Chemistry of fullerene epoxides: synthesis, structure, and nucleophilic substitution-addition reactivity

Fullerene epoxides, C??O(n), having epoxide groups directly attached to the fullerene cage, constitute an interesting class of fullerene derivatives. In particular, the chemical transformations of fullerene epoxides are expected to play an important role in the development of functionalized fullerenes. This is because such transformations can readily afford a variety of mono- or polyfunctionalized fullerene derivatives while conserving the epoxy ring arrangement on the fullerene surface, as seen in representative regioisomeric fullerene polyepoxides. The first part of this review addresses the synthesis and structural characterization of fullerene epoxides. The formation of fullerene epoxides through different oxidation reactions is then explored. Adequate characterization of the isolated fullerene epoxides was achieved by concerted use of NMR and LC-MS techniques. The second part of this review addresses the substitution of fullerene epoxides in the presence of a Lewis acid catalyst. Most major substitution products have been isolated as pure compounds and their structures established through spectroscopic methods. The correlation between the structure of the substitution product and the oxygenation pattern of the starting materials allows elucidation of the mechanistic features of this transformation. This approach promises to lead to rigorous regioselective production of various fullerene derivatives for a wide range of applications.     

Microchip electrophoretic protein separation using electroosmotic flow induced by dynamic sodium dodecyl sulfate-coating of uncoated plastic chips

Separation of sodium dodecyl sulfate (SDS)-protein complexes is difficult on plastic microchips due to protein adsorption onto the wall. In this paper, we elucidated the reasons for the difficulties in separating SDS-protein complexes on plastic microchips, and we then demonstrated an effective method for separating proteins using polymethyl methacrylate (PMMA) microchips. Separation difficulties were found to be dependent on adsorption of SDS onto the hydrophobic surface of the channel, by which cathodic electroosmotic flow (EOF; reversed flow) was generated. Our developed method effectively utilized the reversed flow from this cathodic EOF as a driving force for sample proteins using permanently uncoated but dynamic SDS-coated PMMA microchips. High-speed (6 s) separation of proteins and peptides up to 116 kDa was successfully achieved using this system.     

Micelle structures in aqueous solutions of glucose-based surfactants having an isoprenoid-type hydrophobic chain

Surfactant self-diffusion coefficients have been measured on a binary system of 1-O-beta-3,7-dimethyloctyl-D-maltopyranoside (beta-Mal(2)(Ger))/water and a mixed surfactant system of beta-Mal(2)(Ger)/1-O-beta-3,7-dimethyloctyl-D-glucopyranoside (beta-Glc(Ger))/water at 25 degrees C. For comparison, measurements have also been made on 1-O-beta-decyl-D-maltopyranoside (beta-Mal(2)C(10))/water and beta-Mal(2)C(10)/1-O-beta-decyl-D-glucopyranoside (beta-GlcC(10))/water. The hydrodynamic radius of beta-Mal(2)(Ger) micelles obtained from the micellar diffusion coefficient is around 3 nm and nearly equal to that of beta-GlcC(10) micelles within experimental error. In the mixed surfactant systems, the hydrodynamic radii for both systems increase with increasing X(G) (the mole fraction of beta-Glc(Ger) or beta-GlcC(10) in the total mixed solute) above X(G) congruent with 0.4 when the total surfactant concentration is kept constant at 2 wt%. The R(H) of beta-Glc(Ger)/Mal(2)(Ger) micelles increases more rapidly than beta-GlcC(10)/beta-Mal(2)C(10) micelles, and then phase separation occurs at X(G) congruent with 0.65. On the other hand, the R(H) of beta-GlcC(10)/beta-Mal(2)C(10) micelles continues to increase until the phase separation occurs at X(G) congruent with 0.92. Measurements have also been performed as a function of total surfactant concentration at constant X(G) (=0.6). The CMC of the beta-Glc(Ger)/Mal(2)(Ger) system is larger than that of the beta-GlcC(10)/beta-Mal(2)C(10) system as expected from the results of the pure surfactant systems published previously. The R(H) increases with increasing total surfactant concentration for both systems. At higher concentrations, the R(H) of beta-Glc(Ger)/Mal(2)(Ger) micelles increases more rapidly than beta-GlcC(10)/beta-Mal(2)C(10) micelles. These results can be explained by the fact that the geranyl and decyl chains have the same volume but different chain lengths.     

The Impact of C2 Insertion into a Carbazole Donor on the Physicochemical Properties of Dibenzo[a,j]phenazine-Cored Donor–Acceptor–Donor Triads

Novel electron donor–acceptor–donor (D-A-D) compounds comprising dibenzo[a,j]phenazine as the central acceptor core and two 7-membered diarylamines (iminodibenzyl and iminostilbene) as the donors have been designed and synthesized. Investigation of their physicochemical properties revealed the impact of C₂ insertion into well-known carbazole electron donors on the properties of previously reported twisted dibenzo[a,j]phenazine-core D-A-D triads. Slight structural modification caused a drastic change in conformational preference, allowing unique photophysical behavior of dual emission derived from room-temperature phosphorescence and triplet–triplet annihilation. Furthermore, electrochemical analysis suggested sigma-dimer formation and electrochemical polymerization on the electrode. Quantum chemical calculations also rationalized the experimental results.     

