Simulation and measurement of AES depth profiles; a case study of the C/Ta/C/Si system

A multilayer sample (C (23.3 nm)/Ta (26.5 nm)/C (22.7 nm)/Si substrate) was submitted to AES depth profiling by Ar⁺ ions of energy 1 keV and angles of incidence of 72°, 78°, and 82°. The shapes of the as-measured depth profiles were strongly different emphasizing that the ion-bombardment conditions strongly affects the shapes of measured depth profiles. We simulated the depth profile measured at an angle of incidence of 72° by calculating the backscattering factor, applying attenuation lengths available in the literature, and simulating the ion-bombardment-induced specimen alteration with a TRIDYN simulation and a trial and error method. The good agreement between the calculated and measured depth profiles justified the method applied.     

Three-Color Ramsey Numbers For Paths

We prove—for sufficiently large n—the following conjecture of Faudree and Schelp:

Characterization of Electrospun Polysuccinimide-Dopamine Conjugates and Effect on Cell Viability and Uptake

Biocompatible nanofibrous systems made by electrospinning have been studied widely for pharmaceutical applications since they have a high specific surface and the capability to make the entrapped drug molecule amorphous, which increases bioavailability. By covalently conjugating drugs onto polymers, the degradation of the drug as well as the fast clearance from the circulation can be avoided. Although covalent polymer–drug conjugates have a lot of advantages, there is a lack of research focusing on their nano-formulation by electrospinning. In this study, polysuccinimide (PSI) based electrospun fibrous meshes conjugated with dopamine (DA) are prepared. Fiber diameter, mechanical properties, dissolution kinetics and membrane permeability are thoroughly investigated, as these are crucial for drug delivery and implantation. Dopamine release kinetics prove the prolonged release that influenced the viability and morphology of periodontal ligament stem cells (PDLSCs) and SH-SY5Y cells. The presence of dopamine receptors on both cell types is also demonstrated and the uptake of the conjugates is measured. According to flow cytometry analysis, the conjugates are internalized by both cell types, which is influenced by the chemical structure and physical properties. In conclusion, electrospinning of PSI-DA conjugates alters release kinetics, meanwhile, conjugated dopamine can play a key role in cellular uptake.     

High-Tc superconductors studied by57Co,57Fe,119Sn,and151Eu mössbauer spectroscopy

¹⁵¹Eu,¹¹⁹Sn,⁵⁷Fe, and⁵⁷Co Mössbauer spectroscopy was used to study YBa₂Cu₃O_7– high-T_c superconductors in which sites were replaced by various Mössbauer nuclides in order to get information about site preference and structural changes. By decomposition of the Mössbauer spectra, the Y site substituted by Eu and the Cu sites occupied by Sn, Fe, and Co substituents were identified. It was found that Fe and Co prefer the Cu(1) site while Sn prefers the Cu(2) site in the orthorhombic perovskite lattice of these superconductors. The site preference is enhanced in the presence of additional substituents. A sequence of thermal heat treatments permits reversible cycling of⁵⁷Co between the two copper sites in the YBa₂[Cu(⁵⁷Co)]₃O_7– perovskite. In all cases Eu(III) and Sn(IV) states are determined, but the valence state of Fe and Co can be both three and four. BelowT _c, low-temperature phase transformation and phonon softening were shown from the anomalous temperature dependence of isomer shifts and the area fractions of¹⁵¹Eu and¹¹⁹Sn Mössbauer spectra of EuBa₂(Cu_1-xSn_x)₃O_7- cuprates.     

Electrospray ionization tandem mass spectrometry of the star‐shaped propoxylated diethylenetriamine polyols

The collision‐induced dissociation of the protonated five‐arm star propoxylated diethylenetriamine polyols was studied under electrospray conditions. Two product ion series were detected because of the cleavage of the C? N bonds in the initiator moiety. No backbone fragmentation of the polyether chains was observed, which allowed to explore the initiation and side‐chain propagation process of the oligomers. On the basis of MS/MS spectra, it is probable that the rate of the initiation is larger than that of the chain propagation. The propylene oxide repeat units attach to the five arms with approximately the same probability. Furthermore, it was found that the collision energy necessary to obtain 50% fragmentation (CE₅₀) was linearly dependent on the molecular weight of the polyols. Copyright © 2015 John Wiley & Sons, Ltd.     

Atmospheric pressure photoionization mass spectrometry of polyisobutylene derivatives

Atmospheric pressure photoionization mass spectrometric (APPI-MS) study on three types of polyisobutylene derivatives is reported. Two of the polyisobutylenes investigated were polyisobutylene with dihydroxy and diolefinic end-groups derived from aromatic moieties [dicumyl chloride, 1,4-bis(2-chloro-2-propyl)benzene], and the third contained no aromatic moieties with a monohydroxy end-group. All three polyisobutylene derivatives (PIBs) had an average molecular weight (M(n)) of approximately 2000 g/mol, with a polydispersity lower than 1.2. In the positive ion APPI mode, protonated PIB molecules were formed, but the molecular weights obtained were considerably lower than those expected, indicating fragmentation of the PIB chains. In the negative APPI mode, using solvents such as tetrahydrofuran and toluene as dopants, no signal was obtained. However, in chlorinated solvents, such as CCl(4), CHCl(3), and CH(2)Cl(2), in the presence of toluene dopant, PIB adducts with chloride ions were formed with relatively high signal intensity. In the case of CH(2)Cl(2), no dopant (toluene) was necessary to generate chlorinated adduct ions, albeit increasing the toluene concentration in the flow increased the PIB signal intensity. The effect of the toluene concentration on PIB signal intensity was studied and models that include (1) photoionization of toluene, (2) formation of chloride ions from the chlorinated solvents by dissociative electron capture, (3) formation of chlorinated adduct ions and charge recombination reactions between the toluene radical cation, (4) chloride ions, and (5) chlorinated adduct ions are proposed based on the experimental results.     

