<Emphasis Type="Italic">In situ</Emphasis> detection and identification of microorganisms at single-colony resolution by spectral imaging

The in situ detection and identification of environmental microorganisms is important for general microbial ecology research. In addition, the rapid detection of microbial contamination in food-processing plants is essential. The current paper proposes a method for the rapid detection and identification of microorganisms using spectral imaging. Photosynthetic and non-photosynthetic bacterial colonies with different absorption spectra in the near-infrared wavelength region were measured directly from a Petri dish. The bacterial colonies were distinguished and subsequently typed using multiple discriminant analysis. The accuracy of the detection and identification of colonies of various sizes was evaluated. The results showed that colonies with diameters of 100 and 300 μm could be detected and identified, respectively, with adequate accuracy. Moreover, using our novel application of this spectral-imaging technique, the bacterial detection and identification times were reduced by more than half and by a few weeks, respectively, compared with conventional methods.     

Bifunctional Catalysts Based on m‐Phenylene‐Bridged Porphyrin Dimer and Trimer Platforms: Synthesis of Cyclic Carbonates from Carbon Dioxide and Epoxides

Highly active bifunctional diporphyrin and triporphyrin catalysts were synthesized through Stille coupling reactions. As compared with a porphyrin monomer, both exhibited improved catalytic activities for the reaction of CO₂ with epoxides to form cyclic carbonates, because of the multiple catalytic sites which cooperatively activate the epoxide. Catalytic activities were carefully investigated by controlling temperature, reaction time, and catalyst loading, and very high turnover number and turnover frequency were obtained: 220 000 and 46 000 h^?1, respectively, for the magnesium catalyst, and 310 000 and 40 000 h^?1, respectively, for the zinc catalyst. Results obtained with a zinc/free‐base hybrid diporphyrin catalyst demonstrated that the Br^? ions on the adjacent porphyrin moiety also function as nucleophiles.     

Substituent effects on the structures of silver complexes with monoazatrithia-12-crown-4 ethers bearing substituted aromatic rings

New 4'-methoxybenzyl-, 4'-methylbenzyl-, benzyl-, 3',5'-difluorobenzyl-, 3',5'-dichlorobenzyl-, and 4'-nitrobenzyl-armed monoazatrithia-12-crown-4 ethers were prepared by the reductive amination of monoazatrithia-12-crown-4 with the appropriate benzenecarbaldehyde in the presence of NaBH(OAc)3. Cold electrospray ionization mass spectrometry and X-ray crystallography show that silver complexes with armed monoazatrithia-12-crown-4 ethers bearing aromatic side arms with electron-donating groups or electron-withdrawing groups are coordination polymers and trimers, respectively. The structures of the silver complexes were strongly dependent on the strength of the CH...pi interactions, which are controlled by substituent effects on the aromatic side arms.     

Rhodium‐Catalyzed Synthesis of Chiral Spiro‐9‐silabifluorenes by Dehydrogenative Silylation: Mechanistic Insights into the Construction of Tetraorganosilicon Stereocenters

Mechanistic insight into the construction of quaternary silicon chiral centers by rhodium‐catalyzed synthesis of spiro‐9‐silabifluorenes through dehydrogenative silylation is reported. The C₂‐symmetric bisphosphine ligand, BINAP, was effective in controlling enantioselectivity, and axially chiral spiro‐9‐silabifluorenes were obtained in excellent yields with high enantiomeric excess. Monitoring of the reaction revealed the presence of a monohydrosilane intermediate as a mixture of two constitutional isomers. The reaction proceeded through two consecutive dehydrogenative silylations, and the absolute configuration was determined in the first silylative cyclization. Competitive reactions with electron‐rich and electron‐deficient dihydrosilanes indicated that the rate of silylative cyclization increased with decreasing electron density on the silicon atom of the starting dihydrosilane. Further investigation disclosed a rare interconversion between the two constitutional isomers of the monohydrosilane intermediate with retention of the absolute configuration.     

