Excited-state interactions in diastereomeric flurbiprofen-thymine dyads

Excited-state interactions between (S)- or (R)-flurbiprofen ((S)- or (R)-FBP) and thymidine (dThd) covalently linked in dyads 1 or 2 have been investigated. In both dyads, the only emitting species is (1)FBP*, but with a lower fluorescence quantum yield (?(F)) and a shorter fluorescence lifetime (τ(F)) than when free in solution. These results indicate that dynamic quenching occurs either by electron transfer or via exciplex formation, with FBP as the charge-donating species. In acetonitrile, both mechanisms are favored, while in dioxane exciplex formation is predominating. Isomer 1 displays lower values of ?(F) and τ(F) than its analogue 2, indicating that the relative spatial arrangement of the chromophores plays a significant role. The triplet quantum yields (?(T)) of 1 and 2 are significantly higher than the expectations based solely on (1)FBP*-dThd intersystem crossing quantum yields (?(ISC)), with ?(T) (1) > ?(T) (2). This can be explained in terms of intramolecular charge recombination at the radical ion pairs and/or the exciplexes, which would be again dependent on geometrical factors. The triplet lifetimes (τ(T)) of (3)FBP*-dThd and free (3)FBP* are similar, indicating the lack of excited-state interactions at this stage. The FBP-dThd dyads could, in principle, constitute appropriate model systems for the elucidation of the excited-state interactions in noncovalent DNA-ligand complexes.     

Dinuclear Tin(II) Complex of a Bulky cis‐Oxamide: Synthesis,Characterization, Crystal Structure,and DFT Studies

The reaction of the di‐lithiated oxamide of 1 with two equivalents of SnCl₂ provided the tin trans‐oxamide 3 . In solution, spectroscopic analysis suggests exclusively the formation of a trans‐oxamide (trans‐ 3 ). However, the solid state shows an atypical cis‐oxamide (cis‐ 3 ), where the oxamide fragment acts as an anti‐Janus head ligand. An ¹¹⁹Sn‐NMR variable temperature experiment ([D₈]THF) of the trans‐oxamide (trans‐ 3 ) was performed however, at lower temperature no additional signal was observed, which confirmed the absence of a dynamic equilibrium. Dispersion‐corrected density functional calculations revealed that the cis conformation of this tin(II) oxamide complex is more stable than the trans isomer by 1.4 kcal · mol^–1.     

Identification and quantification of odorous compounds from adhesives used in food packaging materials by headspace solid phase extraction and headspace solid phase microextraction coupled to gas chromatography–olfactometry–mass spectrometry

Adhesives are often responsible for off-flavors in food in contact with packaging. The aim of this investigation was to identify by GC–O–MS the odorous compounds in five different types of adhesive (hotmelt, vinyl acetate ethylene, starch, polyvinyl acetate and acrylic) used in food packaging. In order to obtain a substantial number of compounds, they were extracted by two complementary extraction methods: HS-SPE and HS-SPME. Fifteen minutes extraction time using PDMS fiber for hotmelt adhesive and DVD/CAR/PDMS fiber for the other adhesives were the best conditions for defining a representative solvent-free adhesive extract using a rapid and simple D-GC–O technique. Thirty-three compounds were identified by GC–O–MS. These include butyric acid, acetic acid, methyl butyrate, 1-butanol and nonanal, which were present in most of the adhesives under study producing cheesy, rancid, sour, medicinal and green aromas, respectively. The concentrations were determined, the most abundant compound being acetic acid with concentrations from 22.9 to 8930 μg g⁻¹ of adhesive.     

Mizoroki?Heck and Sonogashira Cross‐Couplings Catalyzed by CNC Palladium Pincer Complexes in Organic and Aqueous Media

The catalytic activity of two CNC palladium pincer complexes is evaluated in two fundamental C? C bond‐forming reactions: Mizoroki? Heck and Sonogashira cross‐couplings. After several optimization attempts and a brief comparison with a PCN pincer catalyst, a number of arylated alkenes and diarylethynes are synthesized by procedures based on the catalytic use of the above mentioned CNC Pd pincers in H₂O and DMF.     

