ARPES and STS investigation of noble metal Shockley states: Confinement in vicinal Au(1 1 1) surfaces and self-organized nanostructures

Spectroscopic effects associated with the superperiodic surface structure have been observed in Au(1 1 1) vicinal surfaces and nanostructured systems. In the vicinal Au(23 23 21) surface, high resolution angle resolved photoemission spectroscopy shows the opening of several gaps in the surface band structure, whereas scanning tunneling spectroscopy reveals the energy dependence of the electronic density. These combined spectroscopic data allow to determine the reconstruction potential by deducing their first Fourier components. We also demonstrate that due to the peculiar growth on this Au vicinal surface, we can obtain a self-assembled superlattice of triangular Ag islands. The high ordering of the nanostructures leads to homogenous electronic properties.     

Stochastic radiative transfer model for mixture of discontinuous vegetation canopies

Modeling of the radiation regime of a mixture of vegetation species is a fundamental problem of the Earth's land remote sensing and climate applications. The major existing approaches, including the linear mixture model and the turbid medium (TM) mixture radiative transfer model, provide only an approximate solution to this problem. In this study, we developed the stochastic mixture radiative transfer (SMRT) model, a mathematically exact tool to evaluate radiation regime in a natural canopy with spatially varying optical properties, that is, canopy, which exhibits a structured mixture of vegetation species and gaps. The model solves for the radiation quantities, direct input to the remote sensing/climate applications: mean radiation fluxes over whole mixture and over individual species. The canopy structure is parameterized in the SMRT model in terms of two stochastic moments: the probability of finding species and the conditional pair-correlation of species. The second moment is responsible for the 3D radiation effects, namely, radiation streaming through gaps without interaction with vegetation and variation of the radiation fluxes between different species. We performed analytical and numerical analysis of the radiation effects, simulated with the SMRT model for the three cases of canopy structure: (a) non-ordered mixture of species and gaps (TM); (b) ordered mixture of species without gaps; and (c) ordered mixture of species with gaps. The analysis indicates that the variation of radiation fluxes between different species is proportional to the variation of species optical properties (leaf albedo, density of foliage, etc.) Gaps introduce significant disturbance to the radiation regime in the canopy as their optical properties constitute major contrast to those of any vegetation species. The SMRT model resolves deficiencies of the major existing mixture models: ignorance of species radiation coupling via multiple scattering of photons (the linear mixture model) or overestimation of this coupling due to neglecting spatial clumping of species (the TM approach). Thus, based on the former experience with mixture modeling, this study establishes an advanced theoretical basis for future mixture applications.     

The Aza‐Morita–Baylis–Hillman Reaction: A Mechanistic and Kinetic Study

The aza‐Morita‐Baylis–Hillman (aza‐MBH) reaction has been studied in a variety of solvents, a selection of imine substrates and with various combinations of PPh₃ and para‐nitrophenol as the catalyst system. The measured kinetic data indicates that the effects of solvent and protic co‐catalyst are strongly interdependent. These results are most easily reconciled with a mechanistic model involving the reversible protonation of zwitterionic intermediates in the catalytic cycle, which is also supported by ³¹P NMR spectroscopy and quantum chemical studies.     

Synthesis of photocleavable poly(methyl methacrylate‐block‐d‐lactide) via atom‐transfer radical polymerization and ring‐opening polymerization

The synthesis and characterization of a photocleavable block copolymer containing an ortho‐nitrobenzyl (ONB) linker between poly(methyl methacrylate) and poly(d ‐lactide) blocks is presented here. The block copolymers were synthesized via atom transfer radical polymerization (ATRP) of MMA followed by ring‐opening polymerization (ROP) of d ‐Lactide and ROP of d ‐lactide followed by ATRP of MMA from a difunctional photoresponsive ONB initiator, respectively. The challenges and limitations during synthesis of the photocleavable block copolymers using the difunctional photoresponsive ONB initiator are discussed. The photocleavage of the copolymers occurs under mild conditions by simple irradiation with 302 nm wavelength UV light (Relative intensity at 7.6 cm: 1500 μW/cm²) for several hours. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4309–4316     

