Group 4 ansa-metallocenes derived from o-carborane and their luminescent properties

Luminescent group 4 complexes derived from o-carborane, M(η⁵:η¹-CpCMe₂CB₁₀H₁₀C)₂ (M = Ti; 1, Zr; 2, Hf; 3) and Me₂Si(η⁵-Ind)[η⁵:η¹-Cp-3-(CMe₂CB₁₀H₁₀C)]ZrCl (4) were explored. While the Ti complex 1 possessing C₂ molecular symmetry shows non-centrosymmetry in the unit cell as identically observed in 2 and 3, the double-ansa Zr complex 4 crystallizes in centrosymmetric P2₁/n space group despite its C₁ molecular symmetry. The non-centrosymmetric crystals of 2 and 3 exhibit blue mechanoluminescence similar to their solution and solid state photoluminescence. In contrast, 1 is lacking mechanoluminescence in crystal and shows much weaker emission than other congeners in solution. The electroluminescence devices based on 2 or 3 doped poly(N-vinylcarbazole) (PVK) as an emitting layer display green electroluminescence, which turned out to be originated from the exciplexes formed between the complex and PVK host. Although the double ansa-Zr complex 4 does not show mechanoluminescence owing to the centrosymmetric nature, it exhibits good electron-transporting properties when incorporated into the electron-transporting layer of Alq₃-based OLEDs.     

超支化聚氨酯热熔胶的合成及性能

采用AA′+bB2法制备了可以直接作为热熔胶使用的超支化聚氨酯(HPU). 以甲苯-2,4-二异氰酸酯(TDI)与聚碳酸酯二醇(PCDL)为原料合成两端为异氰酸根(NCO)封端的低聚物(A2),然后在0 ℃下加入二乙醇胺(DEOA)得AB2型中间物,进一步高温聚合得支化点间含有长链段的超支化聚氨酯. 采用红外光谱 (FTIR)、核磁共振(13C NMR)、GPC对超支化聚氨酯的结构进行了表征. 结果表明,所得到的产物具有超支化结构,在55 ℃下反应20 h后,支化度可达到0.75,重均分子量Mw=7.0×103. 对产物进行了热失重和粘接性能测试. 结果表明,超支化聚氨酯的热分解温度为200 ℃. 产物的粘接剪切强度随着链段长度的增加先增大后减小,最大可达到6.5 MPa.     

Photolysis of organic pollutants in wastewater with 206 nm UV irradiation

A new-type UV light source(206 nm) was explored for the degradation of organic pollutants in wastewater for the first time.The degradation performances of triphenyltin chloride(TPTCl),dimethyl phthalate(DMP),as well as rhodamine B(RhB) were investigated.The results indicated that removal efficiency of 50 mg/L RhB,60 mg/L DMP and 120 mg/L TPTCl can reach 88.6%, 92.5%and 89.4%for 60 min,50 min and 75 min,respectively.By comparison of removal efficiency,we found 206 nm is superior to 253.7 nm UV in wastewat...     

Determination of sulfur anions by ion chromatography-postcolumn derivation and UV detection

A novel method for determination of formaldehyde sulfoxylate,sulfite,thiocyanate,and thiosulfate in foodstuffs by ion chromatography separation with postcolumn derivation and UV detection has been developed.All species are separated at Dionex IonPac AG22A and AS22A with mobile phase of a mixture of 4.5 mmol/L sodium carbonate and 0.8 mmol/L sodium bicarbonate at a flow-rate of 1.0mL/min.The postcolumn derivation solution was 0.24%iodine in 0.2%phosphate acid and the detection wavelength was set at 288 nm...     

Sequential separation of transuranic elements and fission products from uranium metal ingots in electrolytic reduction process of spent PWR fuels

A sequential separation procedure has been developed for the determination of transuranic elements and fission products in uranium metal ingot samples from an electrolytic reduction process for a metallization of uranium dioxide to uranium metal in a medium of LiCl-Li₂O molten salt at 650 °C. Pu, Np and U were separated using anion-exchange and tri-n-butylphosphate (TBP) extraction chromatography. Cs, Sr, Ba, Ce, Pr, Nd, Sm, Eu, Gd, Zr and Mo were separated in several groups from Am and Cm using TBP and di(2-ethylhexyl)phosphoric acid (HDEHP) extraction chromatography. Effect of Fe, Ni, Cr and Mg, which were corrosion products formed through the process, on the separation of the analytes was investigated in detail. The validity of the separation procedure was evaluated by measuring the recovery of the stable metals and ²³⁹Pu, ²³⁷Np, ²⁴¹Am and ²⁴⁴Cm added to a synthetic uranium metal ingot dissolved solution.     

Preparation and characterization of cellulose nanocomposite films with two different organo-micas

The mechanical properties, morphologies, and gas barriers of hybrid films of cellulose with two different organoclays are compared. Dodecyltriphenyl-phosphonium-mica (C₁₂PPh-mica) and hexadecyl-mica (C₁₆-mica) were used as reinforcing fillers in the fabrication of the cellulose hybrid films. The cellulose hybrid films were synthesized from N-methyl-morpholine-N-oxide (NMMO) solutions with the two organo-micas, and solvent-cast at room temperature under vacuum, yielding 15–20 μm thick films of cellulose hybrids with various clay contents. We found that the addition of only a small amount of organoclay is sufficient to improve the mechanical properties and gas barriers of the cellulose hybrid films. Even polymers with low organoclay contents (1–7 wt %) were found to exhibit much higher strength and modulus values than pure cellulose. The addition of C₁₂PPh-mica was more effective than that of C₁₆-mica with regards to the initial tensile modulus, whereas the addition of C₁₆-mica was more effective than that of C₁₂PPh-mica with regards to the gas barrier of the cellulose matrix. The intercalations of the polymer chains in the clays were examined with wide-angle X-ray diffraction (XRD) and electron microscopy (SEM and TEM).     

