An abnormal temperature dependence of alkylpyrazines' retention in reversed-phase liquid chromatography

Retention behaviors of pyrazine and alkylpyrazines on various stationary phases in reversed-phase liquid chromatography were examined. An abnormal temperature effect on the retention of alkylpyrazines with a mobile phase consisting of acetonitrile and water was observed when changing the column temperature. On the other hand, no similar trend was found with a methanol-water mobile phase. For all the columns investigated in this work, the above tendency to the temperature-dependence was consistently observed, suggesting that the abnormal temperature effect on the retention of alkylpyrazines could be mainly induced by an acetonitrile-based mobile phase.     

Doubly activated supramolecular reaction: transesterification of acyclic oligoether esters with metal alkoxides

Transesterification reactions of acyclic oligoether esters E3-E10 with metal alkoxides were accelerated upon noncovalent complexation of the esters with metal ions. In the reaction of monovalent alkaline metal alkoxides, CH(3)ONa and CH(3)OK, plots of the observed rate constants k(obs) with respect to the chain length of E3-E10 showed selective acceleration of the transesterification. Compared with the shortest E3, which can hardly bind metal ion, 4.3- and 6.6-fold accelerations in the maxima were achieved in the combinations of E5/CH(3)ONa and E6/CH(3)OK, respectively. Supramolecular intermediate complex could be spectrometrically visualized by ESI-FT-ICR-MS in the course of reaction. Kinetic experiments, together with structural analyses by means of NMR, mass spectrometry, and DFT calculations of the intermediate complexes, indicate that a size-fit complex of host substitute with alkali metal ion allows strong electron withdrawing due to the close contact of the carbonyl oxygen to the metal ion, resulting in the selective rate enhancement of the reaction, while in the reaction of E3-E10 with a divalent alkaline earth metal alkoxide, (CH(3)CH(2)O)(2)Ba, the k(obs) values increased stepwise with elongation of the side arm to attain an dramatic large acceleration. In comparison with the k(obs) of E3, 4610-fold acceleration was achieved in the reaction of E10. The double activation of the host substrate and guest counter nucleophile at once brings about this extraordinary rate acceleration. The strong wrapping complexation of long oligoether ester with barium ethoxide allows for the effective electron withdrawal from the ester carbonyl group (host activation) as well as separation of the accompanying guest alkoxide anions (guest activation).     

Synthesis of silyl-functionalized oligothiophene-based polymers with bright blue light-emission and high refractive index

In this paper, we report the synthesis of partially conjugated polymers with a silyl-group-substituted oligothiophene and a short alkyl chain in the main chain by hydrosilylation polymerization and describe their optical properties such as luminescence and refractive index. The obtained polymers are found to have good solubility and processability. Moreover, the high steric hindrance of the silyl-group can inhibit the π-π interaction and intermolecular aggregation of the polymers. Hence, the emission of the obtained polymers was similar to that of the corresponding silyl-group-substituted oligothiophene. The polymers exhibit intense light blue fluorescence under UV irradiation and a high refractive index in the visible light region.     

Comparison of biosensor platforms for surface plasmon resonance based detection of paralytic shellfish toxins

Paralytic shellfish poisoning (PSP) toxins are produced by certain marine dinoflagellates and may accumulate in bivalve molluscs through filter feeding. The Mouse Bioassay (MBA) is the internationally recognised reference method of analysis, but it is prone to technical difficulties and regarded with increasing disapproval due to ethical reasons. As such, alternative methods are required. A rapid surface plasmon resonance (SPR) biosensor inhibition assay was developed to detect PSP toxins in shellfish by employing a saxitoxin polyclonal antibody (R895). Using an assay developed for and validated on the Biacore Q biosensor system, this project focused on transferring the assay to a high-throughput, Biacore T100 biosensor in another laboratory. This was achieved using a prototype PSP toxin kit and recommended assay parameters based on the Biacore Q method. A monoclonal antibody (GT13A) was also assessed. Even though these two instruments are based on SPR principles, they vary widely in their mode of operation including differences in the integrated μ-fluidic cartridges, autosampler system, and sensor chip compatibilities. Shellfish samples (n = 60), extracted using a simple, rapid procedure, were analysed using each platform, and results were compared to AOAC high performance liquid chromatography (HPLC) and MBA methods. The overall agreement, based on statistical 2 × 2 comparison tables, between each method ranged from 85% to 94.4% using R895 and 77.8% to 100% using GT13A. The results demonstrated that the antibody based assays with high sensitivity and broad specificity to PSP toxins can be applied to different biosensor platforms.     

