Rotational spectrum of the Ar–dimethyl sulfide complex

The rotational spectra of three isotopomers of the Ar–dimethyl sulfide (DMS) complex – normal, ³⁴S, and ¹³C species – were measured in the frequency region from 3.7 up to 24.1 GHz by Fourier transform microwave spectroscopy. The normal species yielded 43 a-type and 79 c-type transitions. No Ar tunneling splitting was observed, while many transitions were split by the internal rotation of the two methyl tops of the DMS unit. In cases where the K-type splitting was close to that due to methyl internal-rotation, several forbidden transitions were observed that followed b-type selection rules. All of the observed transition frequencies were analyzed simultaneously using a phenomenological Hamiltonian also used in previously published work describing the Ar–dimethyl ether (DME) and Ne–DME complexes. The rotational and centrifugal distortion constants and the potential barrier height to methyl-top internal rotation, V₃, were determined. The rotational constants were consistent with an Ar–DMS center of mass (cm) distance of 3.796 (3) Å and a S–cm–Ar angle of 104.8 (2)°. The V₃ potential barrier obtained, 736.17 (32) cm⁻¹, was 97.8% of the DMS monomer barrier. By assuming a Lennard–Jones-type potential, the dissociation energy was estimated to be 2.4 kJ mol⁻¹, which was close to the value for Ar–DME, 2.5 kJ mol⁻¹.     

Dichloro­oxo(quinoline‐8‐thiolato‐κ2N,S)(triphenyl­phosphine oxide‐κO)rhenium(V) acetone solvate

The complex mol­ecule in the title compound, [Re(C₉H₆NS)Cl₂O(C₁₈H₁₅OP)]·C₃H₆O, has distorted octa­hedral geometry. The Re=O bond occupies the position trans to the triphenyl­phosphine oxide O atom. The Re—Cl bond trans to the thiol­ate S atom is longer than that trans to the quinoline N atom, implying a stronger trans influence of the S atom. Intra‐ and inter­molecular π–π inter­actions are also observed between the π rings in the complex.     

Synthesis and Reactivity of Six‐Membered Oxa‐Nickelacycles: A Ring‐Opening Reaction of Cyclopropyl Ketones

Cyclopropanecarboxaldehyde ( 1 a ), cyclopropyl methyl ketone ( 1 b ), and cyclopropyl phenyl ketone ( 1 c ) were reacted with [Ni(cod)₂] (cod=1,5‐cyclooctadiene) and PBu₃ at 100 °C to give η²‐enonenickel complexes ( 2 a – c ). In the presence of PCy₃ (Cy=cyclohexyl), 1 a and 1 b reacted with [Ni(cod)₂] to give the corresponding μ‐η²:η¹‐enonenickel complexes ( 3 a , 3 b ). However, the reaction of 1 c under the same reaction conditions gave a mixture of 3 c and cyclopentane derivatives ( 4 c , 4 c′ ), that is, a [3+2] cycloaddition product of 1 c with (E)‐1‐phenylbut‐2‐en‐1‐one, an isomer of 1 c . In the presence of a catalytic amount of [Ni(cod)₂] and PCy₃, [3+2] homo‐cycloaddition proceeded to give a mixture of 4 c (76 %) and 4 c′ (17 %). At room temperature, a possible intermediate, 6 c , was observed and isolated by reprecipitation at ?20 °C. In the presence of 1,3‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene (IPr), both 1 a and 1 c rapidly underwent oxidative addition to nickel(0) to give the corresponding six‐membered oxa‐nickelacycles ( 6 ai , 6 ci ). On the other hand, 1 b reacted with nickel(0) to give the corresponding μ‐η²:η¹‐enonenickel complex ( 3 bi ). The molecular structures of 6 ai and 6 ci were confirmed by X‐ray crystallography. The molecular structure of 6 ai shows a dimeric η¹‐nickelenolate structure. However, the molecular structure of 6 ci shows a monomeric η¹‐nickelenolate structure, and the nickel(II) 14‐electron center is regarded as having “an unusual T‐shaped planar” coordination geometry. The insertion of enones into monomeric η¹‐nickelenolate complexes 6 c and 6 ci occurred at room temperature to generate η³‐oxa‐allylnickel complexes ( 8 , 9 ), whereas insertion into dimeric η¹‐nickelenolate complex 6 ai did not take place. The diastereoselectivity of the insertion of an enone into 6 c having PCy₃ as a ligand differs from that into 6 ci having IPr as a ligand. In addition, the stereochemistry of η³‐oxa‐allylnickel complexes having IPr as a ligand is retained during reductive elimination to yield the corresponding [3+2] cycloaddition product, which is consistent with the diastereoselectivity observed in Ni⁰/IPr‐catalyzed [3+2] cycloaddition reactions of cyclopropyl ketones with enones. In contrast, reductive elimination from the η³‐oxa‐allylnickel having PCy₃ as a ligand proceeds with inversion of stereochemistry. This is probably due to rapid isomerization between syn and anti isomers prior to reductive elimination.     

