Thermal stability of poly(mono-n-alkylitaconates) and mono-n-alkylitaconate-co-vinylpyrrolidone copolymers I

Poly(monoitaconates) containing octyl, decyl and dodecyl groups and random monoalkylitaconate-co-vinylpyrrolidone copolymers were studied by thermogravimetric analysis. Copolymers of mono-n-octylitaconate (MOI), mono-n-decylitaconate (MDI), and mono-n-dodecylitaconate (MDoI), respectively, with N-vinyl-2-pyrrolidone (VP) of different compositions were studied by dynamic thermogravimetric analysis. The thermal stability of the copolymers depends on the structure of the monoitaconate comonomer and on the composition of the copolymer The kinetic analysis of the degradation data shows that the thermal decomposition of these copolymers can be described by several kinetic orders depending on the copolymer and on the composition. The relative thermal stability of the copolymers increases as the VP content increases and as the length of the side chain of the itaconate increases, following the same trend as the flexibility of the copolymers in solution.     

Characterization of three agave species by gas chromatography and solid-phase microextraction-gas chromatography-mass spectrometry

Steam distillation (SD) extraction-solid-phase microextraction coupled to GC-MS was developed for the determination of terpenes and Bligh-Dyer extraction-derivatization coupled with GC for the determination of fatty acids such as ethyl esters were used. It was found that the three different Agave species have the same profile of fatty acids; the quantity of these compounds is different in each Agave variety. On the other hand, different terpenes were identified in the three Agave plants studied: nine in A. salmiana, eight in A. angustifolia and 32 in A. tequilana Weber var. azul.     

Metal-catalyzed anaerobic disproportionation of hydroxylamine. Role of diazene and nitroxyl intermediates in the formation of N2, N2O, NO+, and NH3

The catalytic disproportionation of NH(2)OH has been studied in anaerobic aqueous solution, pH 6-9.3, at 25.0 degrees C, with Na(3)[Fe(CN)(5)NH(3)].3H(2)O as a precursor of the catalyst, [Fe(II)(CN)(5)H(2)O](3)(-). The oxidation products are N(2), N(2)O, and NO(+) (bound in the nitroprusside ion, NP), and NH(3) is the reduction product. The yields of N(2)/N(2)O increase with pH and with the concentration of NH(2)OH. Fast regime conditions involve a chain process initiated by the NH(2) radical, generated upon coordination of NH(2)OH to [Fe(II)(CN)(5)H(2)O](3)(-). NH(3) and nitroxyl, HNO, are formed in this fast process, and HNO leads to the production of N(2), N(2)O, and NP. An intermediate absorbing at 440 nm is always observed, whose formation and decay depend on the medium conditions. It was identified by UV-vis, RR, and (15)NMR spectroscopies as the diazene-bound [Fe(II)(CN)(5)N(2)H(2)](3)(-) ion and is formed in a competitive process with the radical path, still under the fast regime. At high pH's or NH(2)OH concentrations, an inhibited regime is reached, with slow production of only N(2) and NH(3). The stable red diazene-bridged [(NC)(5)FeHN=NHFe(CN)(5)](6)(-) ion is formed at an advanced degree of NH(2)OH consumption.     

Partial filling multiple injection affinity capillary electrophoresis (PFMIACE) to estimate binding constants of receptors to ligands

Partial filling multiple injection affinity capillary electrophoresis (PFMIACE) is used to determine binding constants between vancomycin (Van) from Streptomyces orientalis, teicoplanin (Teic) from Actinoplanes teicomyceticus and ristocetin (Rist) from Nocardia lurida to d-Ala-d-Ala terminus peptides and carbonic anhydrase B (CAB, E.C.4.2.1.1) to arylsulfonamides. Two variations of PFMIACE are described herein. In the first technique, the capillary is partially filled with ligand at increasing concentrations, a non-interacting standard, three or four separate plugs of receptor each separated by small plugs of buffer, a plug containing a second non-interacting standard, and then electrophoresed in buffer. Upon continued electrophoresis, equilibrium is established between the ligand and receptors causing a shift in the migration time of the receptors with respect to the non-interacting standards. This change in migration time is utilized for estimating multiple binding constants (K_b) for the same interaction. In the second technique, separate plugs of sample containing non-interacting standards, peptide one, buffer, and peptide two, were injected into the capillary column. The capillary is partially filled with a series of buffers containing an antibiotic at increasing concentrations and electrophoresed. Peptides migrate through the column at similar electrophoretic mobilities since their charge-to-mass ratios are approximately the same but remain as distinct zones due to the buffer plug between peptides. Upon electrophoresis, the plug of antibiotic flows into the peptide plugs affecting a shift in the migration time of the peptides with respect to the non-interacting standards occurs due to formation of the of the antibiotic-peptide complex. The shift in the migration time of the peptides upon binding to the antibiotic is used for the Scatchard analysis and measurement of a K_b. The PFMIACE technique expands the functionality and potential of ACE as an analytical tool to examine receptor-ligand interactions. In PFMIACE, a smaller amount of sample is required in the assay compared to both conventional ACE and MIACE. Furthermore, a wide array of data is obtained from a single experiment, thus, expediting the assay of biological species.     