Adjuvant Effects of Dual Co-stimulatory Molecules on Cellular Responses to HIV Multiple-epitope DNA Vaccination

Designing adjuvants that can induce strong cytotoxic T cell responses is largely required for preparing DNA vaccines. In this study we explored dual costimulatory molecules 4-1BBL and OX40L as adjuvants to improve the efficiency of the HIV multiple-epitope DNA vaccine. When explored in the human dendritic cell-T cell based coculture system,dual costimulatory molecules significantly enhanced the anti-HIV T cell response of the HIV mul-tiple-epitope DNA vaccine,as detected by intracellular cytokine staining t...     

Two manganese(II) complexes based on anthracene-9-carboxylate: Syntheses,crystal structures,and magnetic properties

Abstract  To explore the influence of the anthracene ring skeleton, with a large conjugated π-system, on the structures and properties of its complexes, two Mn^II complexes with anthracene-9-carboxylate ligand were synthesized and structurally characterized: {[Mn(L)₂(H₂O)₂](H₂O)}_∞ (1) and [Mn₂(L)₄(phen)₂(μ-H₂O)](CH₃OH) (2) (L = anthracene-9-carboxylate and phen = 1,10-phenanthroline). Complex (1) has a one-dimensional (1D) chain structure that is further assembled to form a two-dimensional (2D) sheet, and then an overall three-dimensional (3D) network by π···π stacking and/or C–H···π interactions. Complex (2) makes a dinuclear structure by incorporating the chelating phen ligand, which is further interlinked via inter-molecular π···π stacking and C–H···π interactions to generate a higher-dimensional supramolecular network along the different crystallographic directions. The results reveal that the bulky anthracene ring skeleton in L, by virtue of intra- and/or inter-molecular π···π stacking and C–H···π interactions, plays an important role in the formation of complexes (1) and (2). The magnetic properties of (1) and (2) were further investigated. As expected, the very long inter-metallic separations result in weak magnetic coupling, with the corresponding coupling constant values of J = −10 cm⁻¹ for (1) and J = −2.46 cm⁻¹ for (2). Graphical abstract  The constructions of two new Mn^II complexes comprising 1D chain (1) and dinuclear subunit (2) structures have been successfully achieved by using a bulky anthracene-9-carboxylic acid (HL), together with incorporating the chelating 1,10-phenanthroline as a co-ligand for (2). The result reveals that the bulky anthracene ring skeleton of HL, by virtue of intra- and/or inter-molecular π···π stacking and C–H···π interactions, plays an important role in the formation of the supramolecular architectures of (1) and (2). Moreover, magnetic properties of the complexes have been investigated.      

Thermal hazard evaluation of carbon nanotubes with sulfuric acid by DSC

Many concerns over unsafe or unknown properties of multi-walled carbon nanotubes (MWNTs) have been raised. The thermal characteristics regarding stability would represent potential hazards during the production or utilization stage and could be determined by calorimetric tests for various thermokinetic parameters. Differential scanning calorimetry (DSC) was employed to evaluate the thermokinetic parameters for MWNTs at various compositions. Thermoanalytical curves showed that the average heat of decomposition (ΔH _d) of the MWNTs samples in a manufacturing process was about 31,723 J g⁻¹, by identifying them as an inherently hazardous material. In this study, significant thermal analysis appeared in the presence of sulfuric acid (H₂SO₄). From the DSC experiments, the purification process of MWNTs could induce an unexpected reaction in the condition of batch addition with reactants of H₂SO₄. The results can be applied for designing emergency relief system and emergency rescue strategies during a perturbed situation or accident.     

Silver(I) Complexes with a Bulky Anthracene‐Based Dicarboxylic Ligand: Syntheses,Crystal Structures,and Luminescent Properties

To explore the influence of anthracene skeleton with a larger conjugated π‐system on the structures and properties of its complexes, two Ag^I–carboxylate complexes based on anthracene‐9,10‐dicarboxylate (L) were synthesized and characterized: [{[Ag(L)][Ag(dmpy)₂]}_∞] ( 1 ) and [{[Ag₂(L)(bipy)₂]}_∞] ( 2 ) (dmpy = 2,6‐dimethylpyridine and bipy = 4,4′‐bipyridine). Complex 1 has an interesting framework consisting of anionic chains {[Ag(L)]^–}_∞ and the mononuclear cationic units [Ag(dmpy)₂]⁺, which is further assembled to form networks along the different crystallographic directions by the intermolecular C–H ··· Ag hydrogen‐bonding interactions. Complex 2 takes a ladder‐like chain structure by incorporating 4,4′‐bipyridine (bipy) as a bridging co‐ligand, which is further interlinked to generate a planar network through interchain Ag–Ag bonding contacts. The steric bulk of anthracene ring in L may play an important role in the formation of 1 and 2 . Moreover, the luminescent properties of the 1 and 2 were investigated in detail.