Improving ADMMs for solving doubly nonnegative programs through dual factorization

4OR - Alternating direction methods of multipliers (ADMMs) are popular approaches to handle large scale semidefinite programs that gained attention during the past decade. In this paper, we focus...     

Surface chemistry, reactivity, and pore structure of porous silicon oxidized by various methods

Oxidation is the most commonly used method of passivating porous silicon (PSi) surfaces against unwanted reactions with guest molecules and temporal changes during storage or use. In the present study, several oxidation methods were compared in order to find optimal methods able to generate inert surfaces free of reactive hydrides but would cause minimal changes in the pore structure of PSi. The studied methods included thermal oxidations, liquid-phase oxidations, annealings, and their combinations. The surface-oxidized samples were studied by Fourier transform infrared spectroscopy, isothermal titration microcalorimetry, nitrogen sorption, ellipsometry, X-ray diffraction, electron paramagnetic resonance spectroscopy, and scanning electron microscopy imaging. Treatment at high temperature was found to have two advantages. First, it enables the generation of surfaces free of hydrides, which is not possible at low temperatures in a liquid or a gas phase. Second, it allows the silicon framework to partially accommodate a volume expansion because of oxidation, whereas at low temperature the volume expansion significantly consumes the free pore volume. The most promising methods were further optimized to minimize the negative effects on the pore structure. Simple thermal oxidation at 700 °C was found to be an effective oxidation method although it causes a large decrease in the pore volume. A novel combination of thermal oxidation, annealing, and liquid-phase oxidation was also effective and caused a smaller decrease in the pore volume with no significant change in the pore diameter but was more complicated to perform. Both methods produced surfaces that were not found to react with a model drug cinnarizine in isothermal titration microcalorimetry experiments. The study enables a reasonable choice of oxidation method for PSi applications.     

Lower ligand denticity leading to improved thermodynamic and kinetic stability of the Gd3+ complex: the strange case of OBETA

OBETA, OBETA, you bet: Thermodynamic and kinetic measurements show an apparent paradox. The stability of complexes of lanthanide trivalent ions is higher with the heptadentate ligand OBETA (ethylene glycol-bis(2-aminoethyl ether)-N,N,N',N'-tetraacetic acid) than with its octadentate homologue EGTA (2,2'-oxybis(ethylamine)-N,N,N',N'-tetraacetic acid). The unusual properties of Gd(OBETA)(-) (see structure), combined with the presence of two fast exchanging coordinated water molecules, candidates this complex as an MRI contrast agent.     

Real-time assessment of cigarette smoke particle deposition in vitro

Background

Recently, an increased interest in the identification of valuable possibilities for preserving the antioxidant properties of products obtained by thermal processing of fruits rich in bioactive compounds can be noticed. In this regard, an extensive analysis is necessary in terms of thermal processed products behavior in relation to various factors. The purpose of the present study was to assess the effect which processing and storage at 20°C has on the antioxidant properties and color quality of low-sugar bilberry jam with different low-methoxyl pectin (LMP) concentrations.

Results

For all measured parameters, it should be noted that thermal processing induced significant alterations reported to the values registered for fresh fruit. Most important losses due to thermal processing were recorded for total monomeric anthocyanins (TMA) (81-84%), followed by L-ascorbic acid (L-AsAc) content (53-58%), total phenolics (TP) content (42-51%) and FRAP (ferric reducing antioxidant power) values (36-47%). Moreover, depreciation of the investigated compounds occurred during storage at 20°C. Jam storage for 7 months resulted in severe losses in TMA content in the range 58-72% from the value recorded one day after processing. This coincided with marked increases in polymeric color percent of these products after 7 months of storage. Also, bilberry jam storage for 7 months resulted in a decrease in L-AsAc content of 40-53% from the value recorded one day after processing, 41-57% in TP content and 33-46% from the value recorded one day after processing for FRAP values. By decreasing of LMP concentration in the jam recipe from 1 to 0.3% there has been an increase in losses of investigated compounds.

Conclusion

Overall, the results indicated that bilberry jams can also represent a good source of antioxidant compounds, although compared to the fruit, important losses seem to occur. Practical application of this work is that this kind of information will be very useful in optimizing the jam processing technology and storage conditions, in order to improve the quality of these products.     

Symmetry in RLT-type relaxations for the quadratic assignment and standard quadratic optimization problems

The reformulation–linearization technique (RLT), introduced in [Sherali, H. D., Adams. W. P. (1990). A hierarchy of relaxations between the continuous and convex hull representations for zero-one programming problems. SIAM Journal on Discrete Mathematics 3(3), 411–430], provides a way to compute a hierarchy of linear programming bounds on the optimal values of NP-hard combinatorial optimization problems. In this paper we show that, in the presence of suitable algebraic symmetry in the original problem data, it is sometimes possible to compute level two RLT bounds with additional linear matrix inequality constraints. As an illustration of our methodology, we compute the best-known bounds for certain graph partitioning problems on strongly regular graphs.     

