New palladium (II) complexes containing phosphine‐nitrogen ligands and their use as catalysts in aminocarbonylation reaction

Aminocarbonylation of aryl halides, homogeneously catalysed by palladium, is an efficient method that can be employed for obtaining amides for pharmaceutical and synthetic applications. In this work, palladium (II) complexes containing P^N ligands were studied as catalysts in the aminocarbonylation of iodobenzene in the presence of diethylamine. Two types of systems were used: a palladium (II) complex formed in situ; and one prepared prior to the catalytic reaction. In general, the palladium complexes studied achieved high conversions in an average reaction time of less than 2 hr, which is less than that for the standard system (Pd (II)/PPh₃) used. The pre‐synthesized complexes were faster than their in situ counterparts, as the latter require an induction time to form the Pd/P^N species. The structure and electronic properties of the ligand P^N can influence both the activity and the selectivity of the reaction, stabilizing the acyl‐palladium intermediates formed in a better manner.     

Multiplexed therapeutic drug monitoring of antipsychotics in dried plasma spots by LC‐MS/MS

In this work, a convenient method for the therapeutic monitoring of seven common antipsychotic drugs in “dried plasma spot” samples has been developed. It is based on the liquid chromatography tandem mass spectrometry technique, operating in multiple reaction monitoring mode, and a straightforward procedure for the simultaneous extraction of all antipsychotics in a single step, with high extraction yield. The method was fully validated with proper accuracy, precision, selectivity and sensitivity, for all the drugs. Limits of quantification were 0.12, 1.09, 1.46, 1.47, 5.70, 1.32, 1.33 µg/L for haloperidol, aripiprazole, olanzapine, quetiapine, clozapine, risperidone, and paliperidone, respectively. Accuracy, intra‐ and interday precision values were <10% for all drugs at all concentration levels examined. The method was tested in the analysis of 30 plasma samples from real patients for each drug. The proposed analytical approach, by combining practical and logistical advantages of microsampling with liquid chromatography tandem mass spectrometry analytical performance, could offer an ideal strategy for accurate and timely therapeutic drug monitoring of antipsychotic drugs in most clinical settings, even in remote centers and/or in out‐patient settings, bringing so many potential improvements in psychiatric patient care.     

Silicon‐containing trifunctional and tetrafunctional cyanate esters: Synthesis,cure kinetics,and network properties

The synthesis and physical properties of new silicon‐containing polyfunctional cyanate ester monomers methyl[tris(4‐cyanatophenyl)]silane and tetrakis(4‐cyanatophenyl)silane, as well as polycyanurate networks formed from these monomers are reported. The higher crosslinking functionality compared to di(cyanate ester) monomers enables much higher ultimate glass transition temperatures to be obtained as a result of thermal cyclotrimerization. The ability to reach complete conversion is greatly enhanced by cocure of the new monomers with di(cyanate ester) monomers such as 1,1‐bis(4‐cyanatophenyl)ethane. The presence of silicon in these polycyanurate networks imparts improved resistance to rapid oxidation at elevated temperatures, resulting in char yields as high as 70% under nitrogen and 56% in air in the best‐performing networks. The water uptake in the silicon‐containing networks examined is 4–6 wt % after 96 h of immersion at 85 °C, considerably higher than both carbon‐containing and/or di(cyanate ester) analogs. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 767–779     

Onion‐like Multifunctional Microtrap Vehicles for Attraction–Trapping–Destruction of Biological Threats

A multifunctional motile microtrap is developed that is capable of autonomously attracting, trapping, and destroying pathogens by controlled chemoattractant and therapeutic agent release. The onion‐inspired multi‐layer structure contains a magnesium engine core and inner chemoattractant and therapeutic layers. Upon chemical propulsion, the magnesium core is depleted, resulting in a hollow structure that exposes the inner layers and serves as structural trap. The sequential dissolution and autonomous release of the chemoattractant and killing agents result in long‐range chemotactic attraction, trapping, and destruction of motile pathogens. The dissolved chemoattractant (l ‐serine) significantly increases the accumulation and capture of motile pathogens (E. coli) within the microtrap structure, while the internal release of silver ions (Ag⁺) leads to lysis of the pathogen accumulated within the microtrap cavity.     

