General Method to Increase Carboxylic Acid Content on Nanodiamonds

Carboxylic acid is a commonly utilized functional group for covalent surface conjugation of carbon nanoparticles that is typically generated by acid oxidation. However, acid oxidation generates additional oxygen containing groups, including epoxides, ketones, aldehydes, lactones, and alcohols. We present a method to specifically enrich the carboxylic acid content on fluorescent nanodiamond (FND) surfaces. Lithium aluminum hydride is used to reduce oxygen containing surface groups to alcohols. The alcohols are then converted to carboxylic acids through a rhodium (II) acetate catalyzed carbene insertion reaction with tert–butyl diazoacetate and subsequent ester cleavage with trifluoroacetic acid. This carboxylic acid enrichment process significantly enhanced nanodiamond homogeneity and improved the efficiency of functionalizing the FND surface. Biotin functionalized fluorescent nanodiamonds were demonstrated to be robust and stable single-molecule fluorescence and optical trapping probes.     

Selenadiazolopyridine: a synthon for supramolecular assembly and complexes with metallophilic interactions

The synthesis and characterization of the complexes of Cu(I), Ag(I), Cu(II), and Co(II) ions with 1,2,5-selenadiazolopyridine (psd) is reported. The following complexes have been prepared: [Cu(2)(psd)(3)(CH(3)CN)(2)](2+)2(PF(6)(-)); [(CuCl)(2)(psd)(3)]; [Cu(2)(psd)(6)](2+)2(ClO(4))(-); [Ag(2)(psd)(2)](2+)2(NO(3))(-); [Ag(2)(psd)(2)](2+)2(CF(3)COO)(-); [Cu(psd)(2)(H(2)O)(3)](2+)2(ClO(4))(-)·(psd)(2); [Cu(psd)(4)(H(2)O)](2+)2(ClO(4))(-)·(CHCl(3)); [Cu(psd)(2)(H(2)O)(3)](2+)2(NO(3))(-)·(H(2)O)·(psd)(2), and [Co(psd)(2)(H(2)O)(4)](2+)2(ClO(4))(-)·(psd)(2). The electronic structure of ligand psd, in particular the bond order of Se-N bonds, has been probed by X-ray diffraction, (77)Se NMR, and computational studies. A detailed analysis of the crystal structures of the ligand and the complexes revealed interesting supramolecular assembly. The assembly was further facilitated by the presence of neutral ligands for some complexes (Cu(II) and Co(II)). The molecular structure of the ligand showed that it was present as a dimer in the solid state where the monomers were linked by strong secondary bonding Se···N interactions. The crystal structures of Cu(I) and Ag(I) complexes revealed the dinuclear nature with characteristic metallophilic interactions [M···M] (M = Cu, Ag), while the Cu(II) and Co(II) complexes were mononuclear. The presence of M···M interactions has been further probed by Atoms in Molecules (AIM) calculations. The paramagnetic Cu(II) and Co(II) complexes have been characterized by UV-vis, ESI spectroscopy, and room temperature magnetic measurements.     

Short and Stereoselective Syntheses of Pheromone Components of Aproaerema Modicella

Efficient syntheses of pheromone components of Aproaerema modicella starting from a common intermediate 7-octyn-1-ol is described.     

Improved semiempirical heats of formation through the use of bond and group equivalents

Deficiencies in energetics obtained using the common semiempirical methods, AM1, PM3, and MNDO, may partly be traced to the use of pseudoatomic equivalents for conversion of molecular energies to heats of formation at 298 K. We present an alternative scheme based on the use of bond and group equivalents. Values for the 61 bond and group equivalents necessary for treatment of molecules containing the common organic elements, hydrogen, carbon, nitrogen, and oxygen have been derived. For a set of 583 neutral, closed-shell molecules mean absolute errors in AM1, PM3, and MNDO heats of formation are reduced from 6.6, 4.2, and 8.2 kcal/mol to 2.3, 2.2, and 3.0 kcal/mol, respectively. Several systematic problems are overcome in the present scheme including relative stabilities of branched hydrocarbons, energetics of conjugated systems, heats of formation of long chain hydrocarbons, and enthalpies of molecules containing multiple heteroatoms. Although the approach is restricted to molecules with well-defined functional groups, the equivalents are easy to incorporate and are chemically relevant. This revised procedure allows semiempirical methods to be used for far more reliable evaluations of heats of reactions. Estimates are made of the errors inherent in these semiempirical formalisms, arising from integral approximations and the neglect of explicit treatment of electron correlation effects, while excluding those from inadequate parameterization.     

