Electronic spectra of jet-cooled calix[4]arene and its van der Waals clusters: encapsulation of a neutral atom in a molecular bowl

The encapsulation of neutral guest has been studied for calix[4]arene (C4A) by forming van der Waals clusters with Ar and Ne in supersonic jets. The electronic transitions of these clusters suggest that the first Ar (Ne) is encapsulated inside the C4A cavity, while the next atoms are bound outside.     

Hexameric subphthalocyanine rosette

A highly congested hexameric subphthalocyanine array was synthesized by axial chlorine-to-phenoxy substitution of a hexakis(4-hydroxyphenyl)benzene based subphthalocyanine, and photoinduced symmetry-breaking charge separation was demonstrated in polar solvent.     

Laser spectroscopic and theoretical studies of encapsulation complexes of calix[4]arene

The complexes between the host calix[4]arene (C4A) and various guest molecules such as NH(3), N(2), CH(4), and C(2)H(2) have been investigated via experimental and theoretical methods. The S(1)-S(0) electronic spectra of these guest-host complexes are observed by mass-selected resonant two-photon ionization (R2PI) and laser-induced fluorescence (LIF) spectroscopy. The IR spectra of the complexes formed in molecular beams are obtained by IR-UV double resonance (IR-UV DR) and IR photodissociation (IRPD) spectroscopy. The supramolecular structures of the complexes are investigated by electronic structure methods (density functional and second order perturbation theory). The current results for the various molecular guests are put in perspective with the previously reported ones for the C4A-rare gas (Rg) (Phys. Chem. Chem. Phys. 2007, 126, 141101) and C4A-H(2)O complexes (J. Phys. Chem. A, 2010, 114, 2967). The electronic spectra of the complexes of C4A with N(2), CH(4), and C(2)H(2) exhibit red-shifts of similar magnitudes with the ones observed for the C4A-Rg complexes, whereas the complexes of C4A with H(2)O and NH(3) show much larger red-shifts. Most of the IR-UV DR spectra of the complexes, except for C4A-C(2)H(2), show a broad hydrogen-bonded OH stretching band with a peak at ~3160 cm(-1). The analysis of the experimental results, in agreement with the ones resulting from the electronic structure calculations, suggest that C4A preferentially forms endo-complexes (guests inside the host calizarene cavity) with all the guest species reported in this study. We discuss the similarities and differences of the structures, binding energies, and the nature of the interaction between the C4A host and the various guest species.     

High-energy, broadly tunable, narrow-bandwidth mid-infrared optical parametric system pumped by quasi-phase-matched devices

We have developed a tunable, narrow-bandwidth (<2 cm(-1)) mid-infrared (MIR) optical parametric system with a large-aperture periodically poled Mg-doped LiNbO(3) (LA-PPMgLN)-based high-energy pump source. The system has a continuously tunable tuning range from 4.6 to 11.2 mum and produces a maximum output energy of 2.0 mJ at 5.1 mum. Practical use of the MIR source is demonstrated by MIR-UV double-resonance spectroscopy of jet-cooled acetanilide.     

Oncogenic KRAS G12D mutation promotes dimerization through a second,phosphatidylserine–dependent interface: a model for KRAS oligomerization

KRAS forms transient dimers and higher-order multimers (nanoclusters) on the plasma membrane, which drive MAPK signaling and cell proliferation. KRAS is a frequently mutated oncogene, and while it is well known that the most prevalent mutation, G12D, impairs GTP hydrolysis, thereby increasing KRAS activation, G12D has also been shown to enhance nanoclustering. Elucidating structures of dynamic KRAS assemblies on a membrane has been challenging, thus we have refined our NMR approach that uses nanodiscs to study KRAS associated with membranes. We incorporated paramagnetic relaxation enhancement (PRE) titrations and interface mutagenesis, which revealed that, in addition to the symmetric ‘α–α’ dimerization interface shared with wild-type KRAS, the G12D mutant also self-associates through an asymmetric ‘α–β’ interface. The ‘α–β’ association is dependent on the presence of phosphatidylserine lipids, consistent with previous reports that this lipid promotes KRAS self-assembly on the plasma membrane in cells. Experiments using engineered mutants to spoil each interface, together with PRE probes attached to the membrane or free in solvent, suggest that dimerization through the primary ‘α–α’ interface releases β interfaces from the membrane promoting formation of the secondary ‘α–β’ interaction, potentially initiating nanoclustering. In addition, the small molecule BI-2852 binds at a β–β interface, stabilizing a new dimer configuration that outcompetes native dimerization and blocks the effector-binding site. Our data indicate that KRAS self-association involves a delicately balanced conformational equilibrium between transient states, which is sensitive to disease-associated mutation and small molecule inhibitors. The methods developed here are applicable to biologically important transient interactions involving other membrane-associated proteins.

Studies of membrane-dependent dimerization of KRAS on nanodiscs using paramagnetic NMR titrations and mutagenesis revealed a novel asymmetric ‘α–β’ interface that provides a potential mechanism for the enhanced assembly of KRAS–G12D nanoclusters.     

Development and application of a system for analysis of mixed cultures of microorganisms

Development and application of a system for real-time quantitative assessment of individual cell activities in a mixed culture system was investigated. This was based on a concept that the activities of individual cells in a mixed culture can be assessed if the cells are physically separated (in separate compartments) in a vessel while the culture conditions, including the broth components, are maintained the same in all the compartments during the cultivation. On this basis, three different apparatus (M-1, M-2, and M-3) were constructed using various types of membranes. In terms of mass transfer characteristics and membrane fouling, the M-3 apparatus was the most effective system for analysis of mixed cultures at high cell densities. With the M-3 apparatus, the interrelationships between two alcohol-producing strains (Saccharomyces cerevisiae and Zymomonas mobilis) under anaerobic and aerobic conditions were studied. Under anaerobic condition, except for possible competition for nutrients, there were no significant effects of the activities of one microorganism on the other. However, under aerobic condition, amensalism was observed because acetaldehyde that was produced by Z. mobilis inhibited the growth of S. cerevisiae.     

Regio‐ and Stereochemistry in Propylene Polymerization Catalyzed with Bis(phenoxy‐imine) Zr and Hf Complexes/MAO Systems

End‐group analyses of the oligo‐ and polypropylenes produced with bis(phenoxy‐imine) Zr and Hf complexes with methylaluminoxane (MAO) indicate that the polymerization is initiated by two consecutive 1,2‐insertions and is terminated by a β‐H transfer following a 2,1‐insertion. Our data indicate that chain propagation occurs with prevailing 1,2‐regiochemistry but with considerable regioerrors, and with virtually no stereoselectivity.

The polymerization of propylene mediated by bis(phenoxy‐imine) Zr and Hf complexes with MAO.     

Organic Solvent‐Free Enzymatic Transformation of Poly(ϵ‐caprolactone) into Repolymerizable Oligomers in Supercritical Carbon Dioxide

The enzymatic transformation of poly(ϵ‐caprolactone) (PCL) into repolymerizable oligomers in supercritical carbon dioxide (scCO₂) using an enzyme was carried out in order to establish a sustainable chemical recycling system for PCL, which is a typical biodegradable synthetic plastic. The enzymatic conversion of PCL beads having an M̄_n of 110 000 using Candida antarctica lipase (lipase CA) in scCO₂ containing small amounts of water quantitatively afforded CL oligomers at 40°C. The CL oligomers were readily repolymerized using the same enzyme to produce high‐molecular weight PCL.