Solid-State NMR Spectroscopy: A Key Tool to Unravel the Supramolecular Structure of Drug Delivery Systems

In the past decades, nanosized drug delivery systems (DDS) have been extensively developed and studied as a promising way to improve the performance of a drug and reduce its undesirable side effects. DDSs are usually very complex supramolecular assemblies made of a core that contains the active substance(s) and ensures a controlled release, which is surrounded by a corona that stabilizes the particles and ensures the delivery to the targeted cells. To optimize the design of engineered DDSs, it is essential to gain a comprehensive understanding of these core–shell assemblies at the atomic level. In this review, we illustrate how solid-state nuclear magnetic resonance (ssNMR) spectroscopy has become an essential tool in DDS design.     

Monochelic Versus Telechelic Poly(Methyl Methacrylate) as a Matrix for Photoluminescent Nanocomposites with Quantum Dots

Nanocomposites based on CdSe or CdSe/ZnS quantum dots (QDs) and poly(methyl methacrylate) (PMMA) of different molecular weights and functionality were synthesized by ligand exchange of oleic acid with RAFT-based PMMA. The successful ligand exchange was confirmed by dynamic light scattering in combination with the approach “macromolecules—ghosts” and transmission electron microscopy. Comparative study of mono- and telechelics of PMMA revealed the similarities and differences in their behavior in formation of complexes with QDs and the optical properties of the corresponding nanocomposites. Telechelics exhibited higher efficiency in the complex formation and seemed to be promising candidates for the construction of devices based on QDs and polymer matrix for optical applications.     

Reinforced nickel catalysts for steam reforming of methane to synthesis gas

XRD, mercury porosimetry, low-temperature nitrogen adsorption and electron microscopy were used to study peculiarities of the formation of reinforced composite nickel catalysts. The catalysts were prepared by sintering powdered metallic nickel with a supported nickel catalyst (GIAP-3 or NIAP-18) applied to a reinforcing stainless steel gauze. It was found that a metal matrix, in the pores of which supported catalyst particles were distributed, was formed in the composite catalysts. The NIAP-18-based catalyst exceeded the GIAP-3-based catalyst in activity toward the methane steam reforming. The NIAP-18-based catalyst was as active as the Cr₂O₃-doped NIAP-18-based catalyst, but showed a worse coke-resistance. A chromium oxide additive increased the activity of the GIAP-3-based catalyst.     

Cryo-bioorganic chemistry: freezing effect on stereoselection of DL-alanine-N-carboxyanhydride oligomerization in dioxane solution

The possibility of stereoselection through the DL-alanine-N-carboxyanhydride (NCA-DL-Ala) oligomerization, and the effect of freezing on it have been investigated. To this end, the chirality of peptides obtained by oligomerization for 1 and 3 days, respectively, in liquid (+22 degree celsius) and frozen (-18 degree celsius) dioxane solutions, was analyzed. These water-soluble samples were fractionated by gel filtration, aliquots of the fractions were completely hydrolyzed and then derivatized with Marfey reagent (1-fluoro-2,4-dinitrophenyl-5-L-alanine amide). These derivatives were traced and evaluated by RP-HPLC analysis. The relatively best effects appeared in a given fraction, where after 1 day of oligomerization the L-alanine enantiomeric excess (ee) was 3.8 percent in liquid and 8.6 percent in frozen conditions. After 3 days, however, the ee contents decreased to 2.0 percent and 4.1 percent. The mass spectrometric data of the peptides pointed to the formation of open chain and cyclic peptide mixtures, where the residue numbers of 8-11 and 4-5 dominated. The formation of some chiral peptides from a racemic amino acid suggests the possibility of preferential incorporation of the L-enantiomer into the growing chain, beside the achiral statistical succession of residues. Here we provide the first example of the role of freezing in the increased formation of chirality from racemic amino-acid through oligomerization, together with some speculations about the implications of our model in the events of prebiotic chemistry.     

Conformational restriction via cyclization in beta-amyloid peptide Abeta(1-28) leads to an inhibitor of Abeta(1-28) amyloidogenesis and cytotoxicity

The aggregation process of beta-amyloid peptide Abeta into amyloid is strongly associated with the pathology of Alzheimer's disease (AD). Aggregation may involve a transition of an alpha helix in Abeta(1-28) into beta sheets and interactions between residues 18-20 of the "Abeta amyloid core." We applied an i, i+4 cyclic conformational constraint to the Abeta amyloid core and devised side chain-to-side chain lactam-bridged cyclo(17, 21)-[Lys(17), Asp(21)]Abeta(1-28). In contrast to Abeta(1-28) and [Lys(17), Asp(21)]Abeta(1-28), cyclo(17, 21)-[Lys(17), Asp(21)]Abeta(1-28) was not able to form beta sheets and cytotoxic amyloid aggregates. Cyclo(17, 21)-[Lys(17), Asp(21)]Abeta(1-28) was able to interact with Abeta(1-28) and to inhibit amyloid formation and cytotoxicity. Cyclo(17, 21)-[Lys(17), Asp(21)]Abeta(1-28) also interacted with Abeta(1-40) and interfered with its amyloidogenesis. Cyclo(17, 21)-[Lys(17), Asp(21)]Abeta(1-28) or similarly constrained Abeta sequences may find therapeutic and diagnostic applications in AD.