Comparative bioavailability of two zolpidem hemitartrate formulations in healthy human Brazilian volunteers using high-performance liquid chromatography coupled to tandem mass spectrometry

To assess the bioequivalence of two zolpidem hemitartrate formulations in 30 healthy volunteers. Plasma samples were obtained over a 24 h period. Plasma concentrations of zolpidem were analyzed by liquid chromatography coupled to tandem mass spectrometry with positive ion electrospray ionization using multiple reaction monitoring. Values of peak concentration (C_max), area under curve (AUC), half-life, elimination constant, volume of distribution and clearance showed statistically significant differences when comparing women (604.34 ng h/ml, 127.36 ng/ml, 4.4 h, 0.18 1/h, 50.56 L and 8.55 L/h, respectively) and men (276.1 ng h/ml, 70.9 ng/ml, 3.3 h, 0.26 1/h, 91.42 L and 24.34 L/h, respectively), receiving the same dose (5 mg), respectively. The geometric means with corresponding 90% confidence interval for Test/Reference percentage ratios were 99.73% (CI 93.69–106.16) for C_max, 97.44% (90% CI = 91.85–103.37%) for area under curve of plasma concentration until the last concentration observed (AUC_last) and 98.30% (90% CI = 92.48–104.49) for the area under curve between the first sample (pre-dosage) and infinity (AUC_0–inf). Since the 90% CI for AUC_last, AUC_0–inf and C_max ratios were within the 80–125% interval proposed by the US Food and Drug Administration, it was concluded that zolpidem hemitartrate formulation (5 mg orodispersible tablet) is bioequivalent to the zolpidem hemitartrate formulation (Patz SL 5 mg sublingual tablet) with regard to both the rate and the extent of absorption. A new formulation of zolpidem 2.5 mg may be useful in women for the same clinical benefits as the 5 mg formulation in men.     

Tetramethyl guanidine-assisted synthesis and thermal crosslinking of multifunctional benzoxazine monomers based on natural phloretic acid

An efficient strategy to synthesize novel biobased multifunctional benzoxazine compounds was developed using the 1,1,3,3-tetramethyl guanidine (TMG)-triggered esterification of natural phloretic acid with organic halides as a key synthetic step. First, phloretic acid was combined with either aniline or furfurylamine to prepare the corresponding carboxylic acid-functional monobenzoxazine monomer. Next, the use of TMG enabled an efficient esterification of these compounds with di-, tri-, and tetra-functional benzyl bromide compounds at room temperature to afford a series of new multi-benzoxazine monomers tethered to an aromatic core. The effect of the functionality of the monomers on the curing process was analyzed, indicating that the reactivity during the thermally induced ring-opening increases with the number of furan and oxazine rings in the monomers. The resulting thermosets revealed good correlation between the number of oxazine rings in the structure of the monomer and the properties of the crosslinked materials. Furfurylamine-based polybenzoxazines showed improved thermal behavior compared to the aniline-based systems, due to the role of furan rings. All materials showed high T_g, good thermal stability, and promising flame retardancy properties.     

Electronic Structure Modulation in an Exceptionally Stable Non‐Heme Nitrosyl Iron(II) Spin‐Crossover Complex

The highly stable nitrosyl iron(II) mononuclear complex [Fe(bztpen)(NO)](PF₆)₂ (bztpen=N‐benzyl‐N,N′,N′‐tris(2‐pyridylmethyl)ethylenediamine) displays an S=1/2?S=3/2 spin crossover (SCO) behavior (T_1/2=370 K, ΔH=12.48 kJ mol^?1, ΔS=33 J K^?1 mol^?1) stemming from strong magnetic coupling between the NO radical (S=1/2) and thermally interconverted (S=0?S=2) ferrous spin states. The crystal structure of this robust complex has been investigated in the temperature range 120–420 K affording a detailed picture of how the electronic distribution of the t_2g–e_g orbitals modulates the structure of the {FeNO}⁷ bond, providing valuable magneto–structural and spectroscopic correlations and DFT analysis.     

