Shell effects in the evolution of the mass asymmetry in heavy-ion collisions leading to composite systems withZ=108

Fragment mass distributions are presented obtained in the heavy-ion reactions²²Ne+²⁴⁹Cf,³²S+²³⁸U,⁴⁰Ar+²³²Th and⁵⁶Fe+²⁰⁸Pb leading to composite systems with equal nuclear charge numberZ=108. The experiments were performed at the heavy-ion cyclotron U 300 of the Laboratory of Nuclear Reactions in Dubna. The spectrometer DEMAS was used to measure the time-of-flight values and the laboratory angles of the correlated fragments. The shape of the mass distributions strongly depends on the initial mass asymmetry. When decreasing the bombarding energy down to values near the Coulomb barrier, the mass distributions obtained in the reactions³²S+²³⁸U and⁴⁰Ar+²³²Th exhibit relative maxima ofM≈205 interpreted to be due to stabilizing effects of nuclear shells during the fragmentation process.     

Advanced solvent signal suppression for the acquisition of 1D and 2D NMR spectra of Scotch Whisky

A simple and robust solvent suppression technique that enables acquisition of high‐quality 1D ¹H nuclear magnetic resonance (NMR) spectra of alcoholic beverages on cryoprobe instruments was developed and applied to acquire NMR spectra of Scotch Whisky. The method uses 3 channels to suppress signals of water and ethanol, including those of ¹³C satellites of ethanol. It is executed in automation allowing high throughput investigations of alcoholic beverages. On the basis of the well‐established 1D nuclear Overhauser spectroscopy (NOESY) solvent suppression technique, this method suppresses the solvent at the beginning of the pulse sequence, producing pure phase signals minimally affected by the relaxation. The developed solvent suppression procedure was integrated into several homocorrelated and heterocorrelated 2D NMR experiments, including 2D correlation spectroscopy (COSY), 2D total correlation spectroscopy (TOCSY), 2D band‐selective TOCSY, 2D J‐resolved spectroscopy, 2D ¹H, ¹³C heteronuclear single‐quantum correlation spectroscopy (HSQC), 2D ¹H, ¹³C HSQC‐TOCSY, and 2D ¹H, ¹³C heteronuclear multiple‐bond correlation spectroscopy (HMBC). A 1D chemical‐shift‐selective TOCSY experiments was also modified. The wealth of information obtained by these experiments will assist in NMR structure elucidation of Scotch Whisky congeners and generally the composition of alcoholic beverages at the molecular level.     

C-H functionalization logic in total synthesis

In this critical review, the strategic and economic benefits of C-H functionalization logic will be analyzed through the critical lens of total synthesis. In order to illustrate the dramatically simplifying effects this type of logic can potentially have on synthetic planning, we take the reader through a series of case studies in which it has already been successfully applied. In the first section, a chronological look at key historical syntheses will be examined, leading into modern day examples. In the second section, our own experience with applying and executing synthesis with a C-H functionalization "mindset" will be discussed (114 references).     

A theory for the anisotropic and inhomogeneous dielectric properties of proteins

Using results from the dielectric theory of polar solids and liquids, we calculate the mesoscopic, spatially-varying dielectric constant at points in and around a protein by combining a generalization Kirkwood-Fr?hlich theory along with short all-atom molecular dynamics simulations of equilibrium protein fluctuations. The resulting dielectric permittivity tensor is found to exhibit significant heterogeneity and anisotropy in the protein interior. Around the surface of the protein it may exceed the dielectric constant of bulk water, especially near the mobile side chains of polar residues, such as K, N, Q, and E. The anisotropic character of the protein dielectric selectively modulates the attractions and repulsions between charged groups in close proximity.     

Issues in the numerical solution of evolutionary delay differential equations

Delay differential equations are of sufficient importance in modelling real-life phenomena to merit the attention of numerical analysts. In this paper, we discuss key features of delay differential equations (DDEs) and consider the main issues to be addressed when constructing robust numerical codes for their solution. We provide an introduction to the existing literature and numerical codes, and in particular we indicate the approaches adopted by the authors. We also indicate some of the unresolved issues in the numerical solution of DDEs. Communicated by J.C. Mason     

Synthesis,structural analysis,and self-assembly of phenylene ethynylene oligomers and their ?F, ?CF3, and ?CH3 substituted derivatives

Oligomers consisting of aromatic building blocks separated by alkynyl units were synthesized by Sonogashira cross-coupling of aryl halides with terminal acetylenes. Strong electron acceptors such as  F and  CF₃ and weak electron donors like  CH₃ were placed as substituents on one of the benzene rings. Acetyl-protected sulfhydryl groups were attached to one end of these molecules to promote their self-organization on gold surfaces. The electron-transport properties of such self-assembled monolayers (SAMs) are highly sensitive to the local order of the molecules in the solid state. Single crystals were analyzed by X-ray diffraction experiments that revealed structural details that could lead to a better understanding of the electron-transport properties. The unsymmetrical substitution of the aromatic rings by electron-active groups in the ortho-, meta-, or para positions resulted in changes of such molecular parameters as bonding and torsion angles and planarity. These parameters, in turn, can affect the angle of the molecular attachment to a gold substrate and the density of the resulting SAMs. Patterned SAMs of some of these molecules and comparison alkane thiols were obtained on gold by microcontact printing or flooding. The SAM thickness was determined by spectroscopic ellipsometry. Surface potential differences between adjacent SAMs or between SAMs and the gold substrate were measured by scanning surface potential microscopy under ambient conditions. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 541–550, 2004