Determination of Carbon‐based Engineered Nanoparticles in Marketed Fish by Microwave‐assisted Extraction and Liquid Chromatography‐atmospheric Pressure Photoionization‐tandem Mass Spectrometry

An optimized method for the determination of two major carbon‐based engineered nanoparticles (C₆₀ and C₇₀) in marketed fish samples is described. The method involves the use of microwave‐assisted extraction (MAE) coupled with liquid chromatography ‐ tandem mass spectrometry with atmospheric pressure photoionization (LC‐APPI‐MS/MS). Factors affecting the extraction efficiency of the analytes from fish samples were optimized by a central composite design method. The optimal extraction temperature and time for MAE were found to be 233 °C for 22 min, and the extraction solution was composed of toluene and acetone in a ratio of 4.64:1. The limits of quantitation (LOQs) were 0.1 and 0.05 ng/g for C₆₀ and C₇₀, respectively. The precision for these analytes at two spiked levels, as indicated by relative standard deviations (RSDs), were less than 10% for both intra‐ and inter‐day analysis. Accuracy, expressed as the mean extraction recovery, was between 85 and 98%. The method was further validated based on EU Commission Decision 2002/657/EC, including a decision limit (CCα) and detection capability (CCβ) for marketed fish samples.     

Effects of the temperature and beam parameters on depth profiles in X-ray photoelectron spectrometry and secondary ion mass spectrometry under C60–Ar cosputtering

Polymethylmethacrylate (PMMA) is widely used in various fields, including the semiconductor, biomaterial and microelectronic fields. Obtaining the correct depth profiles of PMMA is essential, especially when it is used as a thin-film. There have been many studies that have used earlier generation of cluster ion (SF₅⁺) as the sputtering source to profile PMMA films, but few reports have discussed the use of the more recently developed C₆₀⁺ in the PMMA sputtering process. In this study, X-ray photoelectron spectroscopy (XPS) and dynamic secondary ion mass spectroscopy (D-SIMS) were used concurrently to monitor the depth profiles of PMMA under C₆₀⁺ bombardment. Additionally, the cosputtering technique (C₆₀⁺ sputtering with auxiliary, low-kinetic-energy Ar⁺) was introduced to improve the analytical results. The proper cosputtering conditions could eliminate the signal enhancement near the interface that occurred with C₆₀⁺ sputtering and enhance the sputtering yield of the characteristic signals. Atomic force microscopy (AFM) was also used to measure the ion-induced topography. Furthermore, the effect of the specimen temperature on the PMMA depth profile was also examined. At higher temperatures (+120 °C), the depolymerization reaction that corresponded to main-chain scission dominated the sputtering process. At lower temperatures (−120 °C), the cross-linking mechanism was retarded significantly due to the immobilization of free radicals. Both the higher and lower sample temperatures were found to further improve the resulting depth profiles.     

Thermal‐ and Photo‐Induced Phase‐Transition Behaviors of a Tapered Dendritic Liquid Crystal with Photochromic Azobenzene Mesogens and a Bicyclic Chiral Center

A ribbon‐shaped chiral liquid crystalline (LC) dendrimer with photochromic azobenzene mesogens and an isosorbide chiral center (abbreviated as AZ₃DLC) was successfully synthesized and its major phase transitions were studied by using differential scanning calorimetry (DSC) and linear polarized optical microscopy (POM). Its ordered structures at different temperatures were further identified through structure‐sensitive diffraction techniques. Based on the experimental results, it was found that the AZ₃DLC molecule exhibited the low‐ordered chiral smectic (Sm*) LC phase with 6.31 nm periodicity at a high‐temperature phase region. AZ₃DLC showed the reversible photoisomerization in both organic solvents and nematic (N) LC media. As a chiral‐inducing agent, it exhibited a good solubility, a high helical‐twisting power, and a large change in the helical‐twisting power due to its photochemical isomerization in the commercially available N LC hosts. Therefore, we were able to reversibly “remote‐control” the colors in the whole visible region by finely tuning the helical pitch of the spontaneously formed helical superstructures.     

para‐Quinodimethane‐Bridged Perylene Dimers and Pericondensed Quaterrylenes: The Effect of the Fusion Mode on the Ground States and Physical Properties

Polycyclic hydrocarbon compounds with a singlet biradical ground state show unique physical properties and promising material applications; therefore, it is important to understand the fundamental structure/biradical character/physical properties relationships. In this study, para‐quinodimethane (p‐QDM)‐bridged quinoidal perylene dimers 4 and 5 with different fusion modes and their corresponding aromatic counterparts, the pericondensed quaterrylenes 6 and 7 , were synthesized. Their ground‐state electronic structures and physical properties were studied by using various experiments assisted with DFT calculations. The proaromatic p‐QDM‐bridged perylene monoimide dimer 4 has a singlet biradical ground state with a small singlet/triplet energy gap (?2.97 kcal mol^?1), whereas the antiaromatic s‐indacene‐bridged N‐annulated perylene dimer 5 exists as a closed‐shell quinoid with an obvious intramolecular charge‐transfer character. Both of these dimers showed shorter singlet excited‐state lifetimes, larger two‐photon‐absorption cross sections, and smaller energy gaps than the corresponding aromatic quaterrylene derivatives 6 and 7 , respectively. Our studies revealed how the fusion mode and aromaticity affect the ground state and, consequently, the photophysical properties and electronic properties of a series of extended polycyclic hydrocarbon compounds.     

