Chitosan-based nanocomposite matrices: Development and characterization.

Chitosan-based nanocomposites have a significant industrial impact related to the possibility to design and create new materials and structures. Cellulose nanocrystals (CNC) can be extracted from microcrystalline cellulose (MCC) by controlled acid hydrolysis with H2SO4. This work was focused on: to study the microstructure of CNC isolated from MCC after different hydrolysis times; to develop nanocomposites chitosan-based films; to characterize their structural and thermo-mechanical properties; to analyze the spectral differences among samples by means of ATR-FTIR in combination with principal component analysis (PCA) and square partial minimums model (PLS). It is worth noting that the selected condition for isolate the CNC from MCC was the acid treatment for 2 h, evidenced by size measurements. This fact was supported by transmission electron microscope (TEM) and dynamic light scattering (DLS). In this regard, SEM studies of films showed an assembly process between the nanocelluloses and the CH matrix. The incorporation of CNC into the films resulted in strong interactions between the filler and the matrix demonstrating the affinity between the phases and modifying the mechanical profiles. In summary, CNC was found to be a satisfactory reinforcing agent in biodegradable nanocomposite chitosan-based packaging and are promising as a means to develop tailor-made materials.

An approach for degradation of grape seed and skin proanthocyanidin polymers into oligomers by sulphurous acid.

To develop an efficient method for degradation of grape seed and skin proanthocyanidins polymers into oligomers, an optimized sulphurous acid degradation conditions for grape seed with the temperature of 60 °C, reaction time of 60 min and sample-sulphurous acid ratio of 1:0.2, and for grape skin with the temperature of 40 °C, reaction time of 60 min and sample-sulphurous acid ratio of 1:0.2, were established. Afterwards, HSCCC and prep-HPLC were used to fractionate and isolate individual proanthocyanidin oligomers from the degradation products. Total of ten dimeric or trimeric procyanidins were obtained, and most of them presented high yield (from 0.7 mg to 13.6 mg per run in grape seed and from 0.5 mg to 4.1 mg per run in grape skin) and high purity (over 90%). The proposed method provides a new way for large preparation of oligomeric proanthocyanidins from naturally abundant and wasted polymeric ones.

Pretreatment of Sugar Beet Pulp with Dilute Sulfurous Acid is Effective for Multipurpose Usage of Carbohydrates.

Sulfurous acid was used for pretreatment of sugar beet pulp (SBP) in order to achieve high efficiency of both extraction of carbohydrates and subsequent enzymatic hydrolysis of the remaining solids. The main advantage of sulfurous acid usage as pretreatment agent is the possibility of its regeneration. Application of sulfurous acid as hydrolyzing agent in relatively low concentrations (0.6-1.0 %) during a short period of time (10-20 min) and low solid to liquid ratio (1:3, 1:6) allowed effective extraction of carbohydrates from SBP and provided positive effect on subsequent enzymatic hydrolysis. The highest obtained concentration of reducing substances (RS) in hydrolysates was 8.5 %; up to 33.6 % of all carbohydrates present in SBP could be extracted. The major obtained monosaccharides were arabinose and glucose (9.4 and 7.3 g/l, respectively). Pretreatment of SBP with sulfurous acid increased 4.6 times the yield of glucose during subsequent enzymatic hydrolysis of remaining solids with cellulase cocktail, as compared to the untreated SBP. Total yield of glucose during SBP pretreatment and subsequent enzymatic hydrolysis amounted to 89.4 % of the theoretical yield. The approach can be applied directly to the wet SBP. Hydrolysis of sugar beet pulp with sulfurous acid is recommended for obtaining of individual monosaccharides, as well as nutritional media.

The control of emerging haloacetamide DBP precursors with UV/persulfate treatment.

Haloacetamides (HAcAms), an emerging class of nitrogen-containing disinfection byproducts (N-DBPs) of health concern in drinking water, have been reported to occur in treated drinking waters at low µg/L levels typically. The objective of this study was to examine the potential of an ultraviolet light/persulfate (UV/PS) oxidation technology to reduce the precursors of HAcAms and also minimize the formation of other N-DBPs upon subsequent chlorination. Low-pressure UV photolysis alone and PS pre-oxidation alone did not significantly affect HAcAm formation, however UV/PS pre-oxidation achieved a statistically significant reduction in HAcAm formation and also reduced bromine incorporation into the HAcAms. UV/PS also showed a good performance in removing the precursors of haloacetonitriles and halonitromethanes prior to chlorination. Therefore, UV/PS has the potential to minimize the formation of a range of N-DBPs in organic nitrogen-rich waters where N-DBP precursors are prevalent. However, these benefits should be weighed against the potential drawbacks of increased bromate and sulfate formation, particularly in high-bromide waters.