Oxidation kinetics of thin copper films and wetting behaviour of copper and Organic Solderability Preservatives (OSP) with lead-free solder

The oxide formation on thin copper films deposited on Si wafer was studied by XPS, SEM and Sequential Electrochemical Reduction Analysis SERA. The surfaces were oxidized in air with a reflow oven as used in electronic assembly at temperatures of 100 °C, 155 °C, 200 °C, 230 °C and 260 °C. The SERA analyses detected only the formation of Cu₂O but the XPS analysis done for the calibration of the SERA equipment proved also the presence of a CuO layer smaller than 2 nm above the Cu₂O oxide. The oxide growth follows a power-law dependence on time within this temperature range and an activation energy of 33.1 kJ/mol was obtained. The wettability of these surfaces was also determined by measuring the contact angle between solder and copper substrate after the soldering process. A correlation between oxide thickness and wetting angle was established. It was found that the wetting is acceptable only when the oxide thickness is smaller than 16 nm. An activation energy of 27 kJ/mol was acquired for the spreading of lead free solder on oxidized copper surfaces.From wetting tests on copper surfaces protected by Organic Solderability Preservatives (OSP), it was possible to calculate the activation energy for the thermal decomposition of these protective layers.     

Solubility of methane in pure non-ionic surfactants and pure and mixtures of linear alcohols at 298 K and 101.3 kPa

The emissions of methane (CH₄), a powerful greenhouse gas (GES), contribute to the increase in GES concentration level in the atmosphere. For this reason, the importance of controlling CH₄ emissions of anthropogenic origin has increased over the last decades. Physicochemical and biological processes are available for treating CH₄. For this reason, such properties as the solubility of CH₄ in aqueous solutions and organic solvents are of great relevance in different applications in environmental engineering and biotechnology. In this study, the solubility of CH₄ was determined at 298 K and 101.3 kPa in organic solvents, such as polyoxyethylenesorbates (Tween 20, Tween 40, and Tween 60), and linear alcohols (methanol, ethanol, and butan-1-ol) alone and in their admixtures. Admixtures of methanol with butan-1-ol exhibited the highest solubility of CH₄, of around 0.49 g m⁻³ of solvent, whereas the solubility of CH₄ in linear alcohols varied from 0.167 g m⁻³ to 0.41 g m⁻³ of solvent. In the case of Tweens, CH₄ solubility decreased with the hydrophilic-lipophilic balance (HLB) number.     

Longitudinal 3D Blood Flow Distribution Provided by Diffuse Correlation Tomography during Bone Healing in a Murine Fracture Model

Noninvasive monitoring of vascularization can potentially diagnose impaired bone healing earlier than current radiographic methods. In this study, a noncontact diffuse correlation tomography (DCT) technique was employed to measure longitudinal blood flow changes during bone healing in a murine femoral fracture model. The three-dimensional distribution of the relative blood flow was quantified from one day pre-fracture to 48 days post-fracture. For three mice, frequent DCT measurements were performed every other day for one week after fracture, and then weekly thereafter. A decrease in blood flow was observed in the bone fracture region at one day post-fracture, followed by a monotonic increase in blood flow beyond the pre-injury baseline until five to seven days post-fracture. For the remaining 12 mice, only weekly DCT measurements were performed. Data collected on a weekly basis show the blood flow for most mice was elevated above baseline during the first two post-fracture weeks, followed by a subsequent decrease. Torsional strength of the excised femurs was measured for all 15 mice after 7 weeks of healing. A metric based on the early blood flow changes shows a statistically significant difference between the high strength group and the low strength group.