Energy contribution of heterocyclic sulfur and a disulfide bond in solid and gaseous phase

Structural Chemistry - In the present work, the energy contribution of the sulfur atom in a heterocycle and in a disulfide bond in solid and gas phases was calculated. To achieve this goal,...     

Reversible Activation of Water by an Air- and Moisture-Stable Frustrated Rhodium Nitrogen Lewis Pair

[Cp*Rh(κ³N,N′,P- L )][SbF₆] (Cp*=C₅Me₅), bearing a guanidine-derived phosphano ligand L , behaves as a “dormant” frustrated Lewis pair and activates H₂ and H₂O in a reversible manner. When D₂O is employed, a facile H/D exchange at the Cp* ring takes place through sequential C(sp³)−H bond activation.     

Ultrafast gas chromatography coupled to electronic nose to identify volatile biomarkers in exhaled breath from chronic obstructive pulmonary disease patients: A pilot study

An analytical method to identify volatile organic compounds (VOCs) in the exhaled breath from patients with a diagnosis of chronic obstructive pulmonary disease (COPD) using a ultrafast gas chromatography system equipped with an electronic nose detector (FGC eNose) has been developed. A prospective study was performed in 23 COPD patients and 33 healthy volunteers; exhalation breathing tests were performed with Tedlar bags. Each sample was analyzed by FCG eNose and the identification of VOCs was based on the Kovats index. Raw data were reduced by principal component analysis (PCA) and canonical discriminant analysis [canonical analysis of principal coordinates (CAP)]. The FCG eNose technology was able to identify 17 VOCs that distinguish COPD patients from healthy volunteers. At all stages of PCA and CAP the discrimination between groups was obvious. Chemical prints were correctly classified up to 82.2%, and were matched with 78.9% of the VOCs detected in the exhaled breath samples. Receiver operating characteristic curve analysis indicated the sensitivity and specificity to be 96% and 91%, respectively. This pilot study demonstrates that FGC eNose is a useful tool to identify VOCs as biomarkers in exhaled breath from COPD patients. Further studies should be performed to enhance the clinical relevance of this quick and ease methodology for COPD diagnosis.     

Origin of the Photoinduced Geometrical Change of Copper(I) Complexes from the Quantum Chemical Topology View

Copper(I) complexes (CICs) are of great interest due to their applications as redox mediators and molecular switches. CICs present drastic geometrical change in their excited states, which interferes with their luminescence properties. The photophysical process has been extensively studied by several time-resolved methods to gain an understanding of the dynamics and mechanism of the torsion, which has been explained in terms of a Jahn–Teller effect. Here, we propose an alternative explanation for the photoinduced structural change of CICs, based on electron density redistribution. After photoexcitation of a CIC (S₀→S₁), a metal-to-ligand charge transfer stabilizes the ligand and destabilizes the metal. A subsequent electron transfer, through an intersystem crossing process, followed by an internal conversion (S₁→T₂→T₁), intensifies the energetic differences between the metal and ligand within the complex. The energy profile of each state is the result of the balance between metal and ligand energy changes. The loss of electrons originates an increase in the attractive potential energy within the copper basin, which is not compensated by the associated reduction of the repulsive atomic potential. To counterbalance the atomic destabilization, the valence shell of the copper center is polarized (defined by ∇²ρ(r) and ∇²V_ne(r)) during the deactivation path. This polarization increases the magnitude of the intra-atomic nuclear–electron interactions within the copper atom and provokes the flattening of the structure to obtain the geometry with the maximum interaction between the charge depletions of the metal and the charge concentrations of the ligand.     

Drying of guaco leaves: experimental and modeling kinetic,equilibrium isotherms and heat of desorption

Journal of Thermal Analysis and Calorimetry - Due to the huge variety of therapeutic properties found in plant leaves, many of these are widely used in traditional medicine. Among these plants,...     

Determination of cocaine adulterants in human urine by dispersive liquid-liquid microextraction and high-performance liquid chromatography

Analytical and Bioanalytical Chemistry - This study aimed to determine simultaneously five major street cocaine adulterants (caffeine, lidocaine, phenacetin, diltiazem, and hydroxyzine) in human...     

Nowcasting Avalanches as Earthquakes and the Predictability of Strong Avalanches in the Olami-Feder-Christensen Model

Nowcasting earthquakes, suggested recently as a method to estimate the state of a fault and hence the seismic risk, is based on the concept of natural time. Here, we generalize nowcasting to a prediction method the merits of which are evaluated by means of the receiver operating characteristics. This new prediction method is applied to a simple (toy) model for the waiting (natural) time of the stronger earthquakes, real seismicity, and the Olami-Feder-Christensen earthquake model with interesting results revealing acceptable to excellent or even outstanding performance.     

DLSFEM–PML formulation for the steady-state response of a taut string on visco-elastic support under moving load

Meccanica - The numerical solution of the steady-state response of a uniform taut string on visco-elastic support under a concentrated transverse moving load is addressed. By recasting the...