Ultrafast study of 9-diazofluorene: direct observation of the first two singlet states of fluorenylidene

Ultrafast photolysis of 9-diazofluorene (DAF) produces a broadly absorbing transient within the instrument time resolution (300 fs), which is assigned to an excited state of the diazo compound. The diazo excited state fragments to form fluorenylidene (Fl) in both its lowest energy singlet state (1Fl, 405-430 nm, depending on the solvent) and a higher energy singlet state (370 nm, 1Fl*). The excited singlet carbene has a lifetime of 20.9 ps in acetonitrile and decays to the lower energy singlet state (1Fl), which relaxes to the triplet ground state (3Fl) in acetonitrile, cyclohexane, benzene, and hexafluorobenzene. The equilibrium mixture of singlet and triplet fluorenylidene reacts with these solvents. Singlet fluorenylidene reacts with methanol and cyclohexene in competition with relaxation to 3Fl. One of the reaction products in methanol is the 9-fluorenyl cation. The rate of intersystem crossing (ISC) in hexafluorobenzene and other halogenated solvents is remarkably slow given that carbene ISC rates are generally fastest in nonpolar solvents. An explanation of this effect is advanced.     

Highly populated turn conformations in natively unfolded tau protein identified from residual dipolar couplings and molecular simulation

Tau, a natively unstructured protein that regulates the organization of neuronal microtubules, is also found in high concentrations in neurofibrillary tangles of Alzheimer's disease and other neurodegenerative disorders. The conformational transition between these vastly different healthy and pathological forms remains poorly understood. We have measured residual dipolar couplings (RDCs), J-couplings, and nuclear Overhauser enhancement (NOE) in construct K18 of tau, containing all four repeat domains R1-R4. NHN RDCs were compared with prediction on the basis of a statistical model describing the intrinsic conformational sampling of unfolded proteins in solution. While local variation and relative amplitude of RDCs agrees with propensity-based prediction for most of the protein, homologous sequences in each repeat domain (DLKN, DLSN, DLSK, and DKFD in repeats R1-R4) show strong disagreement characterized by inversion of the sign of the central couplings. Accelerated molecular dynamic simulations (AMD) in explicit solvent revealed strong tendencies to form turns, identified as type I beta-turns for repeats R1-R3. Incorporation of the backbone dihedral sampling resulting from AMD into the statistical coil model closely reproduces experimental RDC values. These localized sequence-dependent conformational tendencies interrupt the propensity to sample more extended conformations in adjacent strands and are remarkably resistant to local environmental factors, as demonstrated by the persistence of the RDC signature even under harsh denaturing conditions (8 M urea). The role that this specific conformational behavior may play in the transition to the pathological form is discussed.     

Enrichment of phenols from water with in-situ derivatization by in-tube solid phase microextraction-solvent desorption prior to off-line gas chromatographic determination with large-volume injection

Sorption of phenols from water into the stationary phase of open tubular columns (named in-tube solid phase microextraction) as an enrichment method for gas chromatographic (GC) analysis of aqueous samples was studied. The effect of operating conditions (stationary phase polarity, swelling of the stationary phase by solvents, number of sampling cycles, salting-out effect, sampling velocity, flow rate of desorption solvent) on the process efficiency was evaluated. Real water samples were also used in this study. Swelling of the stationary phase by organic solvent enables the volume of the stationary phase to be increased and its properties to be modified. The use of toluene or tetrachloromethane for the purpose results in high extraction efficiencies for most phenols. The results demonstrated a direct relationship between the extracted amount of phenols and its initial concentration in the sample. The limit of detection in off-line analyses applying large-volume injection was lower than 0.04 μg L⁻¹.These results of the use of in-tube solid phase microextraction with solvent desorption as a non-exhaustive (equilibrium sorptive) enrichment method show a great potential for on-line chromatographic analysis of micropollutants in real water samples.     