First and second deprotonation of H2SO4 on wet hydroxylated (0001) α-quartz.

We present an ab initio molecular dynamics study of deprotonation of sulfuric acid on wet quartz, a topic of atmospheric interest. The process is preferred, with 65% of our trajectories at 250 K showing deprotonation. The time distribution of the deprotonation events shows an exponential behavior and predicts an average deprotonation time of a few picoseconds. The process is exoergic, with most of the temperature increase being due to formation of hydrogen bonds prior to deprotonation. In agreement with existing studies of H2SO4 in water clusters, in liquid water, and at the air-water interface, the main determinant of deprotonation is the degree of solvation of H2SO4 by neighboring water molecules. However, we find that if both hydrogens of H2SO4 are simultaneously donated to water oxygens, deprotonation is disfavored. Predicted spectroscopic signatures showing the presence of solvated hydronium and bisulfate are presented. Increasing the temperature up to 330 K accelerates the process but does not change the main features of the deprotonation mechanisms or the spectroscopic signatures. The second deprotonation of H2SO4, studied only at 250 K, occurs provided there is sufficient solvation of the bisulfate by additional water molecules. In comparison to HCl deprotonation on the identical surface examined in our previous work, the first deprotonation of H2SO4 occurs more readily and releases more energy.

An amide based dipodal Zn(2+) complex: nano-molar detection of HSO(4) (−) in a semi-aqueous system.

A new chromogenic dipodal Zn2+ complex (4) bearing an amide group has been synthesized. The anion binding profile of this sensor was investigated with fluorescence and UV-Vis spectroscopy. The receptor 4 has high affinity for HSO4 − with a binding constant of 3.5 × 104 M−1 and a detection limit of 50 nM. The binding ability was confirmed with spectroscopic methods and density functional theory calculation (DFT).

[Distribution of dimethylsulfoxide (DMSO) in the surface water of the Yellow Sea and the Bohai Sea].

The horizontal distributions and diurnal variations of particulate and dissolved dimethylsulfoxide (DMSOp, DMSOd) were studied in the surface water of the Yellow Sea and the Bohai Sea in June, 2011. The determination of DMSO was based on the DMS produced by NaBH4 reduction, which was analyzed using the purge-and-trap technique coupled with gas chromatographic separation and flame photometric detection. The concentrations of DMSOp and DMSOd ranged from 5.43 to 18.35 nmol x L(-1) and from 4.75 to 43.80 nmol x L(-1), respectively, with average values of (11.47 +/- 0.25) nmol x L(-1) and (13.42 +/- 0.58) nmol x L(-1). The results showed that no relationship was found between DMSOp and environmental factors such as chlorophyll a (Chl-a), temperature and salinity, whereas a positive correlation was observed between DMSOp/Chl-a and salinity, indicating that intracellular DMSO could act as a cryo-osmoregulator. A significant relationship was also found between DMSOd and dimethylsulfide (DMS), whereas there was no relationship between DMSOd and DMSOp or DMSOd and bacteria, implying that DMSOd in the surface water was produced mainly through the photochemical oxidation of DMS. In addition, both the DMSOp and DMSOd concentrations exhibited obvious diurnal variations with the higher values in the day time.

Microwave detection of sulfoxylic acid (HOSOH).

Sulfoxylic acid (HOSOH), a chemical intermediate roughly midway along the path between highly reduced (H2S) and highly oxidized sulfur (H2SO4), has been detected using Fourier transform microwave spectroscopy and double resonance techniques, guided by new high-level CCSD(T) quantum-chemical calculations of its molecular structure. Rotational spectra of the two most stable isomers of HOSOH, the putative ground state with C2 symmetry and the low-lying C(s) rotamer, have been measured to high precision up to 71 GHz, allowing accurate spectroscopic parameters to be derived for both isomers. HOSOH may play a role in atmospheric and interstellar chemistry, and the present work provides the essential data to enable remote sensing and/or radioastronomical searches for these species. Spectroscopic characterization of HOSOH suggests that other transient intermediates in the oxidation of SO2 to H2SO4 may be amenable to laboratory detection as well.

Improving the surface biocompatibility with the use of mixed zwitterionic self-assembled monolayers prepared by a proper solvent.