Molecular functions of PsbP and PsbQ proteins in the photosystem II supercomplex

The PsbP and PsbQ proteins are extrinsic subunits of the photosystem II (PSII) supercomplex, which are found in green plants including higher plants and green algae. These proteins are thought to have evolved from their cyanobacterial homologs; cyanoP and cyanoQ respectively. It has been suggested that the functions of PsbP and PsbQ have largely changed from those of cyanoP and cyanoQ. In addition, multiple isoforms and homologs of PsbP and PsbQ were found in green plants, indicating that the acquisition of PsbP and PsbQ in PSII is not a direct path but a result of intensive functional divergence during evolution from cyanobacterial endosymbiont to chloroplast. In this review, we highlight newly introduced topics related to the functions and structures of both PsbP and PsbQ proteins. The present data suggest that PsbP together with PsbQ have specific and important roles in coordinating the activity of the donor and acceptor sides of PSII and stabilizing the active form of the PSII-light-harvesting complex II (LHCII) supercomplex.     

Doubly doped BaY2F8:Er,Nd VUV scintillator

Doubly doped BaY₂F₈:Er,Nd scintillation crystals were grown by modified micro-pulling-down method. The Er co-doping was chosen to enhance the energy transfer from the host lattice to the Nd³⁺ luminescence center via the 5d-levels of Er³⁺, which can be enabled by the overlap of Er³⁺ 5d-4f emission spectrum with the Nd³⁺ 4f-5d absorption. The energy transfer was clearly evidenced in the BaY₂F₈:Er,Nd. The processes are complicated by energy migration to killer centres and/or cross-relaxation processes. The luminescence and energy transfer mechanism are discussed.     

Non-Orthogonality Measure for a Collection of Pure Quantum States

Modern optical communication technology can realize a large-scale multilevel (or M-ary) optical signal. Investigating the quantum mechanical nature of such a large-scale M-ary optical signal is essential for a unified understanding of quantum information science and optical communication technology. This article focuses on the quantum-mechanical non-orthogonality for a collection of pure quantum states and proposes a non-orthogonality index based on the least squares error criterion in quantum detection theory. First, we define the index for linearly independent signals, and the proposed index is analyzed through numerical simulations. Next, the index is applied to a highly large-scale M-ary phase-shift keying (PSK) coherent state signal. Furthermore, the index is compared with the capacity of the pure state channel with the PSK signal. As a result, it is shown that a highly large-scale M-ary PSK coherent state signal exhibits a quantum nature even when the signal transmission power is very high. Thus, the theoretical characterization of a highly large-scale M-ary coherent state signal based on the proposed index will be the first step toward a better understanding of cutting-edge optical communication technologies such as the quantum stream cipher Y00.     

Synthesis of Highly Emissive Fluorophores Based on Multiply Stacked Anthracene Arrangement

Newly designed fluorophore systems with feather-like structures were constructed by connecting bisanthracene building units via a concise reaction sequence of bromination, etherification, and desilylation. Spectroscopic characterizations revealed that all of the fluorophore systems achieved high light absorptivity and high emission efficiency by preventing closely spaced anthracene chromophores from mutual interactions to reduce concomitant energy loss by fluorescence quenching. The application of fluorophore systems for the preparation of light-harvesting dyad materials has successfully demonstrated their potential utility as versatile photofunctional tools.