High resolution electron energy loss spectroscopy surface studies of hydrogenated detonation nano-diamond spray-deposited films

Nano-diamond films composed of 3–5 nm grains prepared by the detonation method and spray deposited onto silicon substrates were examined by high resolution electron energy loss spectroscopy (HR-EELS), Raman spectroscopy and transmission electron microscopy. The HR-EEL spectrum of the annealed and hydrogenated films displays dominant C–H losses at 360–365 meV; the diamond optical phonon and its overtones. These results suggest that the films reveal well defined hydrogenated diamond surfaces on the nanometric scale. Detailed analysis of the diamond optical phonon overtone revealed a red-shift of the basic C–C vibration by 5 meV. We attribute this shift to a phonon quantum confinement effect detected by HR-EELS spectroscopy.     

Workshop on Timing Modes for Low-Emittance Storage Rings

A three-day workshop was held in Lund, Sweden, from March 25 to 27, 2015, with a focus on timing modes for low-emittance storage rings. The MAX IV Laboratory, currently under construction in Lund, will provide a 1.5 GeV storage ring for soft X-rays and a 3 GeV storage ring with an ultralow emittance down to 0.2 nm rad for hard X-rays [1 M. Eriksson, Proceedings of 2011 PAC, TUOBS4, 737–741 (2011). [Google Scholar]]. Both rings are designed to operate with a uniform multibunch filling pattern with a 100 MHz RF system and employ passive harmonic cavities [2 Å. Andersson, Proceedings of IPAC 2011, MOPC051, 193–195 (2011). [Google Scholar]] to damp instabilities and increase the Touschek lifetime. For the 3 GeV ring, the harmonic cavities are also required to conserve the ultralow emittance at high bunch charge [3 S. C. Leemann, Phys. Rev. ST Accel. Beams 17, 050705 (2014).[Crossref] , [Google Scholar]]. The facility will include a short pulse facility delivering 100 fs FWHM X-ray pulses at a repetition rate of 100 Hz.     

Comparative study of polymeric stabilizers for magnetite nanoparticles using ATRP

A series of polyelectrolytes with controlled molecular weight, a narrow chain-length distribution, and systematic structural differences were synthesized using atom-transfer radical polymerization and investigated as stabilizers for magnetite nanoparticles in aqueous suspensions. Structural differences include the degree of polymerization, the chain architecture, and the identity of the charged functional unit. The synthesized polymers are sulfonated poly(2-hydroxyethyl methacrylate), a block copolymer of the former with poly(n-butyl methacrylate), poly(sodium styrene sulfonate), poly(sodium acrylate), and poly(sodium vinylphosphonate). The colloidal stability is assessed by measuring the fraction of particles, based on turbidity, that sediment after a period of time at increasing ionic strength. Sedimentation results are complimented by dynamic light scattering determinations of the hydrodynamic diameter of the particles that remain suspended. When adsorption and sedimentation are conducted at high pH, poly(sodium acrylate) and poly(sodium vinylphosphonate) yield the most stable suspensions because of their strong coordinative interactions with the iron oxide surface. At low pH, the polymers that retain pendant negative charges (each of the sulfonated polymers) yield high stable fractions at all ionic strengths investigated up to 100 mM (NaCl), whereas polyelectrolytes that become protonated with decreasing pH, poly(sodium acrylate) and poly(sodium vinylphosphonate), lose their stabilizing capacity even at low ionic strengths. The chain-length distribution profoundly alters a polymer's stabilization tendencies. Two poly(sodium acrylate) samples with the same number-average molecular weight but widely different chain-length distributions proved to have opposite tendencies, with the polydisperse sample being a good stabilizer and the low polydispersity one being a strong flocculant. This investigation provides guidelines for the design of polymeric stabilizers for magnetite nanoparticles according to the pH and ionic strength of the intended application.     