Heisenberg's microscope—A misleading illustration

According to the Rayleigh criterion of classical optics, the finite resolving power of a microscope is due to the width of the central peak of the Fraunhofer diffraction pattern produced by the microscope's finite lens aperture. During the last few decades, theories and techniques for superresolution beyond the Rayleigh criterion have been developed in classical optics. Thus, Heisenberg's microscope could also in principle be made to give superresolution and thereby appear to violate the uncertainty relation. We believe that this paradox is due to the inappropriate use of a definition, based purely on experimental convenience, to support a quantum mechanical theorem.     

Short range orientational order in nematic liquid crystals

The different approximations that have been used in applying Bethe’s cluster model to the nematic-isotropic phase transition are examined. It is shown that the introduction of a higher order term in the mean field potential of an outer molecule of the cluster improves the consistency of the theory considerably. In particular, the importance of satisfying Chang’s relation is emphasized. Calculations are presented of the long and short range order parameters, heat of transition and specific heat for different values ofz, the number of nearest neighbours around any given molecule, for both nonpolar and antiparallel near neighbour correlations. Even the new mean field potential appears to be inadequate forz=3.     

Nucleation of superconductivity in mesoscopic star-shaped superconductors

We study the phase transition of a star-shaped superconductor, which covers smoothly the range from zero to two dimensions with respect to the superconducting coherence length . Detailed measurements and numerical calculations show that the nucleation of superconductivity in this device is very inhomogeneous: the superconducting order parameter is strongly enhanced and mostly robust in regions close to multiple boundaries. The strong inhomogeneity of the order parameter results in a rich structure of the superconducting transition as a function of temperature and magnetic field.Received: 26 February 2003, Published online: 4 August 2003PACS: 74.78.-w Superconducting films and low-dimensional structures - 74.78.Na Mesoscopic and nanoscale systems - 74.20.De Phenomenological theories D.A. Dikin: On leave from: Institute for Low Temperature Physics and Engineering, 61164 Kharkov, UkraineV.R. Misko: On leave from: Institute of Applied Physics, 2028 Kishinev, Republic of MoldovaV.M. Fomin: On leave from: State University of Moldova, 2009 Kishinev, Republic of Moldova; Also at: Technische Universiteit Eindhoven, 5600 MB Eindhoven, The NetherlandsJ.T. Devreese: Also at: Universiteit Antwerpen (RUCA), B-2020 Antwerpen, Belgium and Technische Universiteit Eindhoven, 5600 MB Eindhoven, The Netherlands     

Evaluation of Generic Gradients, Sample Pooling and MS Detection as Chiral Resolution Screening Strategies on Diverse Chiral Stationary Phases

Increased throughput in medicinal chemistry has substantially increased the production of new chiral chemical entities with diverse structural features, requiring fast chiral screening strategies. In an effort to explore screening methods we have developed and evaluated gradients in polar organic and normal phase modes on three popular chiral stationary phases using a sample set of 19 racemic compounds. When compared, gradients performed on par with the isocratic methods besides proving to be advantageous in terms of speed of analysis and elution capacity. MS detection was successfully applied to the analysis of a pooled sample consisting 19 compounds to speed-up the screening process.     

Reductive opening of aziridines with polymethylhydrosiloxane

Regio and chemoselective reductive opening of aziridines is achieved using catalytic palladium on charcoal and polymethylhydrosiloxane (PMHS) as a soluble hydrogen source.     

Si-O and P-O motifs in inorganic rings and clusters

This article presents a brief overview of different kinds of silanols and the important reactions of N-bonded silanetriols. The synthesis and characterization of silanediols containing Si-N and Si-C bonds, (2,4,6-Me₃C₆H₂)N(SiMe₃)Si(Me)(OH)₂ (1e) is described. 1e shows a polymeric crinkled tape type of structure due to extensive intermolecular hydrogen bonding. We also describe the formation of a neutral copper(II) complex derived from the reaction of CuCl₂ with (O)P(3,5-Me₂Pz)₃ where the ligand undergoes a facile P-N bond cleavage and functions as an N₂O type of tridentate ligand.