Unified approach to the sesquiterpenoids,lauranes and cyclolauranes: Total synthesis of (±)-isolaurene

A general approach to the total synthesis of sesquiterpene, isolaurene (1a) and cyclolaurene (2a) is featured from commercially available 3-methyl cyclopenten-2-one. The strategy includes a Stork-Danheiser sequence concomitant with a Ni(II)-catalyzed conjugate addition of methyl group onto 3-aryl 2-methyl cyclopenten-2-one to afford the advanced intermediate 11. A methyllithium addition onto compound 11 with an eventual dehydration completed the total synthesis of isolaurene (1a) in 5 steps (58.3% overall yields).     

Diels-Alder chemistry of graphite and graphene: graphene as diene and dienophile

The zero-band-gap electronic structure of graphene enables it to function as either the diene or the dienophile in the Diels-Alder reaction, and this versatile synthetic method offers a powerful strategy for the reversible modification of the electronic properties of graphene under very mild conditions.     

On the dispersion of a solute in oscillating flow through a channel

The paper presents an exact analysis of the dispersion of a solute in an incompressible viscous fluid flowing slowly in a parallel plate channel under the influence of a periodic pressure gradient. Using a generalised dispersion model which is valid for all times after the solute injection, the diffusion coefficientsK _i (τ)(i=1,2,3,…) are determined as functions of timeτ when the initial distribution of the solute is in the form of a slug of finite extent. The second coefficientK ₂(τ) gives a measure of the longitudinal dispersion of the solute due to the combined influence of molecular diffusion and nonuniform velocity across the channel cross-section. The analysis leads to the novel result thatK ₂(τ) consists of a steady partS and a fluctuating partD ₂(τ) due to the pulsatility of the flow. It is shown thatS increases with increase inλ (the amplitude of pressure pulsation) for small values ofω (the frequency of the pulsation). But for largeω, S decreases with increase inλ. It is also found that for fixedλ, there is very little fluctuation inD ₂(τ) forω=1, butD ₂(τ) shows fluctuation with large amplitude whenω slightly exceeds unity. The amplitude ofD ₂(τ) then decreases with further increase inω. Thus the variation of bothS andD ₂(τ) withω is non-monotonic. Finally,? _m , the average concentration of the solute over the channel cross-section is determined for various values ofλ andω.     

Solution properties of graphite and graphene

Covalent derivatization of the acidic functional groups in oxidized graphite with octadecylamine renders graphite soluble in common organic solvents. Atomic force microscopic characterization of the soluble species supports the idea that the solutions consist of single and few layer graphene sheets, and we report the first solution properties of graphite.     

Kinetic modeling of charge-transfer quenching in the CP29 minor complex

We performed transient absorption (TA) measurements on CP29 minor light-harvesting complexes that were reconstituted in vitro with either violaxanthin (Vio) or zeaxanthin (Zea) and demonstrate that the Zea-bound CP29 complexes exhibit charge-transfer (CT) quenching that has been correlated with the energy-dependent quenching (qE) in higher plants. Simulations of the difference TA kinetics reveal two-phase kinetics for intracomplex energy transfer to the CT quenching site in CP29 complexes, with a fast <500 fs component and a approximately 6 ps component. Specific chlorophyll sites within CP29 are identified as likely locations for CT quenching. We also construct a kinetic model for CT quenching during qE in an intact system that incorporates CP29 as a CT trap and show that the model is consistent with previous in vivo measurements on spinach thylakoid membranes. Finally, we compare simulations of CT quenching in thylakoids with those of the individual CP29 complexes and propose that CP29 rather than LHCII is a site of CT quenching.     

Artifacts in T1 rho-weighted imaging: compensation for B(1) and B(0) field imperfections

The origin of spin locking image artifacts in the presence of B(0) and B(1) magnetic field imperfections is shown theoretically using the Bloch equations and experimentally at low (omega(1) < Delta omega(0)), intermediate (omega(1) approximately Delta omega(0)) and high (omega(1) > Delta omega(0)) spin locking field strengths. At low spin locking fields, the magnetization is shown to oscillate about an effective field in the rotating frame causing signature banding artifacts in the image. At high spin lock fields, the effect of the resonance offset Deltao mega(0) is quenched, but imperfections in the flip angle cause oscillations about the omega(1) field. A new pulse sequence is presented that consists of an integrated spin echo and spin lock experiment followed by magnetization storage along the -z-axis. It is shown that this sequence almost entirely eliminates banding artifacts from both types of field inhomogeneities at all spin locking field strengths. The sequence was used to obtain artifact free images of agarose in inhomogeneous B(0) and B(1) fields, off-resonance spins in fat and in vivo human brain images at 3 T. The new pulse sequence can be used to probe very low frequency (0-400 Hz) dynamic and static interactions in tissues without contaminating B(0) and B(1) field artifacts.     

Scattering on energy-dependent separable potentials

We derive a coordinate space approach to energy-dependent separable potentials and clearly demonstrate its calculational advantage. The results presented include expressions for (i) low-energy scattering parameters and (ii) off-energy-shellT andK matrices. We study energy dependence of the effective potential with particular emphasis on cross-channel suppression effects.