Synthesis and Characterization of NiIIIN3S2 Complexes as Active Site Models for the Oxidized Form of Nickel Superoxide Dismutase

Nickel complexes, [Ni(H₂BA^RTPP)](ClO₄)₂ (R=Ph for 1 or iPr for 2 ), supported by a pentadentate ligand H₂BA^RTPP were synthesized and oxidized to form Ni^III species having a N3S2 coordination environment to mimic the active site of the oxidized form of nickel superoxide dismutase (NiSODox). The Ni^III species 2 ⁺ exhibited a rhombic signal with g values at 2.15, 2.12 and 2.02 similar to that of NiSODox. DFT calculations revealed that 2 ⁺ has an unpaired electron primarily located in the d orbital of the Ni^III center, which strongly overlaps with the p_z orbital of the axial pyridine nitrogen of H₂BA^PrTPP.     

Chirality Control of Quadruple Helixes of Metal Strings by Peripheral Chiral Ligands

Chirality control of helixes with the Δ (P) or Λ (M) form is interesting in various fields such as extended metal atom chains (EMACs), in which the metal backbones are helically wrapped by four ligands. Herein, we report two EMACs, Δ‐[Ni₅((?)camnpda)₄] and Λ‐[Ni₅((+)camnpda)₄], whose chiralities are controlled by chiral ligands with naphthyridine and camphorsulfonyl groups. There is a large energy difference (108 kcal mol^?1) between the two helical structures with one chiral ligand. Furthermore, the electron communication between [Ni₂]³⁺ units is more pronounced than in [Ni₅(bna)₄Cl₂]²⁺ (bna=binaphthyridylamido). The results demonstrate control of small‐scale helical structure and set the stage for future development of chiral controlled base and nanoelectronic devices.     

Simultaneous detection of single nucleotide polymorphisms and copy number variations in the CYP2D6 gene by multiplex polymerase chain reaction combined with capillary electrophoresis

CYP2D6 (cytochrome P450 2D6) is one of the most important enzymes involved in drug metabolism, and CYP2D6 gene variants may cause toxic effects of therapeutic drugs or treatment failure. In this research, a rapid and simple method for genotyping the most common mutant alleles in the Asian population (CYP2D6*1/*1, CYP2D6*1/*10, CYP2D6*10/*10, CYP2D6*1/*5, CYP2D6*5/*10, and CYP2D6*5/*5) was developed by allele-specific polymerase chain reaction (AS-PCR) combined with capillary electrophoresis (CE). We designed a second mismatch nucleotide next to the single nucleotide polymorphism (SNP) site in allele-specific primers to increase the difference in PCR amplification. Besides, we established simulation equations to predict the CYP2D6 genotypes by analyzing the DNA patterns in the CE chromatograms. The multiplex PCR combined with CE method was applied to test 50 patients, and all of the test results were compared with the DNA sequencing method, long-PCR method and real-time PCR method. The correlation of the analytical results between the proposed method and other methods were higher than 90%, and the proposed method is superior to other methods for being able to simultaneous detection of SNPs and copy number variations (CNV). Furthermore, we compared the plasma concentration of aripiprazole (a CYP2D6 substrate) and its major metabolites with the genotype of 25 patients. The results demonstrate the proposed genotyping method is effective for estimating the activity of the CYP2D6 enzyme and shows potential for application in personalized medicine. Similar approach can be applied to simultaneous detection of SNPs and CNVs of other genes.     

Highly Efficient Proline Ester‐based Nickel Catalysts for Michael Addition of Thiophenols to α,β‐Enones

Two N₃O₂ pentadentate ligands, BMPP and BPPP, were prepared for synthesizing highly efficient nickel catalysts, [Ni(BMPP)(CH₃CN)](ClO₄)₂ ( 1 ) and [Ni(BPPP)(CH₃CN)](BPh₄)(ClO₄) ( 2 ), for thia‐Michael addition of thiophenols to α,β‐enones. X‐ray structures of 1 and 2 revealed that a labile CH₃CN molecule was bound to the nickel center of the catalysts. ESI‐MS spectroscopy indicated that thiolate replaced the bound CH₃CN molecule and coordinated to the nickel center during the catalytic cycle.     

Diterpenoids from the Wood of Cunninghamia konishii

Investigation of the wood of Cunninghamia konishii resulted in the isolation and characterization of one new abietane diterpenoid, (6α,7β)‐7,8‐epoxy‐6‐hydroxyabieta‐9(11),13‐dien‐12‐one ( 1 ), and two new labdane diterpenoids, (12R)‐12‐hydroxylabda‐8(17),13(16),14‐trien‐19‐oic acid ( 2 ) and (12R)‐12‐hydroxylabda‐8(17),13(16),14‐trien‐18‐oic acid ( 3 ). The structures of these new compounds were elucidated by analysis of their spectroscopic data.     

Asymmetric Synthesis and Characterization of Chiral 2,2′‐Diamino‐3,3′‐diethoxycarbonyl‐8,8′‐diphenyl‐1,1′‐biazulene

Abstract

rac‐2,2′‐Diamino‐3,3′‐diethoxycarbonyl‐8,8′‐diphenyl‐1,1′‐biazulene was synthesized from diethyl 2‐aminoazulene‐1,3‐dicarboxylate and was optically resolved into two enantiomers of S‐form and R‐form. The enantioselective oxidative couplings with two chiral amines [(?)‐sparteine and (R)‐(+)‐α‐methylbenzylamine] and ferric chloride catalyst, and the asymmetric couplings with two chiral oxovanadium(IV) complexes of ethyl 2‐amino‐4‐phenylazulene‐1‐carboxylate, easily yielded chiral 2,2′‐diamino‐3,3′‐diethoxycarbonyl‐8,8′‐diphenyl‐1,1′‐biazulene. Therefore, the introduction of two phenyl groups at the 8‐ and 8′‐postions of each azulene ring using phenyl magnesium bromide via an addition–oxidation–decarboxylation mechanism resulted in 1,1′‐biazulene forming a chiral C₂ axis.