Direct Enantioselective Three‐Component Synthesis of Optically Active Propargylamines in Water

An enantioselective three‐component reaction of aldehydes, amines, and alkynes in water by using a bis(imidazoline)–Cu^I catalysts having a hydrophobic substituent and sodium dodecyl sulfate as a surfactant was developed. The reaction was applied to a broad range of aldehydes and alkynes to give optically active propargylamines with excellent yields (up to 99 %) and enantiomeric excesses (up to 99 % ee).     

Copper‐Free Huisgen Cycloaddition for the 14‐3‐3‐Templated Synthesis of Fusicoccin‐Peptide Conjugates

Mid‐sized molecules have emerged as an attractive chemical space and potentially provide a robust basis for the development of synthetic agents to control intracellular protein interactions. However, the limited cell permeability and chemical tractability of such agents remain to be addressed. We envisioned that target‐templated synthesis of such mid‐sized molecules might provide a solution. Here, we exploited a copper‐free Huisgen cycloaddition for template synthesis using a peptide fragment containing a 4,8‐diazacyclononyne (DACN) moiety and an azide‐containing fusicoccin derivative in the presence or absence of recombinant 14‐3‐3ζ protein in vitro. Time‐course changes in the yield of products demonstrated that the reaction was accelerated in the presence of 14‐3‐3 and one of the regioisomers was generated predominantly, supporting the template effect.     

Multiple Fused Anthracenes as Helical Polycyclic Aromatic Hydrocarbon Motif for Chiroptical Performance Enhancement

Polycyclic aromatic hydrocarbons consisting of three fused anthracene units were designed as new π‐conjugated compounds having helical structures. These expanded helicenes were synthesized by Pt‐catalyzed cycloisomerization of the corresponding ethynyl‐substituted precursors. The nonplanar and helical structure was confirmed by X‐ray analysis and DFT calculations, and the barrier to helical inversion was estimated to be 34 kJ mol^?1. The enantiomers of the diphenyl derivative were successfully resolved by chiral HPLC. Enantiopure samples showed good chiroptical performance in the CD (|Δ?| 1380 L mol^?1 cm^?1) and CPL (|g_lum| 0.013) spectra, and these values were considerably large for simple organic molecules. The unique chiroptical properties are discussed on the basis of the molecular structure and the electronic state with the aid of time‐dependent DFT calculations.     

A method to determine effective metamaterial properties based on stratified metafilms

Metamaterials’ properties may be quantified through the assignment of bulk material parameters such as magnetic permeability and electric permittivity. These assignments rely on the assumption that metamaterials are effective media, in this context meaning that their electromagnetic properties are independent of the sample size. This assumption is not always valid, particularly for metafilms, the surface equivalents of metamaterials. However, metamaterials comprised of numerous metafilm and dielectric layers can be uniquely characterized in the effective medium approximation when all aspects of the metamaterial are properly integrated. We present a simple model based on stratified systems to illustrate this fact. The model further assists in the interpretation of novel metamaterial behaviors and offers a rapid and accurate method to determine the functionality of bulk metamaterial-based devices.     

Electron spin torque in atoms

The spin torque and zeta force, which govern spin dynamics, are studied by using monoatoms in their steady states. We find nonzero local spin torque in transition metal atoms, which is in balance with the counter torque, the zeta force. We show that d-orbital electrons have a crucial effect on these torques. Nonzero local chirality density in transition metal atoms is also found, though the electron mass has the effect to wash out nonzero chirality density. Distribution patterns of the chirality density are the same for Sc–Ni atoms, though the electron density distributions are different.     

New phenylethanoid glycosides from Bacopa monniera

Three new phenylethanoid glycosides, viz. monnierasides I-III (1-3) along with the known analogue plantainoside B were isolated from the glycosidic fraction of Bacopa monniera. Their structures were elucidated mainly on the basis of two dimensional (2D) NMR spectral analyses.     

A cyclic oligophenylene containing two 1,8-naphthalene units bridged by two face-to-face biphenyl linkages exhibiting unusual strain and pi-pi interaction

1,8-[1,8-Naphthalenediylbis(4',4-biphenyldiyl)]naphthalene, a very stable strained cyclophane, has been synthesized in moderate yield using the copper-catalyzed coupling of 1, 8-bis(4-(tributylstannyl)phenyl)naphthalene. The X-ray analysis of the titled compound discloses bent p,p'-biphenylylene chains with splayed naphthalene rings, and the p,p'-biphenylylene chains located face-to-face indicate a fairly strong pi-pi interaction.     

ESEEM study of the location of spin-polarized chlorophyll-quinone radical pair in membrane-oriented spinach photosystems I and II complexes

Light-induced spin-polarized radical pairs, P700⁺A₁ ^? in spinach photosystem (PS) I particles and P680⁺Q_A ^? in Zn-substituted PS II core complexes, in oriented membranes were studied by pulsed electron paramagnetic resonance (EPR). Based on the determined distance of 25.2 ± 0.2 Å between P700 and A₁, the angular dependence of the spin-polarized electron spin echo envelope modulation (ESEEM) spectra on the magnetic field suggests that the angle between $R_{P700 - {\rm A}_1 } $ , the radius-vector connecting P700 and A₁, and the membrane normaln was 24 ± 4° in PS I particles. Obtained angle and distance of P700-A₁ axis suggested Q_K side in the molecular geometry of cofactors presented in a recent X-ray crystallography of cyanobacterial PS I reaction center to be an active branch of electron transfer. The distance between P680 and Q_A was determined to be 27.4 ± 0.3 Å for a nonoriented PS II. The angle between $R_{P680 - Q_{\rm A} } $ , the radius-vector connecting P680 and Q_A, andn was determined to be 21 ± 5°. The angle of P680-Q_A axis was close to that of 20° of P870-Q_A axis reported in X-ray analysis of the purple bacterial reaction center crystal.