Random Copolymers of 1,5-Dioxepan-2-one

ABSTRACT

Copolymers of 1,5-dioxepan-2-one (DXO) and e-caprolactone (?-CL), δ-valerolactone (δ-VL) or L-lactide (LLA) have been synthesized and characterized. High molecular weight copolymers were obtained using stannous-2-ethyl hexanoate as catalyst in bulk. Reactivity ratios for the copolymerization of DXO and δ-VL were determined at 110°C as r_VL=0.5 and r_DXO=2.3. At high conversion, depolymerization of δ-VL occurred, resulting in lower molecular weight and variations in the copolymer composition.

Physical properties, such as crystallinity and melting temperature of the DXO-copolymers proved to be strongly dependent on the choice of comonomer and on the molar composition of the copolymers. DXO appears to be incorporated into the poly-?-caprolactone (PCL) crystals and to some extent into the poly-δ-valerolactone (PVL) crystals, resulting in a more gradual decrease in crystallinity with increasing amount of DXO.     

Secondary ion yields produced by keV atomic and polyatomic ion impacts on a self-assembled monolayer surface

A suite of keV polyatomic or 'cluster' projectiles was used to bombard unoxidized and oxidized self-assembled monolayer surfaces. Negative secondary ion yields, collected at the limit of single ion impacts, were measured and compared for both molecular and fragment ions. In contrast to targets that are orders of magnitude thicker than the penetration range of the primary ions, secondary ion yields from polyatomic projectile impacts on self-assembled monolayers show little to no enhancement when compared with monatomic projectiles at the same velocity. This unusual trend is most likely due to the structural arrangement and bonding characteristics of the monolayer molecules with the Au(111). Copyright 1999 John Wiley & Sons, Ltd.     

Fusion around the barrier for 7Li+12C

Fusion cross-sections for the ⁷Li + ¹²C reaction have been measured at energies above the Coulomb barrier by the direct detection of evaporation residues. The heavy evaporation residues with energies below 3 MeV could not be separated out from the α-particles in the spectrum and hence their contribution was estimated using statistical model calculations. The present work indicates that suppression of fusion cross-sections due to the breakup of ⁷Li may not be significant for ⁷Li + ¹²C reaction at energies around the barrier.     

Spectrum of two quasiequal-energy electrons ejected by a high-energy photon

We present numerical results for the photoelectron spectrum in double ionization by keV photons in the quasiequal-energy sharing region. In this region of the spectrum, the relevant ionizing mechanism is due to a mutual sharing of the photon momentum by both electrons, with small momentum transferred to the atomic nucleus. Calculations were performed for photon energies of 25 and 50 keV, where retardation effects are fundamental, while final-state correlations are of minor importance. The spectra present a two-peak structure, with maxima located at the photoelectron energies , with the photon energy in atomic units. We discuss the general features of the spectrum in terms of the picture of the photoionization of two free electrons, and we propose a way of detecting the contribution by experiments. Received 24 January 2000     

Thiolate ligands for synthesis of water-soluble gold clusters

Water-soluble monolayer-protected gold clusters (MPCs) have been an object of investigation by many research groups since their first syntheses were reported in 1998 and 1999. The basic requirements for a ligand to form a monolayer protecting a gold cluster were established some time ago for alkanethiolate MPCs, but there has been no such information published for water-soluble MPCs. We identify 6 new ligands capable of forming water-soluble MPCs, as well as 22 water-soluble ligands that fail to form MPCs. Our findings contribute not only to the definition of the requirements for MPC formation but also to the variety of MPCs available for applications in chemistry and biology.     

Real meromorphic functions and linear differential polynomials

We determine all real meromorphic functions f in the plane such that f has finitely many zeros, the poles of f have bounded multiplicities, and f and F have finitely many non-real zeros, where F is a linear differential polynomial given by F = f (k) +Σk-1j=0ajf(j) , in which k≥2 and the coefficients aj are real numbers with a0≠0.     

Rigid, specific, and discrete gold nanoparticle/antibody conjugates

A general method of rigid, specific labeling of proteins with gold clusters has been devised. The method relies on the conjugation of a glutathione monolayer-protected gold cluster (MPC) with a single chain Fv antibody fragment (scFv), mutated to present an exposed cysteine residue. Efficient formation of a gold-thiolate bond between the MPC and scFv depends on activation of the gold cluster by chemical oxidation. Once formed, the MPC-scFv conjugate is treated with a reductant to quench cluster reactivity. The procedure has been performed with an MPC with an average Au(71) core and an scFv directed against a tetrameric protein, the influenza neuraminidase. A complex of the MPC-scFv conjugate with the neuraminidase was isolated, and the presence of four gold clusters was verified by cryoelectron microscopy.     

Synthesis and characterization of Au102(p-MBA)44 nanoparticles

The synthesis of Au(102)(p-MBA)(44) nanoparticles on a preparative scale in high yield is described. Various analytical methods are shown to give results consistent with the composition and known structure of the particles, showing the preparation is essentially homogeneous, and attesting to the validity of the methods as well. Derivatization of the particles with proteins and DNA is demonstrated, and conditions are described for imaging individual particles by cryo-EM at low electron dose, close to focus, conditions optimal for recording high-resolution details.     

Electronic and vibrational signatures of the Au102(p-MBA)44 cluster

Optical absorption of a gold nanocluster of 102 Au atoms protected by 44 para-mercaptobenzoic acid (p-MBA) ligands is measured in the range of 0.05-6.2 eV (mid-IR to UV) by a combination of several techniques for purified samples in solid and solution phases. The results are compared to calculations for a model cluster Au(102)(SMe)(44) based on the time-dependent density functional theory in the linear-response regime and using the known structure of Au(102)(p-MBA)(44). The measured and calculated molar absorption coefficients in the NIR-vis region are comparable, within a factor of 2, in the absolute scale. Several characteristic features are observed in the absorption in the range of 1.5-3.5 eV. The onset of the electronic transitions in the mid-IR region is experimentally observed at 0.45 ± 0.05 eV which compares well with the lowest calculated transition at 0.55 eV. Vibrations in the ligand layer give rise to fingerprint IR features below the onset of low-energy metal-to-metal electronic transitions. Partial exchange of the p-MBA ligand to glutathione does not affect the onset of the electronic transitions, which indicates that the metal core of the cluster is not affected by the ligand exchange. The full spectroscopic characterization of the Au(102)(p-MBA)(44) reported here for the first time gives benchmarks for further studies of manipulation and functionalization of this nanocluster to various applications.