Proving and Probing the Presence of the Elusive C−H⋅⋅⋅O Hydrogen Bond in Liquid Solutions at Room Temperature

Hydrogen bonds (H bonds) play a major role in defining the structure and properties of many substances, as well as phenomena and processes. Traditional H bonds are ubiquitous in nature, yet the demonstration of weak H bonds that occur between a highly polarized C−H group and an electron-rich oxygen atom, has proven elusive. Detailed here are linear and nonlinear IR spectroscopy experiments that reveal the presence of H bonds between the chloroform C−H group and an amide carbonyl oxygen atom in solution at room temperature. Evidence is provided for an amide solvation shell featuring two clearly distinguishable chloroform arrangements that undergo chemical exchange with a time scale of about 2 ps. Furthermore, the enthalpy of breaking the hydrogen bond is found to be 6–20 kJ mol⁻¹. Ab-initio computations support the findings of two distinct solvation shells formed by three chloroform molecules, where one thermally undergoes hydrogen-bond making and breaking.     

Genome Mining of Oxidation Modules in trans‐Acyltransferase Polyketide Synthases Reveals a Culturable Source for Lobatamides

Bacterial trans‐acyltransferase polyketide synthases (trans‐AT PKSs) are multimodular megaenzymes that biosynthesize many bioactive natural products. They contain a remarkable range of domains and module types that introduce different substituents into growing polyketide chains. As one such modification, we recently reported Baeyer–Villiger‐type oxygen insertion into nascent polyketide backbones, thereby generating malonyl thioester intermediates. In this work, genome mining focusing on architecturally diverse oxidation modules in trans‐AT PKSs led us to the culturable plant symbiont Gynuella sunshinyii, which harbors two distinct modules in one orphan PKS. The PKS product was revealed to be lobatamide A, a potent cytotoxin previously only known from a marine tunicate. Biochemical studies show that one module generates glycolyl thioester intermediates, while the other is proposed to be involved in oxime formation. The data suggest varied roles of oxygenation modules in the biosynthesis of polyketide scaffolds and support the importance of trans‐AT PKSs in the specialized metabolism of symbiotic bacteria.     

A novel polyaddition of bifunctional acetylenes containing electron-withdrawing groups. III. Synthesis of polymers having β-alkoxyenoate moieties by the reaction of internal diynes with diols

Tri-n-butylphosphine-catalyzed polyadditions of activated internal diynes (bifunctional β-substituted propiolate, 1B and 1C ) with diols are described. Although a terminal bispropiolate ( 1A ) could not produce soluble polymers, with secondary diols, the polyaddition of 1B or 1C with primary as well as secondary diols gave corresponding polymers ( 3 , only composed of E isomeric units) in high yield. The rate of the present polyaddition was estimated by a model reaction of benzyl alcohol with methyl 2-heptynoate ( 4 ), from which the introduction of alkyl groups at the β-position of propiolate moieties was found to decrease the rate of the reaction by 80 times. Furthermore, the rate-determining step on this polymerization system was speculated to be a protonation step of zwitterionic intermediates with protons from diols. © 1996 John Wiley & Sons, Inc.     

Synthesis and γ-radiolysis of 2′-deoxy-5-fluorouridine and 5-fluorouridine derivatives

Seventeen compounds having a variety of substituents at the 3- and 5′-positions of 2′-deoxy-5-fluorouridine (5-FUdR) and 5-fluorouridine (5-FUR) were synthesized, and their γ-radiolysis in aqueous solutions were studied. The compounds having thioureido (RNHCSNH, R  H, PhCH₂, acyl) and thiocarbonylamino (XCSNH, X  PhCH₂S, PhO) groups at the 3-position of 5-FUdR were efficiently cleaved to give 5-FUdR with high G values upon γ-irradiation of their aqueous solutions. The active species for these cleavage reactions were hydrated electron (e⁻ _aq), H^• and HO^•. However, the compounds having a dimethylsulfoxyimino group at 3-position of 5-FUdR and 5-FUR afforded 5-FUdR and 5-FUR only under the radiolysis conditions where e⁻ _aq becomes a principal active species. The compound having a 2-benzoylthiazoylthiocarbonylamino group at the 3-position of 5-FUdR showed the highest reactivity toward HO^.. The mechanisms of these γ-radiolysis reactions are discussed. The examination of anticellular activities of γ-irradiated compounds having a thiocarbonylamino group at the 3-position of 5-FUdR toward murine Sarcoma 180 cells revealed that these compounds may be utilized as a candidate for a radiation-induced drug (RID).     

