Mechanisms of water interaction with pore systems of hydrochar and pyrochar from poplar forestry waste.

The aim of this study was to understand the water-surface interactions of two chars obtained by gasification (pyrochar) and hydrothermal carbonization (hydrochar) of a poplar biomass. The two samples revealed different chemical compositions as evidenced by solid state (13)C NMR spectroscopy. In fact, hydrochar resulted in a lignin-like material still containing oxygenated functionalities. Pyrochar was a polyaromatic system in which no heteronuclei were detected. After saturation with water, hydrochar and pyrochar were analyzed by fast field cycling (FFC) NMR relaxometry. Results showed that water movement in hydrochar was mainly confined in very small pores. Conversely, water movement in pyrochar led to the conclusion that a larger number of transitional and very large pores were present. These results were confirmed by porosity evaluation derived from gas adsorption. Variable-temperature FFC NMR experiments confirmed a slow-motion regime due to a preferential diffusion of water on the solid surface. Conversely, the higher number of large pores in pyrochar allowed slow movement only up to 50 °C. As the temperature was raised to 80 °C, water interactions with the pore surface became weaker, thereby allowing a three-dimensional water exchange with the bulk liquid. This paper has shown that pore size distribution was more important than chemical composition in affecting water movement in two chemically different charred systems.

Effect of heating time and temperature on the chemical characteristics of biochar from poultry manure.

Poultry manure (PM) chars were obtained at different temperatures and charring times. Chemical-physical characterization of the different PM chars was conducted by cross-polarization magic angle spinning (CPMAS) (13)C NMR spectroscopy and thermal analysis. CPMAS (13)C NMR spectra showed that the chemical composition of PM char is dependent on production temperature rather than on production duration. Aromatic and alkyl domains in the PM chars obtained at the lowest temperatures remained unchanged at all heating times applied for their production. The PM char obtained at the highest temperature consisted only of aromatic structures having chemical nature that also appeared invariant with heating time. Thermogravimetry revealed differences in the thermo-oxidative stability of the aromatic domains in the different PM chars. The PM char produced at the highest temperature appeared less stable than those produced at the lowest temperatures. This difference was explained by a protective effect of the alkyl groups, which are still present in chars formed at lower temperature. The analysis of the chemical and physicochemical character of poultry manure chars produced at different temperatures can increase understanding of the role of these materials in the properties and behavior of char-amended soils.

Reconstruction of the environmental evolution of a Sicilian saltmarsh (Italy).

The present study deals with the reconstruction of the environmental evolution of a Trapani saltmarsh (southwestern Sicily, Italy) by combining different analytical approaches such as metal content evaluation, low-field nuclear magnetic resonance (NMR) relaxometry, and benthic foraminifera identification. A 41 cm core was collected in the sediments of a Trapani saltmarsh (southwestern Sicily, Italy) at a water depth of about 50 cm. Different time intervals were recognized, each characterized by peculiar features that testify different environmental conditions. In particular, the bottom layers of the sediment core (41-28 cm) comprised the lowest amount of mud fraction, only some selected metals, and the lowest foraminiferal density. Here, co-occurrence of abundant microcrystals of gypsum and Ammonia tepida is indicative of hyper-saline conditions. In the sediments from 28 to 6 cm, mud fraction and number of metal elements resulted higher due to the increase of the anthropogenic pressure. The sediments in the last time interval, corresponding to the environmental recovery of the saltmarsh, showed an increase of foraminiferal density, a decrease of the mud fraction, and a trend in the metal concentration attributable to the protection policy applied since 1990. NMR relaxometry parameters highlighted the changes of sediment chemical-physical heterogeneity going from the bottom to the top of the core. These heterogeneities have been related to the different intervals recognized as aforementioned. The present study highlights how the anthropogenic pressure modifies the environmental conditions of a transitional ecosystem like saltmarshes.

Synthesis and characterization of a novel high luminescent gold-2-mercapto-1-methyl-imidazole complex.

