Synthesis of 1‐Methyl‐3‐aryl‐substituted Titanocene and Zirconocene Dichlorides and Crystal Structure of Bis[η5‐1‐methyl‐3‐(α, α‐dimethylbenzyl) cyclopentadienyl] titanium Dichloride

The syntheses of a series of l‐methyl‐3‐aryl‐substituted titanocene and zirconocene dichlorides are reported. These complexes are synthesized by the reaction of 2‐ and 3‐methyl‐6, 6‐dimethylfulvenes (1:4) with aryllithium, followed by the reaction with TiCl₄·2THF, ZrCl₄ and (CpTiCl₂)₂O respectively, to give complexes 1–5. The complex [η⁵‐1‐methyl‐3‐(α, α‐dimethylbenzyl) cyclopentadienyl] titanium dichloride has been studied by X‐ray diffraction. The red crystal of this complex is monoclinic, space group P2_t/C with unit cell parameters: a =6.973(6) × 10^?1 nm, b =36.91(2) × 10^?1 nm, c = 10.063(4) × 10^?1 nm, α=β= γ = 93.35(5)°, V = 2584(5) × 10^?3 nm³ and Z = 4. Refinement for 1004 observed reflections gives the final R of 0.088. There are four independent molecules per unit cell.     

Studies on the Mass Spectra of N‐Aryl α,β‐Unsaturated γ‐Lactams

The mass spectra of a series of N‐aryl α,β‐unsaturated γ‐lactams were studied. Besides the molecular ion, the three characteristic fragments such as [M⁺‐29], [M⁺‐55], and [M⁺‐82] were commonly found in a series of N‐Aryl α,β‐unsaturated γ‐lactams in EI/MS. Further more the mechanism for the interpretation of these fragments is also de scribed.     

Novel Polymer Clusters with a Uniform Chain Density

The thermal decomposition of polystyrene clusters prepared by using 4‐methacryloyloxy‐2,2,6,6‐tetramethylpiperidine‐N‐oxyl as a branching agent was studied. The weight‐average molar mass (M̄_w) and the radius of gyration (R_g) of the resultant clusters can be scaled as M̄_w ∝︁ R_g^{3.0 ± 0.1}, revealing that these clusters have a uniform chain density. Moreover, the dynamic properties of such clusters converge unexpectedly faster than the static properties as the molar mass decreases.     

Carbon fibre electrodes in flow potentiometric stripping analysis

The construction of carbon fibre flow electrodes suitable for use in connection with potentiometric and constant-current stripping is described, and the fibre electrodes are compared with a glassy carbon disc thin layer cell. The signal-to-background ratio is approximately 1.6 times higher for an 8–10 μm carbon fibre compared to the glassy carbon disc electrode. If an Ag/AgCl tube is used as both counter and reference electrode, the signal-to-noise ratio of the fibre electrode is approximately five times better than for a glassy carbon disc electrode with a calomel reference; the latter electrode design, however, gives slightly better precision. The dead volume and internal potential drop of the fibre electrodes are more than one order of magnitude smaller than for the glassy carbon disc electrode. Because of the simplicity of the manufacturing process and low material cost, the fibre cells can be used as disposable electrodes and the polishing process necessary in connection with glassy carbon disc electrodes can be omitted.     

冰晶石-氧化铝熔体结构的计算机模拟研究

用Monte Carlo法对冰晶石-氧化铝系熔体结构作了计算机模拟研究。结果表明: 熔体中既有含“氧桥”和“氟桥”的“多核”离子集团, 如F3Al-O-AlF_3、F_3Al-AlF_3、F_3Al—F—AlF_3—F等; 也有“单核”离子集团如AlF_5~(2-)、AlOF_3~(2-)等。熔体中还存在较松散的xNa~+·yF~-离子集团。熔体中不存在AlO_2~-或AlO_3~(3-)集团。     

Lipid Production by Culturing Oleaginous Yeast and Algae with Food Waste and Municipal Wastewater in an Integrated Process