Evolutionary computation for optimal knots allocation in smoothing splines

In this paper, a novel methodology is presented for optimal placement and selections of knots, for approximating or fitting curves to data, using smoothing splines. It is well-known that the placement of the knots in smoothing spline approximation has an important and considerable effect on the behavior of the final approximation [1]. However, as pointed out in [2], although spline for approximation is well understood, the knot placement problem has not been dealt with adequately. In the specialized bibliography, several methodologies have been presented for selection and optimization of parameters within B-spline, using techniques based on selecting knots called dominant points, adaptive knots placement, by data selection process, optimal control over the knots, and recently, by using paradigms from computational intelligent, and Bayesian model for automatically determining knot placement in spline modeling. However, a common two-step knot selection strategy, frequently used in the bibliography, is an homogeneous distribution of the knots or equally spaced approach [3].     

Multisite Solid Catalyst for Cascade Reactions: The Direct Synthesis of Benzodiazepines from Nitro Compounds

Substituted 1,5‐benzodiazepines are selectively synthesized in one pot from substituted nitroaromatics and ketones. The reaction is performed in the presence of hydrogen and in the absence of solvent by using a bifunctional solid catalyst with a chemoselective hydrogenation functional group capable of reducing the nitro group to a diamino group and an acid functional group, which catalyzes the cyclocondensation of the amino group with the ketone.     

Assessment of submicron particle zeta potential in simple electrokinetic microdevices

The present communication illustrates the use of simple electrokinetic devices for the assessment of the zeta potential of submicron polystyrene particles. A combination of manual and automatic particle tracking was employed. This approach allows for characterizing particles in the same conditions and devices in which they can be separated, e.g. dielectrophoretic separations; making the resulting data readily applicable.     

On the use of correction factors for the mathematical modeling of insulator based dielectrophoretic devices

Mathematical modeling is a fundamental component in the development of new microfluidics techniques and devices. Modeling allows for the rapid testing of new system configurations while saving resources. Microscale electrokinetic (EK) techniques have significantly benefited by the advances in modeling programs and software packages. However, EK phenomena are complex to model, as they dynamically affect system characteristics, including the physical properties of the particles and fluid within the system. Insulator‐based dielectrophoresis (iDEP) is an EK technique that has received important attention during the last two decades. In particular, numerous research groups that study iDEP systems employ a combination of modeling and experimentation for developing new iDEP systems. An important fraction of these research groups has adopted the practice of employing “correction factors” to account for EK phenomena that cannot be accurately predicted in their models due to model complexity and limitations in computing resources. The present review article aims to provide the reader with an overview of the most common approaches in the use of correction factors for the modeling of iDEP systems.     

Experimental Determination of the Burning Velocity of Mixtures of n-Heptane and Toluene in Engine-like Conditions

Although the burning velocities of fuel-air mixtures have been extensively studied at room temperature and pressure, there is relatively little experimental information available for elevated temperatures and pressures (the so-called engine like conditions). Therefore, the main aim of the present work is to generate accurate experimental burning velocities valid over a range of high unburned gas temperatures and pressures of a variety of mixtures of n-heptane and toluene, varying its proportion by 25% in volume each time. Two experimental combustion facilities have been used and their results compared. One facility consists of a constant volume cylindrical bomb in which Schlieren images can be recorded and used to calculate the flame front development. The second facility is a spherical combustion bomb with centred ignition in which burning velocities are calculated from pressure records by means of a two-zone model. In order to check that the pressure method is reliable, experiments with n-heptane at room temperature and pressure for different equivalence ratios carried out in the spherical combustion bomb were compared with the ones obtained at the same conditions in the cylindrical vessel equipped with the Schlieren technique. Once the validity has been checked, extensive experiments have been carried out for widely varying initial conditions of pressure between 0.3 and 0.7?MPa, temperature between 363?K and 453?K and equivalence ratios from 0.8 to 1.1. Over the ranges studied, by removing the influence of the ignition energy at the earliest stages of combustion and the quenching effects at the later ones, the burning velocities are fitted by a correlation of type $ Cc=Cc_{r}\cdot (T_{ub}/T_{r})^{\varepsilon }\cdot (P/P_{r})^{\beta } $ , where Cc _r , ?? and ?? depend on the equivalence ratio. The ranges of validity of the correlations obtained cover from 370?K to 700?K, from 0.3?MPa to 4.5?MPa, and from 0.8 to 1.1 equivalence ratio. A comparison with previous predicted values is also given.