An uncertainty evaluation for multiple measurements by GUM, III: using a correlation coefficient

After a measurement, a measured value and a measurement uncertainty are produced as a measurement result. By a repeated measurement, another measurement result is produced. Between the individual results of the two measurements, it is shown that there may be a significant correlation. A correlation coefficient can be determined when a GUM-compliant uncertainty budget for a measurement is available. Utilizing the correlations between the N individual results, an equation is derived to combine the N individual uncertainties of N measurements. Using the newly derived equation including the correlation coefficient, three measurement uncertainties of three measurement results are combined as an example. The combined uncertainty is compared with the uncertainty of a measurement which treats the three individual measurements as one process. Papers published in this section do not necessarily reflect the opinion of the editors, the editorial board, or the publisher.     

Tetradentate Gold(III) Complexes as Thermally Activated Delayed Fluorescence (TADF) Emitters: Microwave-Assisted Synthesis and High-Performance OLEDs with Long Operational Lifetime

Structurally robust tetradentate gold(III)-emitters have potent material applications but are rare and unprecedented for those displaying thermally activated delayed fluorescence (TADF). Herein, a novel synthetic route leading to the preparation of highly emissive, charge-neutral tetradentate [C^C^N^C] gold(III) complexes with 5-5-6-membered chelate rings has been developed through microwave-assisted C−H bond activation. These complexes show high thermal stability and with emission origin (³IL, ³ILCT, and TADF) tuned by varying the substituents of the C^C^N^C ligand. With phenoxazine/diphenylamine substituent, we prepared the first tetradentate gold(III) complexes that are TADF emitters with emission quantum yields of up to 94 % and emission lifetimes of down to 0.62 μs in deoxygenated toluene. These tetradentate Au^III TADF emitters showed good performance in vacuum-deposited OLEDs with maximum EQEs of up to 25 % and LT₉₅ of up to 5280 h at 100 cd m⁻².     

Changes in Isoflavone Profile from Soybean Seeds during Cheonggukjang Fermentation Based on High-Resolution UPLC-DAD-QToF/MS: New Succinylated and Phosphorylated Conjugates

In this study, thirty-eight isoflavone derivatives were comprehensively identified and quantified from the raw, steamed and fermented seeds of four selected soybean cultivars based on UPLC-DAD-QToF/MS results with reference to the previously reported LC-MS library and flavonoid database, and summarized by acylated group including glucosides (Glu), malonyl-glucosides (Mal-Glu), acetyl-glucosides (Ac-Glu), succinyl-glucosides (Suc-Glu) and phosphorylated conjugates (Phos) in addition to aglycones. Among them, Suc-Glu and Phos derivatives were newly generated due to fermentation by B. subtilis AFY-2 (cheonggukjang). In particular, Phos were characterized for the first time in fermented soy products using Bacillus species. From a proposed roadmap on isoflavone-based biotransformation, predominant Mal-Glu (77.5–84.2%, raw) decreased rapidly by decarboxylation and deesterification into Ac-Glu and Glu (3.5–8.1% and 50.0–72.2%) during steaming, respectively. As fermentation continued, the increased Glu were mainly succinylated and phosphorylated as well as gradually hydrolyzed into their corresponding aglycones. Thus, Suc-Glu and Phos (17.3–22.4% and 1.5–5.4%, 36 h) determined depending on cultivar type and incubation time, and can be considered as important biomarkers generated during cheonggukjang fermentation. Additionally, the changes of isoflavone profile can be used as a fundamental report in applied microbial science as well as bioavailability research from fermented soy foods.     

Upper bound on the slope of steady water waves with small adverse vorticity

We consider the angle of inclination (with respect to the horizontal) of the profile of a steady 2D inviscid symmetric periodic or solitary water wave subject to gravity. There is an upper bound of 31.15° in the irrotational case [1] and an upper bound of 45° in the case of favorable vorticity [13]. On the other hand, if the vorticity is adverse, the profile can become vertical. We prove here that if the adverse vorticity is sufficiently small, then the angle still has an upper bound which is slightly larger than 45°.     

Influence of basic residues on dissociation kinetics and dynamics of singly protonated peptides: time‐resolved photodissociation study

Product ion yields in postsource decay and time‐resolved photodissociation at 193 and 266 nm were measured for some peptide ions with lysine ([KF₆ + H]⁺, [F₆K + H]⁺, and [F₃KF₃ + H]⁺) formed by matrix‐assisted laser desorption ionization. The critical energy (E₀) and entropy (ΔS^?) were determined by RRKM fitting of the data. The results were similar to those found previously for peptide ions with histidine. To summarize, the presence of a basic residue, histidine or lysine, inside a peptide ion retarded its dissociation by lowering ΔS^?. On the basis of highly negative ΔS^?, presence of intramolecular interaction involving a basic group in the transition structure was proposed. Copyright © 2009 John Wiley & Sons, Ltd.     

Asymmetric cross-benzoin condensation promoted by a chiral triazolium precatalyst bearing a pyridine moiety

Cross-benzoin condensation catalyzed by NHC, prepared from chiral triazolium salts bearing a pyridine ring, afforded α-hydroxy ketones with reasonable chemical yields and enantioselectivities. A wide range of aliphatic and aromatic aldehydes were successfully used in the reaction.     

