Oriented Crystallization on Organic Monolayers to Control Concomitant Polymorphism

Nucleation events and crystal growth can be guided by molecular recognition at interfaces through intermolecular interactions. The short-acting antimicrobial sulfa drug sulfathiazole is known for its concomitant crystallization, which has five known polymorphs, due to conformational flexibility and hydrogen-bond synthon variation. In its development stage of a drug the issue of concomitant crystallization needs to be addressed with respect to patent litigation, including legal actions to protect patents against infringement. A functional self-assembled monolayer (SAM) of organic thiol on a gold surface has been employed as an efficient approach to control concomitant nucleation of such flexible drugs. The crystallization on a SAM surface is mostly kinetically driven and often leads to the nucleation of novel metastable forms. Spectroscopic, thermal analysis and X-ray diffraction studies reveal that a previously unknown, sixth form of the drug nucleates on the designed SAM surface.     

Simultaneous control of nanocrystal size and nanocrystal-nanocrystal separation in CdS nanocrystal assembly

We report an easy, one pot synthesis to prepare ordered CdS nanocrystals with varying inter-particle separation and characterize the particle separation using x-ray diffraction at low and wide angles.     

Nickel boride reductive cleavage of allylic trimethylsilyl ethers

Nickel boride reductive cleavage of allylic trimethylsilyl ethers yielding alkenes is described.     

A comparison between X-ray absorption spectroscopy and Bremsstrahlung Isochromat Spectroscopy: The empty states of Pd−Al alloys and Pd2Si

We present X-ray absorption spectra (XAS) obtained with synchrotron radiaton at the PdL _2,3 edges of Pd–Al alloys and Bremsstrahlung Isochromat Spectra (BIS) at 1,486.7 eV of Pd–Al alloys and of Pd₂Si. The XAS and BIS results for the alloys are very similar indicating that the effect of the core potential (e.g. many-body, electronhole excitation) is negligible. The BIS results on Pd₂Si show differences with respect to Pd–Al due to the more localized bonds. The comparison between XAS and BIS data in Pd₂Si is still an open problem and might indicate a more subtle role of the core-hole potential.     

On the self-trapping of an electron due to lattice interaction

The problem of the sharpness of the polaron self-trapping transition for a single electron placed in the conduction band of an insulator and interacting with the phonons of the underlying lattice is investigated within the Fröhlich Hamiltonian. It is shown that this phenomenon depends sensitively on the lattice dimensionality, the nature of the electron-phonon coupling, the nature of the phonon dispersion; and on the discrete or the continuum nature of the applicable Hamiltonian.     

Silicon-mediated C-isoprenylation of phenols

C-isoprenylation of phenols has been effected using a combination of isoprene and in situ generated iodotrimethylsilane or hydrogen iodide.     

Electronic structure of CaSi and CaSi2

The electronic properties of calcium silicides (CaSi and CaSi₂) are investigated through a joint experimental and theoretical study using Bremsstrahlung Isochromat spectroscopy (BIS) and self-consistent calculation of the electronic states by the Linear Muffin-Tin Orbitals (LMTO) method in the Atomic Sphere Approximation (ASA). The peculiar crystal structure of CaSi₂ with two inequivalent Si atoms is responsible for a well defined BIS feature. We found that the calculated high energy DOS features are consistently lower in energy compared to the BIS spectra. Inclusion of the cross-sections of different states into the calculations improves the agreement between the experimental spectra and the calculated curve. We also show that considerable covalent character is present in the bond of calcium silicides.     

Ruthenium(II) complexes with triphenylphosphine or triphenylarsine and other monodentate ligands

Synthesis and studies on some five-coordinate ruthenium(II) complexes, viz. [Ru(MPh₃)(C₆H₅CHO)₂Cl₂] and [Ru(MPh₃)₂(CO)Cl₂] (where M = P or As) have been described. Reactions of [Ru(MPh3)(C₆H₅CHO)₂Cl₂] with N,N-dimethylformamide, dimethylsulphoxide and pyridine and of [Ru(MPh₃)₂(CO)Cl₂] with pyridine are described.