Nonlinear optical characteristics of carbon disulfide

The nonlinear refractive index γ of CS₂ is studied using laser pulses of various durations (from 110 fs to 75 ns). It is found that γ increases with increasing pulse duration within the picosecond region (from (3 ± 0.6) × 10^?15 cm² W^?1 at 110 fs to (3.5 ± 0.7) × 10^?14 cm² W^?1 at 75 ns) due to orientational nonlinearities. Variations in the sign of γ caused by the thermal effect at different pulse durations and repetition rates are analyzed. It is demonstrated that the fast electronic component, the component associated with molecular processes, causing positive nonlinear refraction, and the acoustic component, responsible for negative nonlinear refraction, manifest themselves simultaneously. The results of a study of the nonlinear absorption of carbon disulfide are presented. The two-and three-photon absorption coefficients of CS₂ are determined to be (5 ± 1.5) × 10^?11 cm W^?1 and (2.8 ± 0.8) × 10^?23 cm³ W^?2, respectively.     

Fourier domain optical coherence tomography using optical demultiplexers imaging at 60,000,000 lines/s

We describe high-speed Fourier domain optical coherence tomography (OCT) using optical demultiplexers (ODs) for spectral dispersion. The OD enables separation of a narrow spectral band of 14 GHz (0.11 nm) from a broadband incident light at 256 different frequencies in 25.0 GHz intervals centered at 192.2 THz (1559.8 nm). OCT imaging of 60,000,000 axial scans per second was achieved through parallel signal acquisition using 256 balanced photoreceivers to simultaneously detect all the output signals from the ODs in a Fourier domain OCT system. OCT imaging at a 16 kHz frame rate, 1100 A-lines per frame, 3 mm depth range, and 23 microm resolution was demonstrated using a resonant scanner for lateral scanning.     

Synthesis of Organosilyl-Functionalized Cage-Type Germanoxanes Containing Fluoride Ions

Eight corners of a double-four ring cage-type germanoxane, containing a fluoride ion, were successfully silylated by the combination of chlorosilanes and silazanes. Three different silyl groups, trimethylsilyl, dimethylsilyl, and dimethylvinylsilyl, were attached on the corners of germanoxane cage. The solubility and reactivity of the cage modified with dimethylvinylsilyl groups were significantly increased, allowing for further reaction. Hydrosilylation reaction between dimethylvinylsilylated cage geramanoxanes and dimethylsilylated cage siloxanes afforded porous solids. Functionalization of the corners of germanoxanes with silyl groups should provide valuable building blocks in various functional materials.     

Germanium lasers in the range from far-infra red to millimetre waves

Recent experimental and theoretical achievements are reviewed on three types of laser oscillation inp-type germanium; the intervalence band (IVB) laser oscillation due to transitions between the light-hole band and the heavy-hole band, the light-hole cyclotron resonance (LHCR) laser oscillation, and the heavy hole cyclotron resonance (HHCR) maser oscillation. Described for the IVB oscillation are fundamental characteristics (such as the wavelength range of oscillation and the cooperation with higherharmonic cyclotron resonances), the polarization characteristics of radiation and influence of uniaxial stress on the oscillation. The present status of the attempt at single line oscillation is also described. As for the LHCR oscillation, the formation of population inversion and the amplification are explained on the basis of quantum mechanical calculations of the valence bands in crossed electric and magnetic fields.