Depth estimation of protoporphyrin IX objects in turbid media considering the fluorescence intensity ratio between two wavelengths of light for application in invasion diagnosis of gastric cancer

Optical Review - This paper demonstrates a method to estimate the depth of a fluorescence object in turbid media using dual-wavelength excited photodynamic diagnosis, to aid in the invasion depth...     

Catalytic direct 1,4-conjugate addition of aldehydes to vinylketones on secondary-amines immobilised in FSM-16 silica

Direct 1,4-conjugate addition of naked aldehydes to vinylketones is catalysed effectively by N-methyl-3-aminopropylated FSM-16 mesoporous silica, which can be regarded as a novel heterogeneous catalysis for a practical C-C bond formation reaction.     

High-resolution analysis of polyprenols by supercritical fluid chromatography

A high-resolution analysis of polyprenol mixtures was achieved by supercritical fluid chromatography (SFC). The separation of polyprenols was examined on an octadecylsilane-packed column with liquid carbon dioxide as the mobile phase and ethanol as modifier. Using this chromatography system, the resolution of separation (Rs) between octadecaprenol (prenol 18) and nonadecaprenol (prenol 19) was two times higher than that using conventional reversed-phase high-performance liquid chromatography. Our SFC technique allows the advantage of baseline separation of polyprenol samples containing hydrophobic components such as terpenes or fatty acids that are unfavorable for good separation. This method is very useful for the analysis of structurally close polyprenol analogues of rubber plant metabolites.     

Efficient synthesis of an optically active tetrahydrozerumbone exhibiting a fragrance and the application of zerumbone derivatives with a medium ring structure

(R)-Tetrahydrozerumbone 2, which has a powerful balmy fragrance, contains a stereogenic carbon at the C2 position and can be easily prepared from zerumbone 1, one of the most important materials displaying an NMRDOS character. The reduction of 2 gave two diastereomers of tetrahydrozerumbol 3, and the optically active (>99%ee) alcohols were obtained by a lipase-catalyzed stereoselective transesterification of each racemic alcohol. A barrier to this development is a long reaction time (about four weeks) and the need to separate the diastereoisomers. The desired (2R)-form of 3 was efficiently obtained by a lipase-catalyzed transesterification under optimized conditions using a diastereomeric mixture of racemic 3 as the starting material without separation of the diastereomers. Using this method, the reaction of other zerumbone derivatives is greatly improved.     

Novel synthesis of zerumbone-pendant derivatives and their biological activity

Zerumbone 1, having powerful latent reactivity and containing two conjugated double bonds and a double conjugated carbonyl group is the major component of the essential oil of wild ginger, Zingiber zerumbet Smith. The conjugation system plays an important role in the expression of biological activity. N-Bromosuccinimide (NBS) reaction of 1 gave high reactive intermediate 2 with an exo-methylene group, which was obtained from 1 quantitatively. Treatment of 2 with nucleophiles gave various zerumbone-pendant derivatives, including C–H, C–O, C–N, and C–C bond formation, maintaining the conjugation system through S_N2′-type reaction. Almost all zerumbone-pendant derivatives showed a good value of IC₅₀ against the suppressive effect of NO generation. Among them, amine derivative 5, binding with 2 mol of zerumbone, showed the strongest activity (IC₅₀: 0.24 μM).     

Preparation and properties of isotactic and syndiotactic poly(methyl methacrylate)s,uniform with respect to molecular weight