Chemical reaction-inspired crystal growth of a coordination polymer toward morphology design and control

This paper reports a novel crystal growth system of a coordination framework {[Cu3(CN)3{hat-(CN)3(OEt)3}]}n (1) (hat-(CN)3(OEt)3 = 2,6,10-tricyano-3,7,11-triethoxy-1,4,5,8,9,12-hexaazatriphenylene). The coordination polymer is crystallized through the reaction of 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (hat-(CN)6), ethanol, and copper(I) complex, involving the breaking and forming of covalent bonds. The crystal morphologies obtained in the present system contain dumbbells, cogwheels, and superlattices. Moreover, in the growth perpendicular to the c-axis, periodic ramification at regular interval is observed, affording superlattice morphologies. Observation of the growth of dumbbell crystals shows that the growth rates parallel and perpendicular to the crystallographic c-axis are quite different: the former shows a drastic change with the reaction duration, while the latter is almost constant. These results are reproduced as a simple reaction-diffusion system, indicating that chemical reactions on crystal surfaces play an important role in determining the macroscopic crystal morphologies.     

Cation-pi interaction in the polyolefin cyclization cascade uncovered by incorporating unnatural amino acids into the catalytic sites of squalene cyclase

It has been assumed that the pi-electrons of aromatic residues in the catalytic sites of triterpene cyclases stabilize the cationic intermediates formed during the polycyclization cascade of squalene or oxidosqualene, but no definitive experimental evidence has been given. To validate this cation-pi interaction, natural and unnatural aromatic amino acids were site-specifically incorporated into squalene-hopene cyclase (SHC) from Alicyclobacillus acidocaldarius and the kinetic data of the mutants were compared with that of the wild-type SHC. The catalytic sites of Phe365 and Phe605 were substituted with O-methyltyrosine, tyrosine, and tryptophan, which have higher cation-pi binding energies than phenylalanine. These replacements actually increased the SHC activity at low temperature, but decreased the activity at high temperature, as compared with the wild-type SHC. This decreased activity is due to the disorganization of the protein architecture caused by the introduction of the amino acids more bulky than phenylalanine. Then, mono-, di-, and trifluorophenylalanines were incorporated at positions 365 and 605; these amino acids reduce cation-pi binding energies but have van der Waals radii similar to that of phenylalanine. The activities of the SHC variants with fluorophenylalanines were found to be inversely proportional to the number of the fluorine atoms on the aromatic ring and clearly correlated with the cation-pi binding energies of the ring moiety. No serious structural alteration was observed for these variants even at high temperature. These results unambiguously show that the pi-electron density of residues 365 and 605 has a crucial role for the efficient polycyclization reaction by SHC. This is the first report to demonstrate experimentally the involvement of cation-pi interaction in triterpene biosynthesis.     