Effects of the biological backbone on stacking interactions at DNA-protein interfaces: the interplay between the backbone···π and π···π components

The (gas-phase) MP2/6-31G*(0.25) π···π stacking interactions between the five natural bases and the aromatic amino acids calculated using (truncated) monomers composed of conjugated rings and/or (extended) monomers containing the biological backbone (either the protein backbone or deoxyribose sugar) were previously compared. Although preliminary energetic results indicated that the protein backbone strengthens, while the deoxyribose sugar either strengthens or weakens, the interaction calculated using truncated models, the reasons for these effects were unknown. The present work explains these observations by dissecting the interaction energy of the extended complexes into individual backbone···π and π···π components. Our calculations reveal that the total interaction energy of the extended complex can be predicted as a sum of the backbone···π and π···π components, which indicates that the biological backbone does not significantly affect the ring system through π-polarization. Instead, we find that the backbone can indirectly affect the magnitude of the π···π contribution by changing the relative ring orientations in extended dimers compared with truncated dimers. Furthermore, the strengths of the individual backbone···π contributions are determined to be significant (up to 18 kJ mol(-1)). Therefore, the origin of the energetic change upon model extension is found to result from a balance between an additional (attractive) backbone···π component and differences in the strength of the π···π interaction. In addition, to understand the effects of the biological backbone on the stacking interactions at DNA-protein interfaces in nature, we analyzed the stacking interactions found in select DNA-protein crystal structures, and verified that an additive approach can be used to examine the strength of these interactions in biological complexes. Interestingly, although the presence of attractive backbone···π contacts is qualitatively confirmed using the quantum theory of atoms in molecules (QTAIM), QTAIM electron density analysis is unable to quantitatively predict the additive relationship of these interactions. Most importantly, this work reveals that both the backbone···π and π···π components must be carefully considered to accurately determine the overall stability of DNA-protein assemblies.     

The high-frequency description of scatter of a plane compressional wave by an elliptic crack

High-frequency approximations that can be interpreted in terms of the Uniform Geometrical Theory of Diffraction (UGTD) and Uniform Kirchhoff Approximation (UKA) are used to develop a code for modeling ultrasonic scatter of a plane compressional wave by an elliptic crack in the radiating near field. The approximations are intercompared and partially validated against a direct numerical code based on an FD (Finite-Difference) scheme. At present, in many realistic situations the approximate codes of the type described here offer the only viable simulation tool; purely numeric codes are not only much slower, they still require too much computer memory to simulate the complex structure of the radiating near fields.     

Dications of 3-phenylindenylidenefluorenes: evaluation of antiaromaticity of indenyl and fluorenyl cations by magnetic measures

Dications of p-substituted 3-phenylindenylidenefluorenes were prepared to examine the response of the resulting indenyl and fluorenyl cationic systems to magnetic measures of antiaromaticity. All measures, (1)H NMR shifts, nucleus independent chemical shifts (NICS(1)(zz)), and magnetic susceptibility exaltation, Lambda, supported the antiaromaticity of the dications 3a-f2+. The 1H NMR shifts and NICS(1)(zz) showed that the indenyl ring system was less antiaromatic than the fluorenyl ring system, contrary to the antiaromaticity of indenyl monocations compared to fluorenyl monocations. The presence of a phenyl substituent in the 3-position was able to stabilize the indenylidene cation through resonance, decreasing its antiaromaticity, but even in the absence of the 3-phenyl substituent, the indenyl system of indenylidenefluorene dications was less antiaromatic than the fluorenyl system. The decreased antiaromaticity of the 3-phenylindenylidenefluorene dications over the unsubstituted indenylidenefluorene dication was supported by (anti)aromatic (de)stabilization energy calculations, ASE.     

Formation of surface-bound acyl groups by reaction of acyl halides on ge(100)-2x1

We have investigated the reaction of a series of acyl halides, including acetyl chloride, acetyl bromide, acetyl-d3 chloride, benzoyl chloride, and pivaloyl chloride, on Ge(100)-2x1 with multiple internal reflection infrared (MIR-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT). Infrared spectra following saturation exposures of acetyl chloride and acetyl bromide to Ge(100)-2x1 at 310 K are nearly identical, both exhibiting strong nu(C=O) stretching peaks near 1685 cm-1 and no vibrational modes in the nu(Ge-H) region. These data provide strong evidence for the presence of a surface-bound acetyl group on Ge(100)-2x1, which results from a C-X dissociation reaction (where X=Cl, Br). For acetyl chloride, DFT calculations predict that the barrier to C-Cl dissociation is only 1 kcal/mol above a chlorine-bound precursor state and is considerably smaller than barriers leading to the [2+2] C=O cycloaddition and alpha-CH dissociation products. In addition to the C-X dissociation product, both infrared and photoelectron results point to the presence of a second structure for acetyl halides where the oxygen of the surface-bound acetyl group donates charge to a nearby surface atom. This interaction is not observed for benzoyl chloride and pivaloyl chloride.     

