Shape‐Selective Alkylation of Naphthalene over Zeolites: Steric Interaction of Reagents with Zeolites

Steric interaction of reagents with zeolites was studied in isopropylation, sec‐butylation, and tert‐butylation of naphthalene (NP) over several large‐pore zeolites to elucidate the mechanism of selective catalysis. Selectivities for dialkylnaphthalene (DAN) isomers were influenced by the type of zeolite and bulkiness of alkylating agent. Selective formation of β,β‐ and 2,6‐diisopropylnaphthalene (DIPN) occurred only over H‐mordenite (MOR) in the isopropylation of NP using propene; bulky transition states of α,α‐ and α,β‐DIPN are excluded because of steric restriction by the channels, resulting in selective formation of β,β‐ and 2,6‐DIPN. However, low selectivities for β,β‐ and 2,6‐DIPN were observed over the zeolites, SSZ‐24 (AFI), SSZ‐55 (ATS), and SSZ‐42 (IFR) with 12‐membered‐ring (12‐MR) pore entrances of one‐dimensional channels, CIT‐5 (CFI), UTD‐1 (DON), and SSZ‐53 (SFH) with 14‐membered‐ring (14‐MR) pore entrances of one‐dimensional channels, and Y‐zeolite (FAU), zeolite β (BEA), and CIT‐1 (CON) with 12‐MR pore entrances of three‐dimensional channels, because their channels are too large for the exclusion of bulky isomers. Catalysis over these zeolites occurs under kinetic and/or thermodynamic control, resulting in predominant formation of α,α‐ and α,β‐DIPN at lower temperatures and an increase of the stable isomer β,β‐DIPN at higher temperatures. The selectivities for β,β‐ and 2,6‐DAN were enhanced with the increase in bulkiness of alkylating agents: 1‐butene for sec‐butylation and 2‐methylpropene for tert‐butylation. In particular, β,β‐di‐tert‐butylnaphthalene (DTBN) was selectively formed in the tert‐butylation. The selectivities for β,β‐ and 2,6‐DAN were enhanced even in large channels: the transition states of the least bulky isomers only fit the channels because other bulky isomers are excluded by steric restriction of the channels. However, tert‐butylation over FAU, BEA, and CON had selectivities for 2,6‐DTBN of around 50–60%, although selectivities for β,β‐DTBN were almost 100% selectivity; these zeolites can hardly recognize the differences between 2,6‐ and 2,7‐DTBN. The results indicate that the fitting of the least bulky isomers to zeolite channels, leading to the exclusion of other bulky isomers, is essential for highly shape‐selective catalysis.     

Influence of head shape of solid body plunging into water on splash formation

Abstract  

We experimentally investigated the influence of a head shape of a solid body plunging into water on splash formation. Three different head shapes were tested: a hemisphere, cone, and circular cylinder. A hemisphere as a tail shape is common to all three head shapes. We captured images of splash formation using a high-speed CMOS camera. We found that a film flow generated at an early stage when a body impacts the water surface influences subsequent events until the splash sequence is completed. We explain the origin of the film flow according to the principle of conservation of momentum. The film flow as the primary splash originates from water displaced by the head. The meridian line, which connects the head to the tail of the body, affects separation of the film flow and causes the secondary splash. The air cavity generated when the body plunges into the water is also influenced by the head shape. The tertiary splash is formed by a reaction of the air cavity, which is detached from the body. We found that the secondary dome-type splash obstructs growth of the tertiary splash. Thus, we conclude that the head shape affects all events of the splash.     

A new Brézis‐Gallouët‐Wainger inequality from the viewpoint of the real interpolation functors

The Brézis‐Gallouët‐Wainger inequality describes a subtle embedding property into . The relation between the Brézis‐Gallouët‐Wainger inequality and the real interpolation functor together with the sharpness of the results is discussed in the present paper. As our first main results shows, it turns out that there are two intermediate terms between and the logarithmic boundedness, which is supposed to be the right‐hand side of the Brézis‐Gallouët‐Wainger inequality. As the second result, the first result is extended to inequalities which reflect the meaning of the second index of Besov spaces and the interpolation theorem.     

A general regularity theory for weak mean curvature flow

We give a new proof of Brakke’s partial regularity theorem up to $C^{1,\varsigma }$ for weak varifold solutions of mean curvature flow by utilizing parabolic monotonicity formula, parabolic Lipschitz approximation and blow-up technique. The new proof extends to a general flow whose velocity is the sum of the mean curvature and any given background flow field in a dimensionally sharp integrability class. It is a natural parabolic generalization of Allard’s regularity theorem in the sense that the special time-independent case reduces to Allard’s theorem.     

