Improvement of pour point and oxidative stability of synthetic ester basestocks for biolubricant applications

For environmental reasons, as well as the dwindling source of petroleum, a new class of environmentally acceptable and renewable biolubricants based on plant oils is available. Even though plant oils possess excellent lubricant-related properties, there are some concerns about using it as biolubricant base oil. In this study we present a series of structures derived from oleic acid to be used as synthetic biolubricant basestocks. Measuring of pour point (PP), flash point, viscosity index (VI), oxidation onset temperature (OT) and signal maximum temperature (SMT) was carried out for each compound. Furthermore, the friction and wear properties were measured using a high-frequency reciprocating rig (HFRR). The resulting product structures were confirmed by NMR and FTIR spectroscopic analysis. The results showed that ethylhexyl 9-(octanoyloxy)-10-(behenoxy)octadecanoate with behenyl mid-chain ester exhibited the most favorable low temperature performance (PP ?48 °C) and ethylhexyl 9-(octanoyloxy)-10-(octyloxy)octadecanoate octyl mid-chain ester exhibited higher oxidation stability (OT 142 °C) than the other synthetic ester oils. On the other hand, the highest ball wear scan diameter was obtained for ethylhexyl 9-(octanoyloxy)-10-(behenoxy)octadecanoate while the lowest value was obtained for 9-hydroxy-10-octyloxyoctadecanoic acid. Overall, it was concluded that these synthetic ester oils have potential in formulation of industrial fluids for different temperature applications.     

Preparation and characterization of 1,2,3‐triazole‐cured polymers from endcapped azides and alkynes

Fourteen commercial polyols have been characterized by GPC, NMR spectroscopy, and elemental analysis. From these, eight corresponding tosylates, six nitrate esters, seven mesylates, 13 alkynes, and 14 azides have been prepared and all these derivatives have been fully characterized. Five alkyne monomers and eight azide monomers were also prepared. Twelve alkynes and 13 azides (functionality 2–4) were combined in 1,3‐dipolar cycloaddition reactions under neat conditions to prepare triazole‐cured polymers, avoiding any heavy metal catalyst. Characterization by NMR spectroscopy, elemental analysis, and gel permeation chromatography indicated triazole polymers 14 , 22 , 23 , 28 , and 30 with degrees of polymerization of 17–28 to be the best candidates for future work. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 238–256, 2008     

Utility of 2-(5-methyl-1-phenyl-1H-pyrazol-4-yl)-2-oxo-N′-phenylaceto-hydrazonoyl bromide as precursor for synthesis of new functionalized heterocycles

2-(5-Methyl-1-phenyl-1H-pyrazol-4-yl)-2-oxo-N′-phenylaceto-hydrazonoyl bromide was synthesized and used as precursor for synthesis of some new 1,3,4-thiadiazoles, pyrrolo[3,4-c]pyrazoles, and 1,2,4-triazolo[4,3-a]pyrimidines. The mechanisms that account for formation of products were discussed. Also, the structures of all the newly synthesized products were confirmed based on elemental analysis, spectral data and by alternative methods.     

Synthesis and biological evaluation of <Superscript>99m</Superscript>Tc labeled aryl piperazine derivatives as cerebral radiotracers

The aim of this study is to develop cerebral radiotracers for central nervous system receptors imaging. The synthesis, characterization and biological evaluation of two aryl piperazine ^99mTc-radiocomplexes based on the piano stool motif [CpM(CO₃)] (Cp = cyclopentadienyl, M = ^99mTc/Re) is reported. The ^99mTc-radiocomplexes were obtained quickly (time < 5 min) with high radiochemical yields. The ^99mTc-radiocomplexes characterized by high performance liquid chromatography comparison with the rhenium surrogates have both a suitable lipophilicity and are able to cross the blood brain barrier with 0.43 ± 0.05 and 1.96 ± 0.06% ID/g of brain uptake, at 10 min post injection.     

Synthesis,structural, spectral,thermal and comparative biological activity studies of [V<Subscript>2</Subscript>O<Subscript>2</Subscript>(SO<Subscript>4</Subscript>)<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)<Subscript>6</Subscript>]