Synthesis and characterization of a new gold-2-mercapto-1-methyl imidazole are reported. This new organic material shows an extraordinary fluorescence activity (superfluorescence) up to 220°C with an unusual quantum yield of 0.2. Both fluorescence and NMR spectroscopy were applied to understand the behavior of the gold-2-mercapto-1-methylimidazole complex. Results suggest that the superfluorescence activity can be attributed to the shrinking of the HOMO-LUMO band gap energy following complexation of the organic imidazole system with gold.

Dynamics of pistachio oils by proton nuclear magnetic resonance relaxation dispersion.

A number of pistachio oils were selected in order to test the efficacy of nuclear magnetic resonance relaxation dispersion (NMRD) technique in the evaluation of differences among oils (1) obtained from seeds subjected to different thermal desiccation processes, (2) retrieved from seeds belonging to the same cultivar grown in different geographical areas and (3) produced by using seed cultivars sampled in the same geographical region. NMRD measures relaxation rate values which are related to the dynamics of the chemical components of complex food systems. Results not only allowed to relate kinematic viscosity to relaxometry parameters but also were successful in the differentiation among the aforementioned oils. In fact, from the one hand, the larger the kinematic viscosity, the faster the rotational motions appeared as compared to the translational ones. On the other hand, relaxation rate curves (NMRD) varied according to the oxidative stresses and chemical composition of each sample. The present study showed for the first time that NMRD is a very promising technique for quick evaluations of pistachio oil quality without the need for time-consuming chemical manipulations.

Dynamics of hyaluronan aqueous solutions as assessed by fast field cycling NMR relaxometry.

Fast field cycling (FFC) NMR relaxometry has been used to study the conformational properties of aqueous solutions of hyaluronan (HYA) at three concentrations in the range 10 to 25 mg mL(-1). Results revealed that, irrespective of the solution concentration, three different hydration layers surround hyaluronan. The inner layer consists of water molecules strongly retained in the proximity of the HYA surface. Because of their strong interactions with HYA, water molecules in this inner hydration layer are subject to very slow dynamics and have the largest correlation times. The other two hydration layers are made of water molecules which are located progressively further from the HYA surface. As a result, decreasing correlation times caused by faster molecular motion were measured. The NMRD profiles obtained by FFC-NMR relaxometry also showed peaks attributable to (1)H-(14)N quadrupole interactions. Changes in intensity and position of the quadrupolar peaks in the NMRD profiles suggested that with increasing concentration the amido group is progressively involved in the formation of weak and transient intramolecular water bridging adjacent hyaluronan chains. In this work, FFC-NMR was used for the first time to obtain deeper insight into HYA-water interactions and proved itself a powerful and promising tool in hyaluronan chemistry.

Dissolution mechanism of crystalline cellulose in H3PO4 as assessed by high-field NMR spectroscopy and fast field cycling NMR relaxometry.

Many processes have been proposed to produce glucose as a substrate for bacterial fermentation to obtain bioethanol. Among others, cellulose degradation appears as the most convenient way to achieve reliable amounts of glucose units. In fact, cellulose is the most widespread biopolymer, and it is considered also as a renewable resource. Due to extended intra- and interchain hydrogen bonds that provide a very efficient packing structure, however, cellulose is also a very stable polymer, the degradation of which is not easily achievable. In the past decade, researchers enhanced cellulose reactivity by increasing its solubility in many solvents, among which concentrated phosphoric acid (H(3)PO(4)) played the major role because of its low volatility and nontoxicity. In the present study, the solubilization mechanism of crystalline cellulose in H(3)PO(4) has been elucidated by using high- and low-field NMR spectroscopy. In particular, high-field NMR spectra showed formation of direct bonding between phosphoric acid and dissolved cellulose. On the other hand, molecular dynamics studies by low-field NMR with a fast field cycling (FFC) setup revealed two different H(3)PO(4) relaxing components. The first component, described by the fastest longitudinal relaxation rate (R(1)), was assigned to the H(3)PO(4) molecules bound to the biopolymer. Conversely, the second component, characterized by the slowest R(1), was attributed to the bulk solvent. The understanding of cellulose dissolution in H(3)PO(4) represents a very important issue because comprehension of chemical mechanisms is fundamental for process ameliorations to produce bioenergy from biomasses.