Highly isotactic (it-) and highly syndiotactic (st-) poly(methyl methacrylate)s (PMMAs) uniform with respect to molecular weight (stereoregular, uniform PMMAs) were isolated up to the 100mer from it- and st-PMMAs by supercritical fluid chromatography (SFC) and characterized by NMR and mass spectroscopies. Glass transition temperatures (Tg's) of the uniform it- and st-PMMAs were higher than those of the corresponding PMMAs with MWD and with similar molecular weight on average. The Tg values of the uniform it-and st-PMMAs series obeyed the relationship, Tg = Tg∞ - K/M, where M and Tg∞ denote molecular weight and Tg at infinite M, respectively. The reciprocal melting points (1/Tm) of uniform it-PMMA (degree of polymerization, DP = 28–44), obtained from methanol solutions by evaporating the solvent, increased linearly with increasing 1/DP. Extrapolation of the linear relation to 1/DP = 0 gave the Tm of it-PMMA with infinite DP; Tm∞ = 171.1°C. Thermal degradation behavior was studied by thermogravimetry and by SFC analysis of degradation products. In gel-permeation chromatography (GPC) measurements, the it-50mer eluted faster than the st-50mer. Calibration curves for it- and st-PMMAs could be obtained using series of the uniform PMMAs. The instrumental spreading factor determined using it-25mer, it-50mer, st-25mer and st-50mer for our GPC chromatograph was 0.070 ml when the volume of the sample solution was 0.003ml. GPC analysis of a mixture of the it- and st-50mers in tetrahydrofuran indicated formation of a stereocomplex in the solution, and was found quite useful to elucidate the minimum sequence length required for complex formation.     

High-performance optical code generation and recognition by use of a 511-chip, 640-Gchip/s phase-shifted superstructured fiber Bragg grating

The generation and recognition of a record-length 511-chip optical code is experimentally demonstrated by use of a superstructured fiber Bragg grating (SSFBG) with a chip rate of 640 Gchips/s. Very high reflectivity (92%) is achieved with high-quality correlation properties. The temperature deviation tolerance is approximately +/- 0.3 degrees C, which is within the package's temperature stability range (+/- 0.1 degrees C). Experimental results show good agreement with the theory. They indicate the SSFBG's potential for processing a long optical code with an ultrahigh chip rate, which could significantly improve the system's performance.     

Pipette tip biosensors for bacterial double-stranded DNA using bioluminescence induced by zinc finger luciferase

The authors describe a pipette type of biosensor for detecting target genes and using a zinc finger protein fused to luciferase (ZF luciferase). The ZF protein binds to a specific DNA sequence, and the target double-stranded (ds) DNA can be detected by monitoring the enzymatic activity of ZF luciferase. A small avidin-immobilized reaction plate is placed on a plastic pipette tip (referred to as Biologi tip). The dsDNA detection procedures are carried out by using a programmable dispensing robot equipped with a photodetector. These procedures include (a) the aspiration of an analyte to capture the biotinylated target dsDNA (a product of a polymerase chain reaction) on the small reaction plate inside the pipette tip, (b) the introduction of ZF luciferase and luciferin into the pipette tip, and (c) migration of the pipette tip to the detection port to measure bioluminescence on the small reaction plate. The emission originating from luciferase activity is observed on the reaction plate containing immobilized biotin-tagged target dsDNA, whereas plates containing non-target or biotinylated single-stranded DNA only do not yield a signal. The intensity of emission increases proportionally to the concentration of dsDNA, and the detection limit of the target dsDNA is as low as 62 pM. An actual genomic DNA sample from Escherichia coli O157 was successfully detected by this automatic analyzer using the Biologi tip equipped with a reaction plate. This indicates that this system has a large potential for practical applications, including in particular point-of-care analyses in hygiene control, food safety testing, and clinical diagnosis.

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Graphical abstract A pipette-type biosensor was developed to detect target genes using a luciferase-fused zinc finger protein, where a small NeutrAvidin-immobilized reaction plate was placed on the tip, and the biotinylated target double-stranded DNA was detected by monitoring the bound luciferase activity.

     

Synthesis of optically active tetrahydrozerumbone

Tetrahydrozerumbone 2, which has a powerful balmy fragrance, has a stereogenic carbon at C2 and can be easily prepared from zerumbone 1, which is one of the most important materials that displays an NMRDOS character. Reduction of 2 gave two diastereomers 3 and 4; their optically active (>99% ee) alcohols were obtained by lipase-catalyzed stereoselective transesterification of each racemic alcohol. The enantioselectivity of tetrahydrozerumbol does not entirely depend on the hydroxyl position but on the 2-methyl position. Compounds (R)-2 and (S)-2 were obtained by Dess–Martin oxidation of the corresponding alcohols. Interestingly, (R)-2 showed a strong balmy fragrance while (S)-2 had hardly any fragrance.