the use of a close structural analogue of sameridine as the imprint species. It was found that a major benefit of the imprinted polymer was its specificity, which lead to distinctly cleaner chromatographic traces and ability to improve sensitivity by extracting sameridine from larger sample volumes.     

Electrochemical formation and composition analysis of Zn x Cd1-x Se solid solutions

The direct growth of ZnSe–CdSe solid solution onto metallic cathodes by electrodeposition from acidic aqueous sulphate solutions is described. The plating process is studied by simple voltammetry, while the structure and composition of the electrolytic deposits are investigated by X-ray diffraction. The experimental d-spacing values of the as-grown mixed lattice are compared to data from reference Zn _x Cd_1-x Se pellets of standard composition, produced by a sintering method. The findings are supplemented with energy-dispersive X-ray (EDX) elemental analysis. Thereupon, the variation of the mole fraction x in Zn _x Cd_1-x Se, and the solid phase constitution of the electrodeposits are determined and correlated to the electrochemical conditions of growth. The resulting films contain admixtures of CdSe compound and metallic Cd.     

Solid phase extraction for analysis of biogenic carbonates by electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS): an investigation of rare earth element signatures in otolith microchemistry

Uptake of trace elements into fish otoliths is governed by several factors such as life histories and environment in addition to stock and species differences. In an attempt to elucidate the elemental signatures of rare earth elements (REEs) in otoliths, a solid phase extraction (SPE) protocol was used in combination with electrothermal vaporization (ETV) as a sample introduction procedure for the determinations by inductively coupled plasma quadrupole mass spectrometry (ICP-MS). Effects of various parameters, such as carrier gas flow rate, atomization temperature and chemical modification, were examined for optimization of the conditions by ETV-ICP-MS. Atomization was achieved at 2800 °C. Lower temperatures (i.e. 2600 °C) resulted in severe memory problems due to incomplete atomization. Palladium was used as a chemical modifier. It was found that an increase in Pd concentration up to 0.5 μg in the injection volume (70 μl) led up to four-fold enhancement in the integrated signals. This phenomenon is attributed to the carrier effect of Pd rather than the stabilization since no significant losses were observed for high temperature drying around 700 °C even in the absence of Pd. Preconcentration was performed on-line at pH 5 by using a mini-column of Toyopearl AF-Chelate 650M chelating resin, which also eliminated the calcium matrix of otolith solutions. After preconcentration of 6.4 ml of solution, the concentrate was collected in 0.65 ml of 0.5% (v/v) HNO₃ in autosampler cups, and then analyzed by ETV-ICP-MS. The method was validated with the analysis of a fish otolith certified reference material (CRM) of emperor snapper, and then applied to samples. Results obtained from otoliths of fish captured in the same habitat indicated that otolith rare earth element concentrations are more dependent on environmental conditions of the habitat than on species differences.     

肿瘤微波热疗的温度场预示及热损伤研究

本文将热损伤的产生和影响引入到肿瘤的微波热疗中。运用微波能量比吸收率SAR的分布分析了微波在组织中的传输和吸收过程,并对微波热疗过程中的温度场、热损伤分布以及血液灌注率的变化进行了数值模拟。     

Investigation of the Li1+xV3O8 electrode–organic electrolyte interface by scanning photoelectron microscopy

To investigate the formation of a solid electrolyte interface (SEI) on the Li_1+xV₃O₈ electrode surface in the thermodynamic stability range of the organic electrolyte, we applied scanning photoelectron microscopy (SPEM) to a pristine electrode and to an electrode after ten cycles. The F K-edge absorption spectrum of the cycled electrode showed that LiF forms on the electrode surface during the lithium insertion–extraction process in the Li_1+xV₃O₈/Li cell. The photoelectron spectrum for the cycled electrode showed intense spectral features corresponding to Li 1s, F 2s, F 2p, and P 2p electron signals, whereas these spectral features were of negligible intensity for the pristine electrode. The above results give strong support for the formation of an SEI that consists of LiF and compounds containing phosphorus during operation of the battery. The SPEM images also revealed that the fluorine distribution on the surface of the cycled electrode was inhomogeneous.     

三羟甲基甲胺、季戊四醇及其二元体系固-固相变的变温红外光谱研究

利用傅里叶变温红外光谱仪分别测定了三羟甲基甲胺（TAM）、季戊四醇（PE）及其二元体系变温红外谱。实验表明，多元醇分子中羟基吸收峰随温度升高耐发生位移向高波数移动，此结果既能反映多元醇及其二体系固－固相变的温度区间，又与转变热相对应，从而揭示了多元醇及其二元体系固－固相变贮热的机理。     

Topochemically Controlled Redox Reactions in the System In/Sn/Cl

The difference in reactivity of the two modifications of InCl in solid state reactions with SnCl₂ is discussed. It is explained on the basis of semi‐empirical and ab initio calculations giving the density of states diagrams of InCl and the energies of possible disproportionation reactions. Their general features are discussed on the basis of a simple bonding picture for open‐packed structures involving inert pair elements. A detailed analysis of the DOS distribution allows to pinpoint the observed redox instability to a specific structural feature of α‐InCl.     

REM树脂的制备及亲核加成应用研究

用Mitsunobu反应及丙烯酰氯酰化反应制备了用于固相有机合成的载体REM树脂，将REM树脂与苄胺加成，考查了所合成REM树脂的反应性能，并通过元素分析测定氮含量，推出REM树脂的烯丙基固载量。利用所合成的REM树脂进行了与胺、酚的加成反应动力学研究。结果表明，REM树脂与脂肪族伯胺和促胺的加成反应能够进行，与苯胺不发生反应；REM树脂与酚不能发生亲核加成反应。