EIS monitoring study of the early microbiologically influenced corrosion of AISI 304L stainless steel condenser tubes in freshwater

This study examined the early stages of tarnishing of American Iron Steel Institute (AISI) 304L austenitic stainless steel (SS) condenser tubes in contact with running freshwater from the Tagus River in Spain. The immersion time of the tubes was 569 days. Tarnishing originated by biofouling was assessed using electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS) analyses in conjunction with argon ion sputtering. The EIS diagrams showed a semicircle that was better defined as the experimental time increased, indicating the decreasing tarnishing resistance of the immersed specimens. The EIS results were validated using Kramers–Kronig relationships. SEM micrographs of biofouling indicated that the number of microorganisms on the SS surfaces increased with immersion time. According to the XPS spectra, the main elements deposited on the tarnished AISI 304L SS layer were calcium, phosphorus, and nitrogen. A mechanism of biofouling and microbiologically influenced corrosion behavior of AISI 304L SS condenser tubes in freshwater is proposed.     

Controlling Proton and Electron Transfer Rates to Enhance the Activity of an Oxygen Reduction Electrocatalyst

An electrochemical approach is developed that allows for the control of both proton and electron transfer rates in the O₂ reduction reaction (ORR). A dinuclear Cu ORR catalyst was prepared that can be covalently attached to thiol‐based self‐assembled monolayers (SAMs) on Au electrodes using azide–alkyne click chemistry. Using this architecture, the electron transfer rate to the catalyst is modulated by changing the length of the SAM, and the proton transfer rate to the catalyst is controlled with an appended lipid membrane modified with proton carriers. By tuning the relative rates of proton and electron transfer, the current density of the lipid‐covered catalyst is enhanced without altering its core molecular structure. This electrochemical platform will help identify optimal thermodynamic and kinetic parameters for ORR catalysts and catalysts of other reactions that involve the transfer of both protons and electrons.     

Noncovalent Interactions of π Systems with Sulfur: The Atomic Chameleon of Molecular Recognition

The relative strength of noncovalent interactions between a thioether sulfur atom and various π systems in designed top pan molecular balances was determined by NMR spectroscopy. Compared to its oxygen counterpart, the sulfur atom displays a remarkable ability to interact with almost equal facility over the entire range of π systems studied, with the simple alkene emerging as the most powerful partner. With the exception of the O???heteroarene interaction, all noncovalent interactions of sulfur with π systems are favoured over oxygen.     

Zel'Manov's Theorem for Primitive Jordan-Banach Algebras

The following result is well known and easy to prove (see [14,Theorem 2.2.6]). Theorem 0. If A is a primitive associative Banach algebra, thenthere exists a Banach space X such that A can be seen as a subalgebraof the Banach algebra BL(X) of all bounded linear operatorson X in such a way that A acts irreducibly on X and the inclusionABL(X) is continuous. In fact, if X is any vector space on which the primitive Banachalgebra A acts faithfully and irreducibly, then X can be convertedin a Banach space in such a way that the requirements in Theorem0 are satisfied and even the inclusion ABL(X) is contractive. Roughly speaking, the aim of this paper is to prove the appropriateJordan variant of Theorem 0.     

A versatile and high-precision solution—reaction isoperibol calorimeter

A new solution-reaction isoperibol calorimeter was developed to measure enthalpies of solution and reaction. A new system of sample cell was developed to avoid the breaking of glass ampoules, hence making the sample cell reusable. The system is suitable for measuring molar enthalpies of solid-liquid and liquid-liquid interactions at different temperatures. The reproducibility and accuracy of the apparatus were tested by measuring the enthalpy of solution of KCl in water at 298.15 K and the enthalpy of protonation of THAM in HCl (0.1 M) at 298.15 K. The results showed the uncertainty taken as the reproducibility was ±0.3% and the difference with the literature values was within ±0.5%.