Hydrolysis of the low gelatinization temperature Araucaria angustifolia pine seed starch

Journal of Thermal Analysis and Calorimetry - The effect of compressor speed, initial refrigerant charge and volume concentrations of SiO2/PAG nanolubricant on the performance of automotive...     

Engineering O-glycosylation points in non-extended peptides: implications for the molecular recognition of short tumor-associated glycopeptides

The ties that bind: The incorporation of non-natural residues in the peptide backbone allows the design of O-glycosylation points in helical segments. This strategy could help to modulate the binding properties between glycopeptides and their protein receptors, such as lectins and antibodies.     

A review of recent, unconventional applications of ion mobility spectrometry (IMS)

The applications of ion mobility spectrometry (IMS) have grown exponentially beyond its uses for explosive, illicit drug and chemical warfare agent monitoring in recent years. Instrumental developments including new drift tube materials and ionization sources have enabled the manufacturing of more sophisticated and affordable IMS equipment for the advantageous analysis of samples with no pretreatment. The most recent applications of IMS include quality control and cleaning validation procedures in the pharmaceutical industry; determinations of contaminants in food samples; clinical analyses of biological fluids; environmental analyses of contaminants in gaseous, liquid and solid samples; and (bio)process quality control monitoring. Coupling IMS with MSⁿ has enabled the analysis of very complex samples and the extraction of knowledge unavailable from isolated MS measurements, especially in the polymer and petroleomic industries.     

A robust method to quantify low molecular weight contaminants in heparin: detection of tris(2-n-butoxyethyl) phosphate

Recently, oversulfated chondroitin sulfate (OSCS) was identified in contaminated heparin preparations, which were linked to several adverse clinical events and deaths. Orthogonal analytical techniques, namely nuclear magnetic resonance (NMR) and capillary electrophoresis (CE), have since been applied by several authors for the evaluation of heparin purity and safety. NMR identification and quantification of residual solvents and non-volatile low molecular contaminants with USP acceptance levels of toxicity was achieved 40-fold faster than the traditional GC-headspace technique, which takes ~120 min against ~3 min to obtain a (1)H NMR spectrum with a signal/noise ratio of at least 1000/1. The procedure allowed detection of Class 1 residual solvents at 2 ppm and quantification was possible above 10 ppm. 2D NMR techniques (edited-HSQC (1)H/(13)C) permitted visualization of otherwise masked EDTA signals at 3.68/59.7 ppm and 3.34/53.5 ppm, which may be overlapping mononuclear heparin signals, or those of ethanol and methanol. Detailed NMR and ESI-MS/MS studies revealed a hitherto unknown contaminant, tris(2-n-butoxyethyl) phosphate (TBEP), which has potential health risks.     

Adsorption of cobalt ferrite nanoparticles within layer-by-layer films: a kinetic study carried out using quartz crystal microbalance

The paper reports on the successful use of the quartz crystal microbalance technique to assess accurate kinetics and equilibrium parameters regarding the investigation of in situ adsorption of nanosized cobalt ferrite particles (CoFe(2)O(4)--10.5 nm-diameter) onto two different surfaces. Firstly, a single layer of nanoparticles was deposited onto the surface provided by the gold-coated quartz resonator functionalized with sodium 3-mercapto propanesulfonate (3-MPS). Secondly, the layer-by-layer (LbL) technique was used to build multilayers in which the CoFe(2)O(4) nanoparticle-based layer alternates with the sodium sulfonated polystyrene (PSS) layer. The adsorption experiments were conducted by modulating the number of adsorbed CoFe(2)O(4)/PSS bilayers (n) and/or by changing the CoFe(2)O(4) nanoparticle concentration while suspended as a stable colloidal dispersion. Adsorption of CoFe(2)O(4) nanoparticles onto the 3-MPS-functionalized surface follows perfectly a first order kinetic process in a wide range (two orders of magnitude) of nanoparticle concentrations. These data were used to assess the equilibrium constant and the adsorption free energy. Alternatively, the Langmuir adsorption constant was obtained while analyzing the isotherm data at the equilibrium. Adsorption of CoFe(2)O(4) nanoparticles while growing multilayers of CoFe(2)O(4)/PSS was conducted using colloidal suspensions with CoFe(2)O(4) concentration in the range of 10(-8) to 10(-6) (moles of cobalt ferrite per litre) and for different numbers of cycles n = 1, 3, 5, and 10. We found the adsorption of CoFe(2)O(4) nanoparticles within the CoFe(2)O(4)/PSS bilayers perfectly following a first order kinetic process, with the characteristic rate constant growing with the increase of CoFe(2)O(4) nanoparticle concentration and decreasing with the rise of the number of LbL cycles (n). Additionally, atomic force microscopy was employed for assessing the LbL film roughness and thickness. We found the film thickness increasing from about 20 to 120 nm while shifting from 3 to 10 CoFe(2)O(4)/PSS bilayers, using the 8.9 × 10(-6) (moles of cobalt ferrite per litre) suspension.     