Dissociative recombination of the deuterated acetaldehyde ion, CD3CDO(+): product branching fractions, absolute cross sections and thermal rate coefficient

Dissociative recombination of the deuterated acetaldehyde ion CD3CDO(+) has been studied at the heavy-ion storage ring CRYRING, located at the Manne Siegbahn Laboratory, Stockholm, Sweden. Product branching fractions together with absolute DR cross-sections were measured. The branching fractions were determined at a relative collision energy between the ions and the electrons of approximately 0 eV. With a probability of 34% the DR events resulted in no ruptures of bonds between heavy atoms (i.e. no breakage of the C-C bond or the C[double bond, length as m-dash]O bond). In the remaining 66% of the events one of the bonds between the heavy atoms was broken. The energy-dependent cross-section for the DR reaction was measured between approximately 0 and 1 eV relative kinetic energy. In the energy region between 1 meV and 0.2 eV the absolute cross section could be fitted by the expression sigma(E) = 6.8 x 10(-16)E(-1.28) cm(2), whereas in the energy interval between 0.2 and 1 eV the data were best fitted by sigma(E) = 4.1 x 10(-16)E(-1.60) cm(2). From these cross section data the thermal rate coefficient (as a function of the electron temperature), alpha(T) = 9.2 x 10(-7) (T/300)(-0.72) cm(3) s(-1) was obtained.     

Validation of the HS-GC-FID method for the determination of ethanol residue in tablets

This paper describes the validation of a HS-GC-FID method (based on the Pharmacopeia’s method) for the determination of ethanol content in tablets. A general view of the procedure development/optimization process is presented. The main point of this study is the calculation of validation parameters. Selectivity of the method was determined. Linearity (r > 0.997) was observed in the range from 9.0 to 3,040 μg of ethanol per sample (because the mass of the tablets used was around 200 mg, this corresponds to 45–15,200 μg g⁻¹). The method showed good recoveries (average 99.0%), and a relative standard deviation for repeatability and intermediate precision of 4.5% and 5.5% respectively. The limit of detection was calculated to be 3.0 μg of ethanol per sample (15 μg g⁻¹). The uncertainty budget was done according to the "Guide to the Expression of Uncertainty in Measurement" (GUM)[1], and a relative expanded uncertainty was estimated as 4.8%.     

Calixarenes in a membrane environment: a monolayer study on the miscibility of three p-tert-butylcalix[4]arene beta-lactam derivatives with 1,2-dimyristoyl-sn-glycero-3-phosphoethanolamine

Literature data indicate that some calixarene derivatives with antimicrobial activities may be useful as drugs; one of the aspects of the biological activity of different classes of antibiotics concerns interactions with lipid membranes. Here, the possibility of incorporation and/or translocation of three amphiphilic p-tert-butylcalix[4]arene derivatives across membranes was studied using lipid monolayers. The derivatives used have 6-aminopenicillanic acid or benzylpenicillin moieties grafted in alternate positions at the calixarene lower rim; 1,2-dimyristoyl-sn-glycero-3-phosphoethanolamine (DMPE), a model bacterial membrane lipid, was used to prepare the monolayers. The miscibility of calixarene-antibiotic conjugates with lipid films was studied using surface pressure and surface potential measurements, as well as Brewster angle microscopy. The results obtained show that the miscibility is significantly different for the 6-aminopenicillanic acid and the two benzylpenicillin derivatives. Molecular modeling allowed the assessment of the lowest energy conformations of the calixarene derivatives and gave more insight into the interactions with the DMPE films.     

Adsorption of N-Decyl-N,N,N-trimethylammonium triflate (DeTATf), a cationic surfactant, on the Au(111) electrode surface

The adsorption behavior of the cationic surfactant N-decyl-N,N,N-trimethylammonium triflate (DeTATf) on the Au(111) electrode surface was characterized using cyclic voltammetry, differential capacity, and chronocoulometry. The thermodynamics of the ideally polarized electrode have been employed to determine the Gibbs excess and the Gibbs energy of adsorption. The results show that the adsorption of DeTATf has a multistate character. At low bulk DeTATf concentrations, the adsorption state is consistent with the formation of an adsorbed film of nearly flat molecules. At higher concentrations this film may represent a three-dimensional aggregated state. At negative potentials and charge densities close to 0 microC cm-2, the data suggest the formation of a film of tilted molecules oriented with the hydrocarbon tail toward the metal surface and the polar head toward the solution. A surprising result of this study is that DeTATf displays adsorption characteristics of a zwitterionic rather than a cationic surfactant. This behavior indicates that the adsorbed species is an ion pair.     