Extended resolution wide-field optical imaging: objective-launched standing-wave total internal reflection fluorescence microscopy

Standing-wave total-internal-reflection fluorescence (SW-TIRF) microscopy uses a super-diffraction-limited standing evanescent wave to extract the high-spatial-frequency content of an object through a diffraction-limited optical imaging system. The effective point-spread function is better than a quarter of the emission wavelength. With a 1.45 numerical aperture objective and 532 nm excitation wavelength, a Rayleigh resolution of approximately 100 nm can be achieved, which is better than twice the resolution of conventional TIRF microscopy. This first experimental realization of SW-TIRF in an objective-launched geometry demonstrates the potential for extended resolution imaging at high speed by using wide-field microscopy.     

Genetic analyzer-dependent DNA methylation detection and its application to existing age prediction models

DNA methylation is the most promising biomarker for estimating human age. There are various methods used for analyzing DNA methylation. Among those, the SNaPshot assay-based method provides a semi-quantitative measurement of DNA methylation using capillary electrophoresis on genetic analyzers. However, DNA methylation measures produced using different types of genetic analyzers have never been compared, although differences in methylation values can directly affect age estimates. To evaluate the differences between the results generated by different genetic analyzers, we analyzed the same blood, saliva, and control methylated DNA using three genetic analyzers—the Applied Biosystems 3130, 3500, and SeqStudio—and compared the methylation values at five CpG sites: ELOVL2, FHL2, KLF14, MIR29B2C, and TRIM59. The methylation value at each of the five CpG sites decreased in the order 3130, 3500, and SeqStudio. The differences in the results produced by the different genetic analyzers resulted in significant errors when applying the 3500 and SeqStudio data to a previous age estimation model constructed using the 3130 Genetic Analyzer data. Therefore, DNA methylation measurements from 3500 and SeqStudio were corrected using the regression functions obtained by plotting the DNA methylation data of one instrument versus the other to facilitate the application of DNA methylation data from one instrument to the age prediction model based on other instruments. The age prediction accuracy obtained by applying corrected 3500 and SeqStudio data to the existing age estimation model was as high as observed in the 3130 data.     

Scalar coupling across [C-H···F-C] interactions in (σ-aryl)-chelating post-metallocenes

The nature and importance of C-H···F-C interactions is a topical yet controversial issue, and the development of spectroscopic methods to probe such contacts is therefore warranted. A series of Group 4 bis(benzyl) complexes supported by (σ-aryl)-2-phenolate-6-pyridyl [O,C,N-R(1)] ligands bearing a fluorinated R(1) group (CF(3) or F) in the vicinity of the metal has been prepared. The X-ray crystal structure of the CF(3)-substituted Hf derivative features intramolecular C-H···F-C and Hf···F-C contacts. All complexes have been characterized by multinuclear NMR spectroscopy. The (1)H and (13)C NMR spectra of [M(O,C,N-CF(3))(CH(2)Ph)(2)] derivatives display coupling (assigned to (1h)J(HF) and (2h)J(CF) for Ti; (3)J(HF) and (2)J(CF) (through M···F) for Hf and Zr) between the benzyl CH(2) and CF(3) moieties. [(1)H,(19)F]-HMBC NMR experiments have been performed for the M-[O,C,N-R(1)] complexes and their [O,N,C] counterparts, revealing significant scalar coupling across the C-H···F-C interactions for Ti-[O,C,N] and [O,N,C] species.     

Nuclear magnetic resonance-based metabolomics for prediction of gastric damage induced by indomethacin in rats

Non-steroidal anti-inflammatory drugs (NSAIDs) have side effects including gastric erosions, ulceration and bleeding. In this study, pattern recognition analysis of the ¹H-nuclear magnetic resonance (NMR) spectra of urine was performed to develop surrogate biomarkers related to the gastrointestinal (GI) damage induced by indomethacin in rats. Urine was collected for 5 h after oral administration of indomethacin (25 mg kg⁻¹) or co-administration with cimetidine (100 mg kg⁻¹), which protects against GI damage. The ¹H-NMR urine spectra were divided into spectral bins (0.04 ppm) for global profiling, and 36 endogenous metabolites were assigned for targeted profiling. The level of gastric damage in each animal was also determined. Indomethacin caused severe gastric damage; however, indomethacin administered with cimetidine did not. Simultaneously, the patterns of changes in their endogenous metabolites were different. Multivariate data analyses were carried out to recognize the spectral pattern of endogenous metabolites related to indomethacin using partial least square-discrimination analysis. In targeted profiling, a few endogenous metabolites, 2-oxoglutarate, acetate, taurine and hippurate, were selected as putative biomarkers for the gastric damage induced by indomethacin. These metabolites changed depending on the degree of GI damage, although the same dose of indomethacin (10 mg kg⁻¹) was administered to rats. The results of global and targeted profiling suggest that the gastric damage induced by NSAIDs can be screened in the preclinical stage of drug development using a NMR based metabolomics approach.