The hydrothermal reaction of a mixture of V₂O₅, VCl₃, 2,5-pyridinedicarboxylic acid and diluted H₂SO₄ for 68 h at 180°C gives a blue colored solution which yields prismatic blue crystals of IV ₂ ^IV O₂(SO₄)₂(H₂O)₆] (1) in 32% yield (based on V). Complex 1 was investigated by means of elemental analysis (C, H and S), TGA, FT-IR, manganometric titration, Single Crystal X-ray Diffraction Methods and also comparative antimicrobial activities. Crystal data for the compound: monoclinic space group P2₁/c and unit cell parameters are a = 7.3850(12) Å, b = 7.3990(7) Å, c = 12.229(2) Å, β = 108.976(12)° and Z = 2. Although structure of 1 as a natural mineral has been previously determined, this work covers new preparation method and full characterization of 1 along with comparison of antibacterial activity between 1 and the commercial vanadium(IV) oxide sulfate hydrate compounds, VOSO₄ · xH₂O (Riedel-de Haën and Alfa Aesar brand names). 1 was evaluated for the antimicrobial activity against gram-positive, gram-negative bacteria, yeasts and mould compared with the commercial VOSO₄ · xH₂O compounds. 1 showed weak activity against bacteria Bacillus cereus, Nocardia asteroides and yeast Candida albicans. A good antimicrobial activity was recorded against Cirtobacter freundii (15 mm). There are only a few reproducible well-defined vanadium(IV) starting materials to use for exploring the synthesis of new materials. VCl₄, VO(acac)₂, VOSO₄ · xH₂O and [V(IV)OSO₄(H₂O)₄] · SO₄ · [H₂N(C₂H₄)₂NH₂] are common starting materials for such applications. In addition to these compounds, 1 can be used as an oxovanadium precursor.     

Deuteration of Water Enables Self‐Organization of Phospholipid‐Based Reverse Micelles

Phospholipid‐based reverse micelles are composed of branched cylinders. Their branching points are known to attract themselves and to slide along branches. The rate of this sliding is governed by the lifetime of H(D)‐bonded water bridges between phospholipid molecules. This lifetime is increased when the water is deuterated. On condition that the water contains at least 40 D atoms %, water/dipalmitoylphosphatidylcholine (DPPC)/deuterated pyridine reverse micelles with the composition 1.1:1:250 (v/v) have been shown to self‐organize into a liquid crystal in the 310–316 K temperature range. The mechanism of this self‐organization is unraveled by following the FTIR and ¹H NMR spectra of more concentrated micelles upon heating. During the preparation of micelles, pyridine‐(D⁺)H⁺ ions are formed. They give rise to hydron transfers, under the influence of the DPPC electric charges, evidenced by two broad FTIR absorptions above (BB1) and below (BB2) the ν(C? O) stretch. These hydron transfers occur along strong (D⁺)H⁺ bonds of pyridinium ions with pyridine (BB1) and DPPC C?O groups (BB2). The proton transfers at the interface of micelles, relayed in the continuous pyridine medium, create a tenuous link between separated micelles, thus facilitating their organization. Upon heating, DPPC heads shrink and DPPC chains expand to make wedge‐shaped DPPC molecules. The micelles then change in shape: cylinders constrict and enclosed water drifts towards branching points, which swell. Branching points of neighboring micelles come into contact. Due to the deuteration of water these contacts are prolonged and H bonds are formed between DPPC molecules located in each branching point. Upon storage at 39 °C, these branching points fuse. The lateral diffusion of DPPC molecules becomes free, as evidenced by a narrowing of all ¹H NMR resonances. Upon further heating, reorganization into a liquid crystal occurs.     

Étude structurale de britholite au césium Sr7La2Cs(PO4)5(SiO4)F2

Several studies demonstrated the ability of britholites to retain radionuclides such as the caesium and actinides. Therefore, three compounds with formulas Sr₈LaCs(PO₄)₆F₂, Sr₇La₂Cs(PO₄)₅(SiO₄)F₂ and Sr₂La₇Cs(SiO₄)₆F₂, were prepared by solid state reaction. However, it seems that only the mono-silicated composition was obtained in a pure state. In this present work, the X-ray diffraction and magnetic nuclear resonance have been used to investigate the structure for this composition. The results showed that in fact this phase was not pure, but it was mixed with a secondary phase, SrLaCs(PO₄)₂. The refinement by the Rietveld method allowed also to precise the distribution of La³⁺ and Cs⁺ ions between the two cationic sites of the apatite.     

<Superscript>18</Superscript>F- and <Superscript>11</Superscript>C-labelling of quantum dots with n.c.a. [<Superscript>18</Superscript>F]fluoroethyltosylate and [<Superscript>11</Superscript>C]methyliodide: a feasibility study

Quantum dots functionalized on the outer surface with either amino- or carboxyl functions were labelled with [¹⁸F]fluoroethyltosylate and [¹¹C]methyliodide in order to use the positron emitter-labelled fluorescence agents for multimodality imaging techniques, i.e. fluorescence imaging and positron emission tomography. ¹⁸F-Labelling of both compounds was realized with yields up to 5% as determined by size exclusion chromatography, which is twice as much as reported in literature before [1]. ¹¹C-Labelling of amino- and carboxyl-QDs proceeded with good yields (up to 45 and 35%, respectively) under optimized reaction conditions. In general for both QD-types and both labelling agents the labelling yield increased with the amount of QDs used in the reaction as well as with reaction time and reaction temperature.