Evaluation of the Sanita-kun coliforms, a dehydrated medium sheet for coliform detection. Performance-Tested Method 100402

The Sanita-kun Coliforms consists of a transparent cover film, an adhesive sheet, a layer of nonwoven fabric, and a water-soluble compound film, including a culture medium formula for the detection of coliforms. The medium sheet was validated with 26 food types belonging to 9 food categories (meat, poultry, fish and seafood, fruits and vegetable, dairy, chocolate or bakery, animal feeds, pasta, and miscellaneous) using violet red bile (VRB) agar method in the U.S. Food and Drug Administration's Bacteriological Analytical Manual as a reference according to the AOAC guideline. The medium sheet showed 100% inclusivity and exclusivity. Ruggedness study suggested allowances in the incubation temperature and time as 33-35 degrees C and 24 +/- 4 h, respectively. The performance of 3 different lots of the medium sheets was equivalent and suggested no change of the performance at least for 3 years. In the comparative recovery study, many samples (84.6%), which were inoculated with a coliform strain, showed no significant difference between the 2 methods. The linear correlation coefficient (r2) to the VRB agar was calculated as 0.94. In the repeatability study, the average relative standard deviation of total foods was 0.10 in the medium sheet. In the independent study, the medium sheet detected significantly more colonies than VRB plates in the frozen raw milk sample, while there was no significant difference between the 2 methods in raw ground beef sample. Comparative recovery study on foods, inoculated and then frozen, showed the medium sheet detected injured cells with better recovery than VRB agar. The analysts in the independent study wrote that the medium sheet was easy to use and read overall. The Sanita-kun sheet provides an alternative method to coliform count agar.     

Efficient construction of the hexacyclic ring core of palau'amine: the pKa concept for proceeding with unfavorable equilibrium reactions

Palau''amine has received a great deal of attention as an attractive synthetic target due to its intriguing molecular architecture and significant immunosuppressive activity, and we achieved its total synthesis in 2015. However, the synthesized palau''amine has not been readily applicable to the mechanistic study of immunosuppressive activity, because it requires 45 longest linear steps from a commercially available compound. Here, we report the short-step construction of the ABCDEF hexacyclic ring core of palau''amine. The construction of the CDE tricyclic ring core in a single step is achieved by our pK_a concept for proceeding with unfavorable equilibrium reactions, and a palau''amine analog without the aminomethyl and chloride groups is synthesized in 20 longest linear steps from the same starting material. The palau''amine analog is confirmed to retain the immunosuppressive activity. The present synthetic approach for a palau''amine analog has the potential for use in the development of palau''amine probes for mechanistic elucidation.

A palau''amine analog (2) was synthesized from 2-cyclopentenone in 20 steps. The construction of the CDE tricyclic ring core in a single step is achieved by our pK_a concept for proceeding with the unfavorable equilibrium reactions.     

Reduction of thermal fluctuations in a cryogenic laser interferometric gravitational wave detector

The thermal fluctuation of mirror surfaces is the fundamental limitation for interferometric gravitational wave (GW) detectors. Here, we experimentally demonstrate for the first time a reduction in a mirror's thermal fluctuation in a GW detector with sapphire mirrors from the Cryogenic Laser Interferometer Observatory at 17 and 18 K. The detector sensitivity, which was limited by the mirror's thermal fluctuation at room temperature, was improved in the frequency range of 90 to 240 Hz by cooling the mirrors. The improved sensitivity reached a maximum of 2.2×10(-19) m/√Hz at 165 Hz.     

Evaluation of zinc self-diffusion at the interface between homoepitaxial ZnO thin films and (0001) ZnO substrates

Isotopic ZnO thin films were deposited on the c-plane of ZnO single crystals by pulsed laser deposition. The isotopic abundance of Zn in the films was determined with a secondary ion mass spectrometry before and after the films was diffusion annealed. The diffusion profiles across the film/substrate interface behaved smooth features. The zinc diffusion coefficient (D_Zn) was obtained by analyzing the slope of the profile in the annealed sample. The temperature dependence of D_Zn was determined to be D_Zn(cm²/s)=8.0×10⁴exp(?417[kJ/mol])/RT, where R and T are gas constant and temperature. The zinc ion diffusion coefficients were of the same order as that in a ZnO single crystal. A comparison of the experimental and theoretical values indicated that the zinc ions diffused in the thin film and the single crystal through a vacancy mechanism.