Photodynamic Diagnosis Using 5‐Aminolevulinic Acid in 41 Biopsies for Primary Central Nervous System Lymphoma

We evaluated the feasibility of 5‐aminolevulinic acid (5‐ALA)‐mediated photodynamic diagnosis (PDD) in the biopsy for primary central nervous system lymphoma (PCNSL). 5‐ALA (20 mg kg^?1) was administered orally 4 hours preoperatively. Forty‐one biopsies obtained under PDD in 47 consecutive biopsies (46 patients) that were finally pathologically diagnosed as PCNSL were evaluated. Positive fluorescence was observed in 34 of those 41 biopsies (82.9%). An intraoperative pathological diagnosis (IOD) of suspected PCNSL was made in 21 of the biopsies with positive fluorescence (61.8%). However, the eight IODs in the remaining 13 biopsies (23.5%) were not correct (atypical cell, 4; high‐grade glioma, 1; gliosis, 1; unremarkable, 2). In those 8 biopsies, PCNSL was confirmed by the final pathological diagnosis. There was no difference in the mean Mib‐1 labeling index between the biopsies with positive fluorescence (86.5%) and those without positive fluorescence (90.0%). IOD was not performed in 6 biopsies; however, 5 of those biopsies (83.3%) showed positive fluorescence and were finally pathologically diagnosed as PCNSL. Use of PDD in biopsies for patients with suspected PCNSL is a reliable way of obtaining specimens of adequate quality for the final pathological diagnosis and may lead to improved diagnostic yield in the biopsy of PCNSL.     

Asymmetric conjugate addition of 5-benzylfurfurals to nitroalkenes using a diaminomethylenemalononitrile organocatalyst

A pyrrolidine–diaminomethylenemalononitrile organocatalyst efficiently promotes the asymmetric direct bisvinylogous Michael addition of 5-benzylfurfural derivatives to nitroalkenes, affording the corresponding ε-regioselective addition products in high yields with up to 86% ee.     

Rapid Evaluation of the Bioremediation of Fuel Oil in Soil by Gas Chromatography–Laser Ionization Time-of-Flight Mass Spectrometry

Gas chromatography–laser ionization time-of-flight mass spectrometry (GC-LI-TOFMS) was applied to the analysis of fuel oil in soil and soil treated by bioremediation. To demonstrate rapid and selective measurement, only filtered samples after extraction of fuel oil from soil were prepared. The required time for preparing three sample solutions from an oil-contaminated soil sample was only ca. 30?min. The degree of the decrease in the fuel oil in a soil sample by vaporization was confirmed by GC-LI-TOFMS, and after 7 days, the five peak areas arising from the constituents in fuel oil were decreased to between 39 and 79% of their original values. Next, the effect of bioremediation was confirmed by the addition of microbes (Rhodococcus sp. and Acinetobacter sp.). As a result, after 7 days, the five peak areas were decreased to between 61 and 81% of the values of the first decreases, after allowing for the effect of vaporization. This method showed sufficient selectivity, robustness, and rapidity for the measurement of oil-contaminated soil treated by bioremediation, which is essential for the evaluation of real environmental remediation.     

Rhodium- and iridium-catalyzed oxidative coupling of benzoic acids with alkynes via regioselective C-H bond cleavage

The oxidative coupling of benzoic acids with internal alkynes effectively proceeds in the presence of [Cp*RhCl2]2 and Cu(OAc)2 x H2O as catalyst and oxidant, respectively, to produce the corresponding isocoumarin derivatives. The copper salt can be reduced to a catalytic quantity under air. Interestingly, by using [Cp*IrCl2]2 in place of [Cp*RhCl2]2, the substrates undergo 1:2 coupling accompanied by decarboxylation to afford naphthalene derivatives exclusively. In this case, Ag2CO3 acts as an effective oxidant.     

Ti-direct, powerful, stereoselective aldol-type additions of esters and thioesters to carbonyl compounds: application to the synthesis and evaluation of lactone analogs of jasmone perfumes

An efficient TiCl(4)-Et(3)N or Bu(3)N-promoted aldol-type addition of phenyl and thiophenyl esters or thioaryl esters with aldehydes and ketones was performed (total 46 examples). The present method is advantageous from atom-economical and cost-effective viewpoints; good to excellent yields, moderate to good syn-selectivity, substrate variations, reagent availability, and simple procedures. Utilizing the present reaction as the key step, an efficient short synthesis of three lactone [2(5H)-furanone] analogs of jasmine perfumes was performed. Among them, the lactone analog of cis-jasmone had a unique perfume property (tabac).     

Self-assembly of semifluorinated minidendrons attached to electron-acceptor groups into pyramidal columns

The synthesis and self-assembly of twelve semifluorinated first-generation dendrons or minidendrons attached to electron-acceptor (n-type) groups generated from various combinations of eight acceptors and three dendrons are reported. Dendrons attached to small electron-acceptor molecules mediate their self-assembly into pi-stacks located in the center of a supramolecular helical pyramidal column with the long axis of the acceptor perpendicular to the long axis of the column. Dendrons attached to large electron-acceptor molecules, such as perylene bisimide, mediate the assembly of their acceptors in an unprecedented arrangement of pi-stacks that have the long axis of the acceptors parallel to the long axis of the supramolecular pyramidal column. All supramolecular columns self-organize into various periodic columnar arrays that exhibit liquid-crystalline phases, crystalline phases, or a liquid-crystalline phase with enhanced intracolumnar order. The present study demonstrates the simplicity and the versatility of the concept of assembly of n-type electroactive groups mediated by semifluorinated dendrons and assesses the scope and limitations of this supramolecular strategy.     

Enantio- and diastereo-controlled synthesis of (+)-juvabione employing organocatalytic desymmetrization and photoinduced fragmentation

(+)-Juvabione, a natural sesquiterpene exhibiting insect juvenile hormone activity, has been synthesized from sigma-symmetric 4-(2-formyl-ethyl)cyclohexanone by employing organocatalytic asymmetric aldolization and Norrish I-type fragmentation as the key steps.     

Rhodium-catalysed addition reaction of aryl- and alkenylboronic acids to isocyanates

The addition reaction of aryl- and alkenylboronic acids to isocyanates is catalysed by a rhodium(I) complex, affording secondary amides under mild conditions.     

Wetting-Dewetting oscillations of liquid films during solution-mediated vacuum deposition of rubrene

We found a novel oscillating phenomenon associated with surface wetting during the vacuum deposition of an organic semiconductor (rubrene) on a liquid film (bis(2-ethylhexyl)sebacate, B2EHS). In-situ observations by an optical microscope revealed that the oscillation was associated with the growth of the rubrene crystals. The oscillation frequency was proportional to the evaporation rate of rubrene. On the basis of the contact angle measurements, it was concluded that the oscillation is probably due to the change in the contact angle of the liquid caused by the formation of ultrathin rubrene films on the liquid surface.     

Highly Efficient,Catalytic Meerwein–Ponndorf–Verley Reduction with a Novel Bidentate Aluminum Catalyst

Double electrophilic activation of carbonyl groups allows a modern variant of the Meerwein–Ponndorf–Verley reduction to be carried out under mild conditions with bidentate catalyst 1 (see reaction). Various carbonyl substrates can be reduced efficiently at room temperature in CH₂Cl₂ with 2-propanol or sec-phenethyl alcohol in the presence of a catalytic amount of 1 . This system is also applicable to the Oppenauer oxidation of secondary alcohols to the corresponding ketones.