Liquid chromatography/mass spectrometry-based metabolic profiling to elucidate chemical differences of tobacco leaves between Zimbabwe and China

An approach was developed for extracting and analyzing the chemical components of tobacco leaves based on solvent extraction and rapid & resolution liquid chromatography/quadrupole time-of-flight mass spectrometry analysis. Two solvents with different polarities were used to extract hydrophilic components and hydrophobic components, respectively, the combined analytical data can provide a "global" view of metabolites. Based on the evaluation of parallel samples, it was found that this approach provided good repeatability, accurate and reliable profiling data, and is suitable for the metabolomics study of tobacco leaves. In order to find the chemical component differences of tobacco leaves, 56 samples from Zimbabwe and China were analyzed using the developed method. The metabolite data were processed by multivariate statistic technique; an obvious group classification between Zimbabwe and China was observed, 14 significantly changed compounds were found, and 9 of them were identified.     

Biomimetic antireflective hierarchical arrays

We report a simple method for the fabrication of biomimetic antireflective hierarchical arrays based on the combination of self-assembled polymer spheres and nanoimprint lithography (NIL). The hierarchical structures are fabricated by creating nanopillars on the microscale round protrusion arrays, which are similar to natural mosquito eyes consisting of combined micro- and nanostructures. The hierarchical arrays dramatically suppress the surface reflection from visible to near-infrared regions with an angle of incidence of up to 70°.     

Study of defect sites in Ce1-xMxO2-δ (x = 0.2) solid solutions using Raman spectroscopy

A series of Ce(1-x)M(x)O(2-δ) (M = Gd, Zr, La, Sm, Y, Lu, and Pr) samples were characterized by Raman spectroscopy to investigate the evolution of defect sites (oxygen vacancies and MO(8)-type complex) and their distributions in the samples. It was found that the evolution of oxygen vacancies was due to the different ionic valence state of dopant from that of Ce(4+), while the evolution of the MO(8)-type complex was due to the different ionic radius of dopant from that of Ce(4+). The distributions of defect sites were investigated using 325 and 514 nm excitation laser lines, indicating that the defect sites were surface enriched. Moreover, the increasing ordering level of the sample led to a decline in the concentration of the MO(8)-type complex in the sample but the constant concentration of oxygen vacancies, implying that the metastable MO(8)-type complex species were more disordered compared to the oxygen vacancies.     

Molecular tilting and its impact on frictional properties of n-alkane self-assembled monolayers

Hydrophobic, methyl-terminated self-assembled monolayer (SAM) surfaces can be used to reduce friction. Among methyl-terminated SAMs, the frictional properties of alkanethiol SAMs and silane SAMs have been well-studied. In this research, we investigated friction of methyl-terminated n-hexatriacontane (C36) SAM and compared its friction properties with the alkanethiol and silane SAMs. Alkane SAM does not have an anchoring group. The alkane molecules stand on the surface by physical adsorption, which leads to a higher surface mobility of alkane molecules. We found that C36 SAM has a higher coefficient of friction than that of octadecyltrichlorosilane (OTS) silane. When an atomic force microscope (AFM) tip was swiped across the alkane SAM with a loading force, we found that the alkane SAM can withstand the tip loading pressure up to 0.48 GPa. Between 0.48 and 0.49Ga, the AFM tip partially penetrated the SAM. When the tip moved away, the deformed SAM healed and maintained the structural integrity. When the loading pressure was higher than 0.49 GPa, the alkane SAM was shaved into small pieces by the tip. In addition, we found that the molecular tilting of C36 molecules interacted with the tribological properties of the alkane SAM surface. On one hand, a higher loading force can push the rod-like alkane molecules to a higher tilting angle; on the other hand, a higher molecular tilting leads to a lower friction surface.     

Metal-free catalysts for hydrogenation of both small and large imines: a computational experiment

This study extends our previous work of using π-FLP strategy to develop metal-free hydrogenation catalysts. Using small MeN=CMe(2) imine (im1) as a model, we previously designed cat1 and cat2 catalysts. But it is unclear whether they are capable of catalyzing the hydrogenations of bulky imines. Using tBuN=C(H)Ph (im2) as a representative of large imines, we assessed the energetics of the cat1- and cat2-catalyzed im2 hydrogenations. The predicted energetics indicates that they can still catalyze large imine hydrogenations with experimentally accessible kinetic barriers, although the energetics becomes less favorable. To improve the catalysis, we proposed new catalysts (cat3 and cat4) by tailoring cat1 and cat2. The study indicates that cat3 and cat4 could have better performance for the hydrogenation of the bulky im2 than cat1 and cat2. Remarkably, cat3 and cat4 are also found suitable for small imine (im1) hydrogenation. Examining the hydrogen transfer substeps in the eight hydrogenations involved in this study, we observed that the mechanism for the hydrogen transfer step in the catalytic cycles depends on the steric effect between catalyst and substrate. The mechanism can be switched from stepwise one in the case of large steric effect (e.g.im2/cat2) to the concerted one in the case of small steric effect (e.g.im1/cat3). The new catalysts could be better targets for experimental realization because of their simpler constructions.     