Food waste and municipal wastewater are promising feedstocks for microbial lipid biofuel production, and corresponding production process is to be developed. In this study, different oleaginous yeast strains were tested to grow in hydrolyzed food waste, and growths of Cryptococcus curvatus, Yarrowia lipolytica, and Rhodotorula glutinis in this condition were at same level as in glucose culture as control. These strains were further tested to grow in municipal primary wastewater. C. curvatus and R. glutinis had higher production than Y. lipolytica in media made from primary wastewater, both with and without glucose supplemented. Finally, a process was tested to grow C. curvatus and R. glutinis in media made from food waste and municipal wastewater, and the effluents from these processes were further treated with yeast culture and phototrophic algae culture; 1.1 g/L C. curvatus and 1.5 g/L R. glutinis biomass were further produced in second-step yeast cultures, as well as 1.53 and 0.58 g/L Chlorella sorokiniana biomass in phototrophic cultures. The residual nitrogen concentrations in final effluents were 33 mg/L and 34 mg/L, respectively, and the residual phosphorus concentrations were 1.5 and 0.6 mg/L, respectively. The lipid contents in the produced biomass were from 18.7% to 28.6%.     

乙二胺铜－铁氰复合修饰电极薄膜的电沉积和结构表征及电化学性质

乙二胺铜－铁氰复合修饰电极薄膜的电沉积和结构表征及电化学性质陈昌国，李海梅，黄宗卿（重庆大学化工学院重庆６３００４４）关键词：铜、乙二胺，铁氰，修饰电极，光谱普鲁士兰（ＰＢ）修饰电极因其独特的电致变色现象而倍受关注。在１９７８年以来的十余年间里已相继...     

Surface-enhanced Raman scattering and DFT investigation of Eriochrome Black T metal chelating compound

The surface-enhanced Raman scattering (SERS) spectra of Eriochrome Black T (EBT) and its Cu(II), Fe(III), Mn(II) and Pb(II) complexes were recorded using a hydroxylamine reduced silver colloid. Molecular geometry optimization, molecular electrostatic potential (MEP) distribution and vibrational frequencies calculation were performed at B3LYP/6-31G(d) level of theory for the EBT molecule and its Cu(EBT), Fe(EBT) and Mn(EBT) metal complexes. Differentiation between EBT complexes of Cu(II), Fe(III), Mn(II) and Pb(II) is shown by the SERS spectral features of each complex.     

Bio‐/Chemosensors and Imaging with Aggregation‐Induced Emission Luminogens

Aggregation‐induced emission (AIE) luminogens show abnormal fluorescent behavior; they are non‐emissive in solution, but they become strongly emissive after aggregation. Sensing and imaging are the major applications of AIE luminogens. By properly manipulating the aggregation and deaggregation of AIE molecules, various bio‐/chemosensors have been developed. Moreover, AIE molecules with targeting groups have been devised for imaging of organelles and cancer cells. In this account, we report our recent work on the application of AIE luminogens for the construction of bio‐/chemosensors and imaging.

     

Correlation‐assisted nearest shrunken centroid classifier with applications for high dimensional spectral data

High throughput data are frequently observed in contemporary chemical studies. Classification through spectral information is an important issue in chemometrics. Linear discriminant analysis (LDA) fails in the large‐p‐small‐n situation for two main reasons: (1) the sample covariance matrix is singular when p > n and (2) there is an accumulation of noise in the estimation of the class centroid in high dimensional feature space. The Independence Rule is a class of methods used to overcome these drawbacks by ignoring the correlation information between spectral variables. However, a strong correlation is an essential characteristic of spectral data. We proposed a new correlation‐assisted nearest shrunken centroid classifier (CA‐NSC) to incorporate correlation information into the classification. CA‐NSC combines two sources of information [class centroid (mean) and correlation structure (variance)] to generate the classification. We used two real data analyses and a simulation study to verify our CA‐NSC method. In addition to NSC, we also performed a comparison with the soft independent modeling of class analogy (SIMCA) approach, which uses only correlation structure information for classification. The results show that CA‐NSC consistently improves on NSC and SIMCA. The misclassification rate of CA‐NSC is reduced by almost half compared with NSC in one of the real data analyses. Generally, correlation among variables will worsen the performance of NSC, even though the discriminatory information contained in the class centroid remains unchanged. If only correlation structure information is used (as in the case of SIMCA), the result will be satisfactory only when the correlation structure alone can provide sufficient information for classification. Copyright © 2015 John Wiley & Sons, Ltd.