Structure and photophysics of 2-(2'-pyridyl)benzindoles: the role of intermolecular hydrogen bonds

The photophysical properties of two isomeric 2-(2'-pyridyl)benzindoles depend on the environment. Strong fluorescence is detected in nonpolar and polar aprotic solvents. In the presence of alcohols, the emission reveals an unusual behavior. Upon titration of n-hexane solutions with ethanol, the fluorescence intensity goes through a minimum and then increases with rising alcohol concentration. Transient absorption and time-resolved emission studies combined with ground- and excited-state geometry optimizations lead to the conclusion that two rotameric forms, syn and anti, coexist in alcohols, whereas in nonpolar and aprotic polar media, only the syn conformation is present. The latter can form cyclic complexes with alcohols, which are rapidly depopulated in the excited state. In the presence of excess alcohol, syn --> anti rotamerization occurs in the ground state, promoted by the cooperative action of nonspecific and specific effects such as solvent polarity increase and the formation of hydrogen bonds to both donor and acceptor sites of the bifunctional compounds.     

Another look at magic-angle-detected fluorescence and emission anisotropy decays in fluorescence microscopy

It is shown that in contrast to a traditional fluorescence spectroscopy with the parallel beams of light, in which the kinetic fluorescence decays are collected at the so-called magic-angle of thetamag=54.7 degrees, in the fluorescence microscopy, the value of the magic-angle depends on the numerical aperture (NA) of a microscope objective and on the refractive index (n) of an immersion liquid used. Two methods enabling the determination of the magic-angle values corresponding to different values of NA/n, are discussed. It is shown that thetamag changes from a value of 54.7 degrees at the NA/n-->0, to a value of 45 degrees with NA/n-->1. Also in contrast to a traditional fluorescence spectroscopy, in the fluorescence microscopy the term I parallel(t)+2I perpendicular (t) does not represent the total fluorescence intensity Itot(t), because the resulting fluorescence decay I parallel(t)+2I perpendicular (t) is contributed by the dynamic evolution of excited fluorophores. A correctly defined total fluorescence intensity solely represents the kinetic evolution of excited fluorophores, and in the fluorescence microscopy it equals Itot(t)=3Imag(t), where Imag(t) represents the fluorescence intensity detected at thetamag corresponding to a particular NA/n value. If the correct (true) decay of Itot(t) is substituted into the denominator in the expression for the emission anisotropy r(t), r(t) is a (multi)exponential function of time and it accounts for the high-aperture excitation-detection conditions.     

Valorization of Cladophora glomerata Biomass and Obtained Bioproducts into Biostimulants of Plant Growth and as Sorbents (Biosorbents) of Metal Ions

The aim of this study was to propose a complete approach for macroalgae biomass valorization into products useful for sustainable agriculture and environmental protection. In the first stage, the effects of macroalgal extracts and ZnO NPs (zinc oxide nanoparticles) on the germination and growth of radish were examined. Macroalgal extract was produced from freshwater macroalga, i.e., Cladophora glomerata by ultrasound assisted extraction (UAE). The extract was used to biosynthesize zinc oxide nanoparticles. In germination tests, extracts and solutions of ZnO NPs were applied on paper substrate before sowing. In the second stage, sorption properties of macroalga, post-extraction residue, and ZnO NPs to absorb Cr(III) ions were examined. In the germination tests, the highest values of hypocotyl length (the edible part of radish), i.e., 3.3 and 2.6 cm were obtained for 60 and 80% extract (among the tested concentrations 20, 40, 60, 80, and 100%) and 10 and 50 mg/L NPs, respectively. The highest sorption capacity of Cr(III) ions (344.8 mg/g) was obtained by both macroalga and post-extraction residue at a pH of 5 and initial Cr(III) ions concentration of 200 mg/L. This study proves that macroalgae and products based on them can be applied in both sustainable agriculture and wastewater treatment.