Acid-base sensors based on novel quinone-type dyes

We present a detailed study on the acid-base behaviour of a family of "potentially antiaromatic" p-benzoquinonediimine ligands. These 12pi electron molecules can be considered as constituted of two chemically connected but electronically not conjugated 6pi-electron subunits. Upon successive protonation, "mono" and "double" cyanine-type chromophores are generated in solution and allow a precise and sensitive spectrophotometric detection. These molecules represent a new class of tunable quinones whose electronic and structural properties can be triggered by proton input, as established by a complete physico-chemical study involving a combination of potentiometric and spectrophotometric methods (absorption and emission).     

Impact of solar ultraviolet radiation on marine phytoplankton of Patagonia, Argentina

Patagonia area is located in close proximity to the Antarctic ozone "hole" and thus receives enhanced ultraviolet B (UV-B) radiation (280-315 nm) in addition to the normal levels of ultraviolet A (UV-A; 315-400 nm) and photosynthetically available radiation (PAR; 400-700 nm). In marine ecosystems of Patagonia, normal ultraviolet radiation (UVR) levels affect phytoplankton assemblages during the three phases of the annual succession: (1) prebloom season (late summer-fall), (2) bloom season (winter-early spring) and (3) postbloom season (late spring-summer). Small-size cells characterize the pre- and postbloom communities, which have a relatively high photosynthetic inhibition because of high UVR levels during those seasons. During the bloom, characterized by microplankton diatoms, photosynthetic inhibition is low because of the low UVR levels reaching the earth's surface during winter; this community, however, is more sensitive to UV-B when inhibition is normalized by irradiance (i.e. biological weighting functions). In situ studies have shown that UVR significantly affects not only photosynthesis but also the DNA molecule, but these negative effects are rapidly reduced in the water column because of the differential attenuation of solar radiation. UVR also affects photosynthesis versus irradiance (P vs E) parameters of some natural phytoplankton assemblages (i.e. during the pre- but not during the postbloom season). However, there is a significant temporal variability of P vs E parameters, which are influenced by the nutrient status of cells and taxonomic composition; taxonomic composition is in turn associated with the stratification conditions (e.g. wind speed and duration). In Patagonia, wind speed is one of the most important variables that conditions the development of the winter bloom by regulating the depth of the upper mixed layer (UML) and hence the mean irradiance received by cells. Studies on the interactive effects of UVR and mixing show that responses of phytoplankton vary according to the taxonomic composition and cell structure of assemblages; therefore cells use UVR if >90% of the euphotic zone is being mixed. In fact, cell size plays a very important role when estimating the impact of UVR on phytoplankton, with large cells being more sensitive when determining photosynthesis inhibition, whereas small cells are more sensitive to DNA damage. Finally, in long-term experiments, it was determined that UVR can shape the diatom community structure in some assemblages of coastal waters, but it is virtually unknown how these changes affect the trophodynamics of marine systems. Future studies should consider the combined effects of UVR on both phytoplankton and grazers to establish potential changes in biodiversity of the area.     

A Convenient Synthesis of Unsymmetrical N,N′-Disubstitutedα,ω-Diaminoalkanes

A general procedure is described for regiospecific construction of unsymmetrical N-alkyl (or aralkyl)-N′-aryl-α,ω-diaminoalkanes 3 (n=2,3,4) by reduction of N-(ω -arylaminoalkyl)amides 2 with borane. Compounds 2 are readily obtained by condensation of N-(ω-haloalkyl)amides 1 with aromatic amines.     

Galvanostatically Deposited PtNi Thin-Films as Electrocatalysts for the Hydrogen Evolution Reaction

The synthesis of hybrid platinum materials is fundamental to enable alkaline water electrolysis for cost-effective H₂ generation. In this work, we have used a galvanostatic method to co-deposit PtNi films onto polycrystalline gold. The surface concentrations of Ni (Γ_Ni) and Pt (Γ_Pt) were calculated from electrochemical measurements; the Γ_Pt/Γ_Ni ratio and electrocatalytic activity of these materials towards hydrogen evolution reaction (HER) in 1 M KOH show a strong dependence on the current density pulse applied during the electrodeposition. Analysis of the Tafel parameters hints that, on these deposits, HER proceeds through a Volmer-Heyrovsky mechanism. The galvanostatically deposited PtNi layers present a high current output per Pt gram, 3199 A g_Pt⁻¹, which is significantly larger compared to other PtNi-based materials obtained by more extended and more complex synthesis methods.     

Impact of Collection Volume and DNA Extraction Method on the Detection of Biomarkers and HPV DNA in First-Void Urine

The potential of first-void (FV) urine as a non-invasive liquid biopsy for detection of human papillomavirus (HPV) DNA and other biomarkers has been increasingly recognized over the past decade. In this study, we investigated whether the volume of this initial urine stream has an impact on the analytical performance of biomarkers. In parallel, we evaluated different DNA extraction protocols and introduced an internal control in the urine preservative. Twenty-five women, diagnosed with high-risk HPV, provided three home-collected FV urine samples using three FV urine collection devices (Colli-Pee) with collector tubes that differ in volume (4, 10, 20 mL). Each collector tube was prefilled with Urine Conservation Medium spiked with phocine herpesvirus 1 (PhHV-1) DNA as internal control. Five different DNA extraction protocols were compared, followed by PCR for GAPDH and PhHV-1 (qPCR), HPV DNA, and HBB (HPV-Risk Assay), and ACTB (methylation-specific qPCR). Results showed limited effects of collection volume on human and HPV DNA endpoints. In contrast, significant variations in yield for human endpoints were observed for different DNA extraction methods (p < 0.05). Additionally, the potential of PhHV-1 as internal control to monitor FV urine collection, storage, and processing was demonstrated.