O-N intramolecular alkoxycarbonyl migration of typical protective groups in hydroxyamino acids

O-N Intramolecular alkoxycarbonyl (carbonate-carbamate) migration was found to occur as a common reaction of hydroxyamino acids under mild basic aqueous conditions with no formation of side products. Carbonate protective groups migrate to produce amino-protected carbamate derivatives of hydroxyamino acids with high efficiency and purity.     

A hybrid density-functional study of the one-dimensional ferromagnetic ordering of (BDTA)[Ni(mnt)2]

The one-dimensional intermolecular ferromagnetic interaction of a charge-transfer (CT) complex, (BDTA)[Ni(mnt)₂] (BDTA: 1,3,2-benzodithiazolyl, mnt: maleonitriledithiolate), is studied by the Kohn–Sham hybrid density functional method, in order to understand the mechanism of the magnetism. All possible effective exchange integrals, J, between the spin pairs of the system indicate that a ferromagnetic interaction (J = 172 cm⁻¹) exists along the b-axis. Magnetic susceptibility, simulated with the ab initio determined J values by the quantum Monte Carlo (QMC) method, is qualitatively consistent with that measured experimentally.     

Generation of nitrile oxides from oximes using t-BuOI and their cycloaddition

tert-Butyl hypoiodite (t-BuOI) was found to be a powerful reagent for the cycloaddition of oximes and alkenes/alkynes, leading to the formation of a variety of isoxazolines or isoxazoles under mild conditions.     

Synthesis of an O-acyl isopeptide by using native chemical ligation to efficiently construct a hydrophobic polypeptide

By using dimethylformamide to suppress the O-to-N acyl migration, we efficiently synthesized an O-acyl isopeptide by native chemical ligation of a peptide-thioester and a Cys-O-acyl isopeptide. The reaction mixture was then loaded onto an octadecylsilane reverse-phase HPLC column, and the isopeptide was purified by using a linear gradient of CH₃CN in 0.1% aqueous trifluoroacetic acid. The recovery rate of the O-acyl isopeptide was considerably higher than that of the corresponding native polypeptide. Synthesis of O-acyl isopeptides via native chemical ligation, with O-to-N acyl migration as the final step to give the native form, has potential as an efficient method of constructing hydrophobic polypeptides.     

7,7,8,8‐Tetraaryl‐o‐quinodimethane Stabilized by Dibenzo Annulation: A Helical π‐Electron System That Exhibits Electrochromic and Unique Chiroptical Properties

When two benzene rings are fused to a tetraaryl‐o‐quinodimethane skeleton, sterically hindered helical molecules 1 acquire a high thermodynamic stability. Because the tetraarylbutadiene subunit contains electron‐donating alkoxy groups, 1 undergo reversible two‐electron oxidation to 2 ²⁺, which can be isolated as deeply colored stable salts. Intramolecular transfer of the point chirality (e.g., sec‐butyl) on the aryl groups to helicity induces a diastereomeric preference in dications 2 b ²⁺ and 2 c ²⁺, which represents an efficient method for enhancing circular‐dichroism signals. Thus, those redox pairs can serve as new electrochiroptical response systems. X‐ray analysis of dication 2 ²⁺ revealed π–π stacking interaction of the diarylmethylium moieties, which is also present in solution. The stacking geometry is the key contributor to the chirosolvatochromic response.     

Rational Design and Identification of a Non‐Peptidic Aggregation Inhibitor of Amyloid‐β Based on a Pharmacophore Motif Obtained from cyclo[‐Lys‐Leu‐Val‐Phe‐Phe‐]

Inhibition of pathogenic protein aggregation may be an important and straightforward therapeutic strategy for curing amyloid diseases. Small‐molecule aggregation inhibitors of Alzheimer’s amyloid‐β (Aβ) are extremely scarce, however, and are mainly restricted to dye‐ and polyphenol‐type compounds that lack drug‐likeness. Based on the structure‐activity relationship of cyclic Aβ16–20 (cyclo‐[KLVFF]), we identified unique pharmacophore motifs comprising side‐chains of Leu², Val³, Phe⁴, and Phe⁵ residues without involvement of the backbone amide bonds to inhibit Aβ aggregation. This finding allowed us to design non‐peptidic, small‐molecule aggregation inhibitors that possess potent activity. These molecules are the first successful non‐peptidic, small‐molecule aggregation inhibitors of amyloids based on rational molecular design.