Energy-dependent collision-induced dissociation study of buprenorphine and its synthetic precursors

The collision-induced dissociation (CID) of protonated buprenorphine ([M+H](+) ) and four related compounds was studied by electrospray quadrupole/time-of-flight mass spectrometry (ESI-QTOF MS). The fragmentation pathways were investigated by using energy-dependent CID and pseudo-MS(3) (in-source CID combined with tandem mass spectrometry (MS/MS)) methods. The first steps of the fragmentation are the parallel losses of the substituents from the non-aromatic ring moieties. Depending on the applied collision energies, a large number of further fragment ions arising from the cross-ring cleavages of the core-ring structure were observed. Based on the experimental results, a generalized fragmentation scheme was developed for the five buprenorphine derivatives highlighting the differences for the alternatively substituted compounds. The collision-energy-dependent fragmentation profile of buprenorphine is visualized in a two-dimensional plot to aid its fingerprint identification.     

Dopant-assisted atmospheric pressure photoionization mass spectrometry of polyisobutylene derivatives initiated by mono- and bifunctional initiators

Nine polyisobutylene (PIB) derivatives with different end groups (chlorine, vinyl, isobutenyl, 2,2-diphenylvinyl, and carboxyl) and molecular weights (1000 to 4500 g/mol), initiated by monofunctional and aromatic bifunctional initiators were studied by atmospheric pressure photoionization mass spectrometry (APPI-MS) in both negative and positive ion modes. Consistent with previous findings, negative ion APPI-MS revealed end-group identities through the formation of PIB adducts with chloride ions formed in situ from a chlorinated solvent (e.g., CCl₄) in the presence of a dopant (toluene). In positive ion mode, considerable fragmentation of these PIB derivatives was observed, rendering end-group determinations very difficult. The M _n values obtained by APPI(−)-MS were considerably lower than those determined by SEC for PIB derivatives with M _n higher than 2000 g/mol. PIBs containing carboxyl termini can undergo collision-induced dissociation, yielding structurally important product ions. The resulting APPI-MS/MS intensities were found to reflect the “arm-length” distribution for PIBs with bifunctional aromatic moieties. In positive ion mode, [M+COCl]⁺ adducts were observed for PIBs with an aromatic initiator moiety. The origin of the COCl⁺ species is also discussed.     

Femtosecond studies of charge-transfer mediated proton transfer in 2-butylamino-6-methyl-4-nitropyridine N-oxide

We have unraveled the effects of an amino substituent in the ortho position on the excited-state dynamics of 4-nitropyridine N-oxide by studying the picosecond fluorescence kinetics and femtosecond transient absorption of a newly synthesized compound, 2-butylamino-6-methyl-4-nitropyridine N-oxide, and by quantum chemical calculations. Similar to the parent compound, the S(1) state of the target molecule has significant charge-transfer character and shows a large (approximately 8000 cm(-1)) static Stokes shift in acetonitrile. Analysis of the experimental and the theoretical results leads, however, to a new scenario in which this intramolecular charge transfer triggers in polar, aprotic solvents an ultrafast (around 100 fs) intramolecular proton transfer between the amino and the N-O group. The electronically excited N-OH tautomer is subsequently subject to solvent relaxation and decays with a lifetime of approximately 150 ps to the ground state.     

Thermodynamic study of aqueous solutions of polyelectrolytes of low and medium charge density without added salt by direct measurement of osmotic pressure

A special block osmometer has been constructed and applied to a systematic study of poly (vinyl alcohol and vinyl sulphate ester) (PVS) sodium salts in dilute and moderately concentrated salt free aqueous solutions. In order to avoid surely ionic contamination all parts of the equipment that can contact with the polyelectrolyte solutions were made of different kinds of plastics and glass. The pressure range spans from (50 to 1.3 · 10⁵) Pa. The measuring system was found to be appropriate for determination of the molar mass of water soluble polymers, too. Above a certain analytical density of dissociable groups (ADDG) an ion size dependent transition was observed on the reduced osmotic pressure vs. concentration curves. The analysis of the osmotic pressure data has clearly revealed that the dependence of the degree of dissociation on ADDG calculated at zero polyelectrolyte concentration contradicts to ‘ion condensation’ theory. With increasing polyelectrolyte concentration the degree of dissociation decreased rather steeply but at very low concentrations sharp maximums appeared due either to the change in conformation of these charged macromolecules, or formation of dynamic clusters induced by salting out of neutral parts of the macromolecules by the ionized groups. The applicability of the scaling concept as well as the many possible ways of characterization of non-ideality of polyelectrolyte solutions will be discussed in detail.