High Pressure Synthesis of Cycloadduct of Fullerene C60 with 2H-Pyran-2-one∗∗

Under high pressure conditions, fullerene C₆₀ smoothly reacts with 2H-pyran-2-one to give a [4+2] cycloadduct, which can be reduced to an alcohol derivative.

     

The Effects of Sulphate and Tartrate Ions on the Molecular Organization of Water: Towards Understanding the Hofmeister Series (VI)

Using the 1-propanol (1P) probing methodology we have developed earlier, we characterized the effects of sulphate and tartrate anions on the molecular organization of H₂O. The results indicate that these two large anions belong to a new class of ??hydrophobe-like hydration center??. That is, sulphate and tartrate ions act as ??hydration centers?? with the hydration number 14±3 for both, and leave the bulk H₂O, away from hydration shells, unperturbed in the absence of the probing 1-propanol. As the mole fraction of the probe increases, however, the hydrogen bond probability of bulk H₂O away from hydration shells appears to decrease smoothly, as occurs with ??hydrophobes?? in H₂O. We plot the negative hydration number against the power to reduce the hydrogen bond probability of bulk H₂O for the two large anions. We also plotted the characteristic indices for ??hydrophiles?? and ??hydration centers?? whose characteristics we determined in the same manner earlier. H₂O defines the origin on this map. We found that a typical Hofmeister ranking for each anion matches reasonably well with that of the distance from the origin for each ion, in decreasing order starting from ions plotted in the north-west quadrant (representing the ??hydrophobe-like?? behavior) of the map and then in increasing order from the origin towards the south on the ordinate, the ??hydrophile-like?? behavior. These findings could be useful in understanding the Hofmeister series, pointing to the importance of the contribution made by the effect of each ion on H₂O, in addition to helping understand direct ion-protein interactions.     

Water inclusion as a trigger for modulation of anthracene arrangement and fluorescence emission of organic salt

An organic salt composed 9,10-bis(4-aminophenyl)anthracene and hypophosphorous acid emits yellow-green fluorescence in the crystalline state. The salt also gives water inclusion crystal which provides blue-green fluorescence. Single X-ray crystal studies revealed that water molecules induced the fluorescence change resulting from reaggregation of molecular packing.     

Fluorine in Shark Teeth: Its Direct Atomic‐Resolution Imaging and Strengthening Function

Atomic‐resolution imaging of beam‐sensitive biominerals is extremely challenging, owing to their fairly complex structures and the damage caused by electron irradiation. Herein, we overcome these difficulties by performing aberration‐corrected electron microscopy with low‐dose imaging techniques, and report the successful direct atomic‐resolution imaging of every individual atomic column in the complex fluorapatite structure of shark tooth enameloid, which can be of paramount importance for teeth in general. We demonstrate that every individual atomic column in shark tooth enameloid can be spatially resolved, and has a complex fluorapatite structure. Furthermore, ab initio calculations show that fluorine atoms can be covalently bound to the surrounding calcium atoms, which improves understanding of their caries‐reducing effects in shark teeth.     

A Nonenzymatic Kinetic Resolution of (±)-trans-2-Arylcyclohexanols via Esterification Using Polymer-Supported DCC,DMAP, and 3β-Acetoxyetienic Acid

A nonenzymatic kinetic resolution of (±)-trans-2-arylcyclohexanols was carried out by esterification using polymer-supported N,N′-dicyclohexylcarbodiimide (DCC), dimethylaminopyridine (DMAP), and 3β-acetoxyetienic acid. The efficiency of the kinetic resolution was comparable to the enzymatic method when arylcyclohexanols bearing a condensed-aromatic ring were used.

Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communication® to view the free supplemental file.     

Proton Order–Disorder Phenomena in a Hydrogen‐Bonded Rhodium–η5‐Semiquinone Complex: A Possible Dielectric Response Mechanism

A newly synthesized one‐dimensional (1D) hydrogen‐bonded (H‐bonded) rhodium(II)–η⁵‐semiquinone complex, [Cp*Rh(η⁵‐p‐HSQ‐Me₄)]PF₆ ([ 1 ]PF₆; Cp*=1,2,3,4,5‐pentamethylcyclopentadienyl; HSQ=semiquinone) exhibits a paraelectric–antiferroelectric second‐order phase transition at 237.1 K. Neutron and X‐ray crystal structure analyses reveal that the H‐bonded proton is disordered over two sites in the room‐temperature (RT) phase. The phase transition would arise from this proton disorder together with rotation or libration of the Cp* ring and PF₆^? ion. The relative permittivity ε_b′ along the H‐bonded chains reaches relatively high values (ca., 130) in the RT phase. The temperature dependence of ¹³C CP/MAS NMR spectra demonstrates that the proton is dynamically disordered in the RT phase and that the proton exchange has already occurred in the low‐temperature (LT) phase. Rate constants for the proton exchange are estimated to be 10^?4–10^?6 s in the temperature range of 240–270 K. DFT calculations predict that the protonation/deprotonation of [ 1 ]⁺ leads to interesting hapticity changes of the semiquinone ligand accompanied by reduction/oxidation by the π‐bonded rhodium fragment, producing the stable η⁶‐hydroquinone complex, [Cp*Rh³⁺(η⁶‐p‐H₂Q‐Me₄)]²⁺ ([ 2 ]²⁺), and η⁴‐benzoquinone complex, [Cp*Rh⁺(η⁴‐p‐BQ‐Me₄)] ([ 3 ]), respectively. Possible mechanisms leading to the dielectric response are discussed on the basis of the migration of the protonic solitons comprising of [ 2 ]²⁺ and [ 3 ], which would be generated in the H‐bonded chain.