[Effects of two Sicilian red wines on some cardiovascular risk factors]. / Effetto di due vini rossi siciliani su alcuni fattori di rischio cardiovascolare.

BACKGROUND: The aim of this study was to evaluate whether Sicilian red wine consumption is associated with a lower cardiovascular risk. METHODS: Forty-eight subjects of both sexes (age range 35-65 years) nondrinkers or rarely drinkers of moderate red wine intake were selected. Subjects were divided into two groups (group A and group B), assigned to receive with a crossover design 250 ml/die (during the meals) of one of two types of Sicilian red wines (Nero d'Avola and Etna Torrepalino respectively). At all visits (-15 days, basal, +4 and +8 weeks) the following parameters were measured: blood glucose, total cholesterol and triglycerides (by enzyme kit methods, Boehringer Mannheim, Milan, Italy), HDL cholesterol (by selective precipitation with dextran-magnesium chloride), LDL cholesterol (by calculation with the Friedewald formula), LDL/HDL ratio, apolipoproteins A1 and B (by radial immunodiffusion, Behring Institute, Scoppito, Italy), lipoprotein(a) (ELISA, Technoclone, Vienna, Austria), plasma C-reactive protein (high-sensitivity, Dade Behring, Marburg, Germany), D-dimer (Turbiquant, Dade Behring), factor VII (coagulant activity, Dade Behring), plasminogen activator inhibitor antigen (ELISA), tissue-type plasminogen activator antigen (ELISA), fibrinogen (coagulant), oxidized LDL antibody (ELISA), total plasma antioxidant capacity (FRAP method). RESULTS: At the end of the red wine intake period, HDL cholesterol was significantly increased (p < 0.01) and the LDL/HDL ratio was significantly decreased (p < 0.05) in both study groups, while apolipoprotein A1 was significantly increased (p < 0.05) only in group A. In both group A and group B fibrinogen (p < 0.01 and p < 0.005, respectively), factor VII (p < 0.01 and p < 0.05, respectively), plasma C-reactive protein (p < 0.005 and p < 0.05, respectively) and oxidized LDL antibody (p < 0.05) were significantly decreased, while tissue-type plasminogen activator (p < 0.005), plasminogen activator inhibitor (p < 0.005) and total plasma antioxidant capacity (p < 0.005) were significantly increased. CONCLUSIONS: Our results show a positive effect of these Sicilian red wines on many risk factors, suggesting a moderate consumption of red wine in the adult population as a component of the Mediterranean diet.

An investigation of the seasonal pattern of mannitol content in deciduous and evergreen species of the oleaceae growing in northern Sicily.

In several species of the Oleaceae, mannitol, already present at considerable levels, accumulates in response to stress. This family comprises both deciduous and evergreen species, and we investigated the role of mannitol in deciduous malacophyll and evergreen sclerophyll species growing under the same conditions in the field. The relationship between mannitol content and changes in rainfall or temperature was also studied. The mannitol content of leaves of Fraxinus ornus L., F. angustifolia Vahl., Olea europaea L. and Phillyrea media L. was determined by gas chromatography. Leaf samples were collected once a month for 1 year. In the two ash species, the seasonal pattern of mannitol content appeared the same: a gradual increase in spring, peaking in summer, followed by a gradual decrease. The mannitol content was similar in both species, ranging between 260 and 720 micromol g(-1) d. wt. The seasonal pattern of mannitol content in Olea and Phillyrea was similar for both species, but unlike that of Fraxinus did not show a summer peak. Rainfall was negatively correlated with the seasonal increase of mannitol content in ash. Mannitol content increased gradually during drought, reaching a maximum value at the end of the dry season. Temperature did not have a direct influence on mannitol content. In Olea and Phillyrea, variations in mannitol content were poorly correlated with rainfall or temperature, indicating that mannitol does not have a primary role in the response of these species to the hot, dry summer conditions.