Solid‐State [2+2] Photodimerization of 1‐Aryl‐4‐pyridylbutadienes in Cation‐π‐Controlled Crystals

Irradiation of HX (X=CF₃SO₃ or CF₃CO₂) salts of 1‐aryl‐4‐pyridylbutadienes 1 a – 1 c in the solid‐state afforded syn head‐to‐tail dimers in good yields among a number of possible dimers, whereas irradiation of the neutral substrates gave a complex mixture or no products. A comparison of the X‐ray crystal structures of the neutral compounds and the HX salts clarified that their orientation modes are head‐to‐head and head‐to‐tail, respectively. Moreover, while the distances between the two neighboring double bonds of the neutral compounds are relatively far apart from each other, those of HX salts are close together, satisfying Schmidt's requirement. These findings suggested that cation‐π interactions between the pyridinium and aromatic rings are effective for the preorientation of the HX salts of substrates, leading to photodimers in high regio‐ and stereoselectivities.     

Children's recognition of American English consonants in noise

In contrast to the availability of consonant confusion studies with adults, to date, no investigators have compared children's consonant confusion patterns in noise to those of adults in a single study. To examine whether children's error patterns are similar to those of adults, three groups of children (24 each in 4-5, 6-7, and 8-9 yrs. old) and 24 adult native speakers of American English (AE) performed a recognition task for 15 AE consonants in /ɑ/-consonant-/ɑ/ nonsense syllables presented in a background of speech-shaped noise. Three signal-to-noise ratios (SNR: 0, +5, and +10 dB) were used. Although the performance improved as a function of age, the overall consonant recognition accuracy as a function of SNR improved at a similar rate for all groups. Detailed analyses using phonetic features (manner, place, and voicing) revealed that stop consonants were the most problematic for all groups. In addition, for the younger children, front consonants presented in the 0 dB SNR condition were more error prone than others. These results suggested that children's use of phonetic cues do not develop at the same rate for all phonetic features.     

Acoustic and perceptual similarity of Japanese and American English vowels

Acoustic and perceptual similarities between Japanese and American English (AE) vowels were investigated in two studies. In study 1, a series of discriminant analyses were performed to determine acoustic similarities between Japanese and AE vowels, each spoken by four native male speakers using F1, F2, and vocalic duration as input parameters. In study 2, the Japanese vowels were presented to native AE listeners in a perceptual assimilation task, in which the listeners categorized each Japanese vowel token as most similar to an AE category and rated its goodness as an exemplar of the chosen AE category. Results showed that the majority of AE listeners assimilated all Japanese vowels into long AE categories, apparently ignoring temporal differences between 1- and 2-mora Japanese vowels. In addition, not all perceptual assimilation patterns reflected context-specific spectral similarity patterns established by discriminant analysis. It was hypothesized that this incongruity between acoustic and perceptual similarity may be due to differences in distributional characteristics of native and non-native vowel categories that affect the listeners' perceptual judgments.     

Fluorescence Quenching‐based Assay for Measuring Golgi endo‐α‐Mannosidase

Golgi endo‐α‐mannosidase (G‐EM) catalyzes an alternative deglucosylation process for N‐glycans and plays important roles in the post‐endoplasmic reticulum (ER) quality control pathway. To understand the post‐ER quality control mechanism, we synthesized a tetrasaccharide probe for the detection of the hydrolytic activity of G‐EM based on a fluorescence quenching assay. The probe was labeled with an N‐methylanthraniloyl group as a reporter dye at the non‐reducing end and a 2,4‐dinitrophenyl group as a quencher at the reducing end. This probe is hydrolyzed to disaccharide derivatives by G‐EM, resulting in increased fluorescence intensity. Thus, the fluorescence signal is directly proportional to the amount of disaccharide derivative present, allowing the G‐EM activity to be evaluated easily and quantitatively.     

Diapolycopenedioic acid xylosyl ester, a novel glyco-C30-carotenoic acid produced by a new marine bacterium Rubritalea squalenifaciens

A novel acyl glyco-carotenoic acid, diapolycopenedioic acid xylosyl ester, was isolated from a marine bacterium Rubritalea squalenifaciens belonging to subdivision 1 of Verrucomicrobia as the major red pigment by using chromatographic methods. The structure of diapolycopenedioic acid xylosyl ester was determined to be 4-[2-O-(12-methyltridecanoyl)-β-xylopyranosyl] hydrogen 4,4′-diapo-ψ,ψ-carotene-4,4′-dioate by analysis of the MS and NMR data for this acid and for the diacetyl diapolycopenedioic acid xylosyl ester. The diapolycopenedioic acid xylosyl ester showed potent antioxidative activity against a lipid peroxidation model.