Dynamic photoelastic analysis by optical heterodyne polarimetry

This paper describes the mapping of the spatiotemporal principal stress distribution evolved with time in an epoxy photoelastic sample. In the optical heterodyne polarimeter exploited, the signal beam of light transmitted by the sample under continuously loaded condition is photomixed with the local oscillator beam of light made up of orthogonal linearly polarized two-frequency components. Every pixel of a MOS video camera used generates a beat photocurrent that possesses the two orthogonal field components of the elliptically polarized signal beam. The spatiotemporal principal stress distributions can be uniquely determined simultaneously and independently from these two orthogonal field components, and are successfully mapped in a time-sequential form. The spatial and temporal resolutions in the maps are 0.18 mm and 2.9 ms, respectively.     

Host-guest interactions in the supramolecular incorporation of fullerenes into tailored holes on porphyrin-modified gold nanoparticles in molecular photovoltaics

Novel gold nanoparticles modified with a mixed self-assembled monolayer of porphyrin alkanethiol and short-chain alkanethiol were prepared (first step) to examine the size and shape effects of surface holes (host) on porphyrin-modified gold nanoparticles. The porphyrin-modified gold nanoparticles with a size of about 10 nm incorporated C60 molecules (guest) into the large, bucket-shaped holes, leading to the formation of a supramolecular complex of porphyrin-C60 composites (second step). Large composite clusters with a size of 200-400 nm were grown from the supramolecular complex of porphyrin-C60 composites in mixed solvents (third step) and deposited electrophoretically onto nanostructured SnO2 electrodes (fourth step). Differences in the porphyrin:C60 ratio were found to affect the structures and photoelectrochemical properties of the composite clusters in mixed solvents as well as on the SnO2 electrodes. The photoelectrochemical performance of a photoelectrochemical device consisting of SnO2 electrodes modified with the porphyrin-C60 composites was enhanced relative to a reference system with small, wedged-shaped surface holes on the gold nanoparticle. Time-resolved transient absorption spectroscopy with fluorescence lifetime measurements suggest the occurrence of ultrafast electron transfer from the porphyrin excited singlet states to C60 or the formation of a partial charge-transfer state in the composite clusters of supramolecular complexes formed between porphyrin and C60 leading to efficient photocurrent generation in the system. Elucidation of the relationship between host-guest interactions and photoelectrochemical function in the present system will provide valuable information on the design of molecular devices and machines including molecular photovoltaics.     

Enantioface-selective palladium-catalyzed silaboration of allenes via double asymmetric induction

Enantioenriched beta-borylallylsilanes were synthesized by palladium-catalyzed enantioface-selective addition of the silicon-boron bond to terminal allenes using a palladium catalyst possessing a chiral monodentate phosphine ligand. Use of a silylborane bearing a chiral auxiliary on the boron atom was beneficial to gain enantioface selectivities as high as 96% de.     

ESR study of Mn2+ in GeTe and GeTeSi glasses

The electron spin resonance spectra of Mn²⁺ ions have been studied in Ge_xTe_100?x with x = 15, 17.5 and 20, and Ge_20?xTe₈₀Si_x with 0 ?x? 20. All samples are found to exhibit six hyperfine lines centered at g = 4.3 with hyperfine interaction constant A = 56 × 10^?4cm^?1. The g = 4.3 line is interpreted as being caused by Mn²⁺ ions incorporated in the amorphous network and surrounded by four Te atoms in an arrangement of orthorhombic symmetry. Some of the samples of GeTe show a g = 2.0 line. This line also appears after heat treatment in air at temperatures above the glass transition temperature. It is concluded that the g = 2.0 line is caused by Mn²⁺ ions in phase separated microcrystalline or concentrated regions of MnO in the glass.     

Rhodium(I)‐Catalyzed Enantioselective Cyclization of Enynes by Intramolecular Cleavage of the Rh−C Bond by a Tethered Hydroxy Group

Rhodium(I)‐catalyzed enantioselective intramolecular cyclization of enynes having a hydroxy group in the tether was investigated, and various cyclic compounds possessing a chiral quaternary carbon center were obtained in high yields with high ees. In this cyclization, a Rh?C(sp²) bond in the rhodacyclopentene intermediate, which was formed by enantioselective oxidative cycloaddition of enynes to a chiral rhodium(I) complex, was intramolecularly cleaved by σ‐bond metathesis of a tethered O?H bond in the substrate. Furthermore, it was found that the cyclic compounds were obtained with high ees even when the starting materials having a racemic secondary alcohol moiety were used in this reaction.