Increasing sensitivity and decreasing spot size using an inexpensive, removable hydrophobic coating for matrix-assisted laser desorption/ionisation plates

Spot size reduction and increased detection sensitivity in matrix-assisted laser desorption/ionisation (MALDI) of small molecules are accomplished by using an inexpensive and removable hydrophobic coating for MALDI targets, based on 3M Scotch Gard surface treatment. Several variations in sample preparation were explored, such as surface coating technique, identity of the matrix, solvent composition, and the type of metal support plate used. These were investigated on both uncoated and coated surfaces and their impact on spot size, crystal coverage, and sensitivity is presented here. Additionally, crystallisation behaviour obtained on coated plates is compared with that on uncoated plates using scanning electron microscope analysis. To demonstrate the potential of the new coating technique, erythromycin A and valinomycin are studied to determine the increase in detection sensitivity of coated plates in comparison to uncoated plates, and to reveal the suitability of the plates for application in combined high-performance liquid chromatography/MALDI (HPLC/MALDI), where widely varying solvent compositions and droplet volumes are observed. It is shown that enhancements in detection sensitivities correlate very well with the achieved spot size reduction. The versatility of the coated plates is also exhibited by the ease of removing the surface layer, after which the plates can be rigorously cleaned without worry about damaging the hydrophobic surface, followed by a quick reapplication of new hydrophobic coating material. This makes the non-polar coating superior to more expensive commercial hydrophobic-coated targets, which are much more delicate to clean. Furthermore, cleaning and reapplication eliminate potential carry-over effects and the easy application procedure also makes the fabrication of inexpensive, disposable MALDI targets readily possible.     

A stable monomeric nickel borohydride

A stable discrete nickel borohydride complex (Tp*NiBH(4) or Tp*NiBD(4)) was prepared using the nitrogen-donor ligand hydrotris(3,5-dimethylpyrazolyl)borate (Tp*-). This complex represents one of the best characterized nickel(II) borohydrides to date. Tp*NiBH(4) and Tp*NiBD(4) are stable toward air, boiling water, and high temperatures (mp > 230 degrees C dec). X-ray crystallographic measurements for Tp*NiBH(4) showed a six-coordinate geometry for the complex, with the nickel(II) center facially coordinated by three bridging hydrogen atoms from borohydride and a tridentate Tp(-) ligand. For Tp*NiBH(4), the empirical formula is C(15)H(26)B(2)N(6)Ni, a = 13.469(9) A, b = 7.740(1) A, c = 18.851(2) A, beta = 107.605(9) degrees, the space group is monoclinic P2(1)/c, and Z = 4. Infrared measurements confirmed the presence of bridging hydrogen atoms; both nu(B[bond]H)(terminal) and nu(B[bond]H)(bridging) are assignable and shifted relative to nu(B-D) of Tp*NiBD(4) by amounts in agreement with theory. Despite their hydrolytic stability, Tp*NiBH(4) and Tp*NiBD(4) readily reduce halocarbon substrates, leading to the complete series of Tp*NiX complexes (X = Cl, Br, I). These reactions showed a pronounced hydrogen/deuterium rate dependence (k(H)/k(D) approximately 3) and sharp isosbestic points in progressive electronic spectra. Nickel K-edge X-ray absorption spectroscopy (XAS) measurements of a hydride-rich nickel center were obtained for Tp*NiBH(4), Tp*NiBD(4), and Tp*NiCl. X-ray absorption near-edge spectroscopy results confirmed the similar six-coordinate geometries for Tp*NiBH(4) and Tp*NiBD(4). These contrasted with XAS results for the crystallographically characterized pseudotetrahedral Tp*NiCl complex. The stability of Tp*Ni-coordinated borohydride is significant given this ion's accelerated decomposition and hydrolysis in the presence of transition metals and simple metal salts.