1H, 13C and 15N NMR spectral analysis of substituted 1,2,3,4‐tetrahydro‐pyrido[1,2‐a]pyrimidines

The NMR spectroscopic data of a series of thirty‐four 3‐acylpyrido[1,2‐a]pyrimidinium salts are analyzed, which were prepared as either perchlorates or chlorides. Methyl group substituted 3‐aroyltetrahydropyrido[1,2‐a]pyrimidines with the methyl substituent in positions 6, 8 and 9 as well as both in positions 6 and 8 were investigated bearing various aroyl substituents. Unequivocal assignment of all resonances was achieved via two‐dimensional ¹H,¹H‐COSY measurements, ¹H,¹³C and ¹H,¹⁵N HSQC as well as HMBC experiments, and important diagnostic CH and NH couplings in the heteroaromatic ring system are evaluated. The influence of the methyl substituents was analyzed on the proton, carbon and nitrogen shifts. A significant effect of the counter ion on some chemical shifts of the nuclei under discussion of the pyridopyrimidines is found, allowing the indirect detection of the anion, which is confirmed by direct measurement of the ³⁵Cl nucleus of the perchlorates. Copyright © 2013 John Wiley & Sons, Ltd.     

Phosphonobetaine/sulfur dioxide copolymer by Butler’s cyclopolymerization process

The zwitterionic monomer, ethyl 3-(N,N-diallylammonio)propanephosphonate and sulfur dioxide were cyclocopolymerized in DMSO using azobisisobutyronitrile or ammonium persulfate as initiators to afford a pH-responsive polyphosphonobetaine/SO₂ (PPB/SO₂) copolymer. The polymers, on treatment with HCl and NaOH, gave the aqueous solutions of the corresponding cationic polyphosphononic acid (CPP) and anionic polyphosphonate (APP). The solution properties of the PPB having two pH-responsive functionalities were investigated in detail by potentiometric and viscometric techniques. Basicity constants of the amine and phosphonate groups in APP were found to be “apparent” and as such follow the modified Henderson–Hasselbalch equation. The incorporation of SO₂ moiety has resulted in the decrease of basicity constant of the nitrogens in the copolymer by staggering ?2 units of log K in compare to that of the corresponding homopolymer. The basicity difference is expected to have an effect on the chelating properties of the polymers. In contrast to many polycarbo- and -sulfobetaines, the PPB was all found to be soluble in salt-free water as well as in salt (including Ca²⁺ and Li⁺)-added solutions. The PPB demonstrated ‘antipolyelectrolyte’ viscosity behavior and found to have higher viscosity values in LiCl than in NaCl or NaI.     

In situ‐generated Ru(III)‐mediated ATRP from the polymeric Ru(III) complex in the absence of activator generation agents

Past research has examined the atom transfer radical polymerization (ATRP) with high oxidation state metal complexes and without the need for any additives such as reducing agent or free radical initiator. To extend this research, half‐metallocene ruthenium(III) (Ru(III)) catalysts were used for the polymerization of methyl methacrylate (MMA) for the first time. These catalysts were generated in situ simply by mixing phosphorus‐containing ligand and pentamethylcyclopentadienyl (Cp*) Ru(III) polymer ((Cp*RuCl₂)_n). The complexes in their higher oxidation state such as Cp*RuCl₂(PPh₃) were air‐stable, highly active, and removable catalysts for the ATRPs of MMA with both precision control of molecular weight and narrow polydispersity index. The addition of ppm amount of metal catalyst contributed to the formation of very well‐defined homopolymers and copolymers. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

A general and convenient route to oxazolyl ligands

A diverse range of chiral and achiral oxazolyl ligands, which have many applications including catalysis and luminescent devices, are synthesized simply in three steps from readily available and inexpensive phenol and amino alcohol starting materials. The method can be applied to ligands with electron-donating/-withdrawing and sterically demanding/undemanding substituents, and can conveniently be scaled up to >25 g of product.     

Chemoenzymatic Synthesis of 2-Arachidonoylglycerol, An Endogenous Ligand for Cannabinoid Receptors

A simple and efficient synthesis of 2-arachidonoyl glycerol, an endogenous agonist for cannabinoid receptors was achieved using Novozym 435, immobilized lipase from Candida antarctica.