Organocatalytic asymmetric conjugate addition and cascade acyl transfer reaction of α-nitroketones

Organocatalytic asymmetric conjugate addition of α-nitroketones to β,γ-unsaturated α-keto esters has been developed. A pyrrolidine-based thiourea-tertiary amine was identified as the best catalyst. The reaction was found to proceed via cascade conjugate addition and acyl transfer reaction. A number of α-nitroketones and β,γ-unsaturated α-keto esters were examined in this transformation. 5-Nitro-2-acyloxypent-2-enoates were obtained in good yields (up to 99%) and enantioselectivities (up to 99% ee). The products could be hydrolyzed to provide 5-nitro-2-oxopentanoates, which are not available from the direct addition of nitromethane to β,γ-unsaturated α-keto esters.     

Palladium-catalyzed coupling of haloalkynes with allyl acetate: a regio- and stereoselective synthesis of (Z)-β-haloenol acetates

A Pd-catalyzed coupling of haloalkynes with allyl acetate has been reported, providing a convenient method for the stereoselective synthesis of (Z)-β-haloenol acetates in good yields. The synthetic utility of this method is demonstrated by the formation of functionalized enol acetates via the Suzuki-Miyaura or Sonogashira coupling of the resulting (Z)-β-haloenol acetate products.     

Luminescent organic 1D nanomaterials based on bis(β-diketone)carbazole derivatives

A series of new triphenylamine-functionalized bis(β-diketone)s bridged by a carbazole (CnBDKC, n=1, 4, 8, 16) with twisted intramolecular charge-transfer emission in polar solvents has been synthesized. The length of the carbon chains has a significant effect on the self-assembling properties of the compounds. Well-defined 1D nanowires were easily generated from C1BDKC with a methyl group by a reprecipitation approach directed by π-stacking interaction, and the molecules packed into J-aggregates in the nanowires. In addition, 1D nanofibers based on C16BDKC bearing a long hexadecyl chain were prepared through the organogelation process, and H-aggregates were formed driven by the synergistic effect of π-stacking interaction and van der Waals force in the gel phase. C4BDKC and C8BDKC containing butyl and octyl side chains, respectively, cannot arrange into dispersed nanostructures, probably because π-π interaction between conjugated moieties might be disturbed by the interaction between the side chains, which is, however, not strong enough to dominate the self-assembling process. Notably, the nanowires based on C1BDKC and the gel nanofibers from C16BDKC can emit strong green light under irradiation, which suggests that these 1D nanomaterials may have potential applications in emitting materials as well as photonic devices.     

铜(Ⅱ)-三氮唑偶氮络合物与脱氧核糖核酸相互作用的电化学行为

运用电化学方法研究了铜（Ⅱ）－三氮唑偶氮（2－[2,3,5-三氮唑偶氮]-5－二甲氨基苯甲酸，TZAMB）络合物与脱氧核糖核酸（DAN）的相互作用。在pH2.5(0.05mol/L）邻苯二甲酸氢钾（PBS）缓冲溶液中，DNA与Cu(Ⅱ）－TZAMB络合物形成一种电惰性结合物，使Cu（Ⅱ）－TZAMB络合物的还原峰电流减小。通过循环伏安法、盐效应以及紫外－可见吸收谱证实了是由Cu(Ⅱ）－TZAMB络合物与DNA形成一种插入式的电惰性结合物而使其峰电流下降。根据这种峰电流下降可以测定DNA，测定结果令人满意。     

单分散聚苯乙烯微球的制备及影响因素研究

以聚乙烯吡咯烷酮为分散剂，无水乙醇为反应介质，偶氮二异丁腈为引发剂，采用分散聚合工艺，通过优化反应条件，制备出了粒径为5μm单分散（分散系数≤5％）聚苯乙烯微球。所制备的聚苯乙烯微球标准偏差δ＝0．16μm，分散系数ε＝0．02，且具有良好的球形度，表面非常光滑，无破损，无缺损。对影响单分散聚苯乙烯微球的因素进行了研究，结果表明：随着分散稳定剂用量的增加，聚苯乙烯微球的粒径减小；随着单体和引发剂用量的增加，聚苯乙烯微球的粒径增大。分散稳定剂和单体用量是影响聚苯乙烯微球粒径分布的两个主要因素。