Aromatic-aromatic interactions in proteins: beyond the dimer

Aromatic residues are key widespread elements of protein structures and have been shown to be important for structure stability, folding, protein-protein recognition, and ligand binding. The interactions of pairs of aromatic residues (aromatic dimers) have been extensively studied in protein structures. Isolated aromatic molecules tend to form higher order clusters, like trimers, tetramers, and pentamers, that adopt particular well-defined structures. Taking this into account, we have surveyed protein structures deposited in the Protein Data Bank in order to find clusters of aromatic residues in proteins larger than dimers and characterized them. Our results show that larger clusters are found in one of every two unique proteins crystallized so far, that the clusters are built adopting the same trimer motifs found for benzene clusters in vacuum, and that they are clearly nonlocal brining primary structure distant sites together. We extensively analyze the trimers and tetramers conformations and found two main cluster types: a symmetric cluster and an extended ladder. Finally, using calmodulin as a test case, we show aromatic clsuters possible role in folding and protein-protein interactions. All together, our study highlights the relevance of aromatic clusters beyond the dimer in protein function, stability, and ligand recognition.     

New organoruthenium complexes with bioactive thiosemicarbazones as co-ligands: potential anti-trypanosomal agents

In the search for new therapeutic tools against neglected diseases produced by trypanosomatid parasites, and particularly against African Trypanosomiasis, whose etiological agent is Trypanosoma brucei, organoruthenium compounds with bioactive nitrofuran containing thiosemicarbazones (L) as co-ligands were obtained. Four ruthenium(II) complexes with the formula [Ru(2)(p-cymene)(2)(L)(2)]X(2), where X = Cl or PF(6), were synthesized and the crystal structures of two of them were solved by X-ray diffraction methods. Two of the complexes show significant in vitro growth inhibition activity against Trypanosoma brucei brucei and are highly selective towards trypanosomal cells with respect to mammalian cells (J774 murine macrophages). These promising results make the title organoruthenium compounds good lead candidates for further developments towards potential antitrypanosomal organometallic drugs.     

Gas-phase thermolysis reaction of formaldehyde diperoxide. Kinetic study and theoretical mechanisms

Gas-phase thermolysis reaction of formaldehyde diperoxide (1,2,4,5-tetroxane) was performed in an injection chamber of a gas chromatograph at a range of 463-503 K. The average Arrhenius activation energy and pre-exponential factor were 29.3 ± 0.8 kcal/mol and 5.2 × 10¹³ s⁻¹, respectively. Critical points and reaction paths of the ground singlet and first triplet potential energy surfaces (PES) were calculated, using DFT method at BHANDHLYP/6-311+G^∗∗ level of the theory. Also, G3 calculations were performed on the reactant and products. Reaction by the ground-singlet and first-triplet states turned out to be endothermic and exothermic, respectively. The mechanism in three steps seemed to be the most probable one. An electronically non-adiabatic process appeared, in which a crossing, at an open diradical structure, from the singlet to the triplet state PES occurred, due to a spin-orbit coupling, yielding an exothermic reaction. Theoretical kinetic constant coming from the non- adiabatic transition from the singlet to the triplet state agrees with the experimental values.     

New insight in the structure–luminescence relationships of Ca9Eu(PO4)7

The double phosphate Ca₉Eu(PO₄)₇, obtained by solid state reaction, was found to be isotypic with Ca₃(PO₄)₂, with space group R3c and unit cell parameters a=10.4546(1) Å, c=37.4050(3) Å, V=3540.67(9) Å³, Z=6. The structure parameters refined using the Rietveld method showed that europium shares positions M1, M2 and M3 with calcium, contradicting previously published Mössbauer results. Low temperature luminescence under selective excitation of Eu³⁺ in Ca₉Y_1−xEu_x(PO₄)₇ and in Ca₉Eu(PO₄)₇ samples was studied, confirming the Eu³⁺ distribution into these sites. At 10 K, ⁵D₀→⁷F₀ emission lines of Eu³⁺ were observed at 578.5, 579.5, 580.1 nm for the M3, M1 and M2 sites, respectively. High temperature X-ray powder diffraction evidenced a second-order phase transition around 573 °C.     

Mannich-type reactions in the gas-phase: the addition of enol silanes to cyclic N-acyliminium ions

The intrinsic gas-phase reactivity of cyclic N-acyliminium ions in Mannich-type reactions with the parent enol silane, vinyloxytrimethylsilane, has been investigated by double- and triple-stage pentaquadrupole mass spectrometric experiments. Remarkably distinct reactivities are observed for cyclic N-acyliminium ions bearing either endocyclic or exocyclic carbonyl groups. NH-Acyliminium ions with endocyclic carbonyl groups locked in s-trans forms participate in a novel tandem N-acyliminium ion reaction: the nascent adduct formed by simple addition is unstable and rearranges by intramolecular trimethylsilyl cation shift to the ring nitrogen, and an acetaldehyde enol molecule is eliminated. An NSi(CH(3))(3)-acyliminium ion is formed, and this intermediate ion reacts with a second molecule of vinyloxytrimethylsilane by simple addition to form a stable acyclic adduct. N-Acyl and N,N-diacyliminium ions with endocyclic carbonyl groups, for which the s-cis conformation is favored, react distinctively by mono polar [4(+) + 2] cycloaddition yielding stable, ressonance-stabilized cycloadducts. Product ions were isolated via mass-selection and structurally characterized by triple-stage mass spectrometric experiments. B3LYP/6-311G(d,p) calculations corroborate the proposed reaction mechanisms.