In this study, the mixed self-assembled monolayers (SAMs) containing the mixture of long-chain alkanethiol, SH(CH(2))(11)NH(2) and SH(CH(2))(10)SO(3)H, was prepared as a model surface to examine the interaction between the biological environment and artificial surface. The 10% (v/v) NH(4)OH ethanolic solution and DMSO were chosen as the solvents for the preparation of these mixed SAMs and the "solvent effect" was discussed. X-ray photoelectron spectroscopy (XPS) has indicated that -SO(3)H/-NH(2) mixed SAMs formed from 10% (v/v) NH(4)OH ethanolic solution were surface "-SO(3)H poor", while a nearly equivalent amount of surface -SO(3)H functionality was presented on the mixed SAMs formed from DMSO. This has resulted from the different solvation capability between solvent molecules and the alkanethiol. Such solvent effects were also reflected in various surface properties such as surface wettability and surface zeta potential. The mixed SAMs formed from DMSO were more surface hydrophilic and less negatively surface charged than from 10% (v/v) NH(4)OH ethanolic solution. In addition, these mixed SAMs formed from DMSO exhibited the least amount of protein adsorbed as well as a better platelet compatibility than its counterpart from 10% (v/v) NH(4)OH ethanolic solution. These findings indicated that choosing a proper solvent for mixed zwitterionic SAM can greatly affect its surface properties and biocompatibility, such as to form a surface with near neutrality for reducing protein adsorption and subsequent platelet adhesion and activation.

Coupling interactions between sulfurous acid and the hydroperoxyl radical.

Radical-molecule complexes associated with the hydroperoxyl radical (HOO) play an important role in atmospheric chemistry. Herein, the nature of the coupling interactions between sulfurous acid (H(2)SO(3)) and the HOO radical is systematically investigated at the B3LYP/6-311++G(3df,3pd) level of theory in combination with the atoms in molecules (AIM) theory, the natural bond orbital (NBO) method, and energy decomposition analyses (EDA). Eight stable stationary points possessing double H-bonding features were located on the H(2)SO(3)...HOO potential energy surface. The largest binding energies of -12.27 and -11.72 kcal mol(-1) are observed for the two most stable complexes, where both of them possess strong double intermolecular H-bonds of partially covalence. Moreover, the characteristics of the IR spectra for the two most stable complexes are discussed to provide some help for their possible experimental identification.

Ethanol production from H(2)SO (3)-steam-pretreated fresh sweet sorghum stem by simultaneous saccharification and fermentation.

The present work presents an alternative approach to ethanol production from sweet sorghum: without detoxification, acid-impregnated fresh sweet sorghum stem which contains soluble (glucose and sucrose) and insoluble carbohydrates (cellulose and hemicellulose) was steam pretreated under mild temperature of 100 degrees C. Simultaneous saccharification and fermentation experiments were performed on the pretreated slurries using Saccharomyces cerevisiae. Experimentally, ground fresh sweet sorghum stem was combined with H(2)SO(3) at dosages of 0.25, 0.50, and 0.75 g/g dry matter (DM) and steam pretreated by varying the residence time (60, 120, or 240 min). According to enzymatic hydrolysis results and ethanol yields, H(2)SO(3) was a powerful and mild acid for improving enzymatic digestibility of sorghum stem. At a solid loading of 10% (w/v) and acid dosage of 0.25 g/g DM H(2)SO(3) at 100 degrees C for 120 min, 44.5 g/L ethanol was obtained after 48 +/- 4 h of simultaneous saccharification and fermentation. This corresponded to an overall ethanol yield of 110% of the theoretical one, based on the soluble carbohydrates in the fresh sweet sorghum stem. The concentrations of hydroxymethylfurfural and furfural of the sulfurous acid pretreated samples were below 0.4 g/L. Ethanol would not inhibit the cellulase activity, at least under the concentration of 34 g/L.

[Effect of acid and alkali on phosphorus release from sewage sludge in the microwave treatment process].

Impacts of acid and alkali addition on phosphorus release from sewage sludge were investigated in a microwave reactor at atmospheric pressure. Results showed that in the microwave irradiation process, though NaOH pretreatment increased the release efficiency of phosphorus from 28.8% to 59.1%, large amounts of carbon and nitrogen were correspondingly released into the supernatant. Compared to the alkali pretreatment, pretreatment of H2SO4 not only resulted in the higher release efficiency of phosphorus by 3 times (up to 84.5%), but also sharply reduced the amount of carbon and nitrogen released into the supernatant. These results suggest that H2SO4 pretreatment of sewage sludge can selectively release carbon, nitrogen and phosphorus, which is more suitable for phosphorus recovery from sewage sludge. Meanwhile, the pH range of 2.1-2.2 was optimal for phosphorus release from sewage sludge in the microwave treatment process.

The role of copper in cysteine oxidation: study of intra- and inter-molecular reactions in mass spectrometry.

Cysteine-containing peptide oxidation was studied both by using an inert platinum electrode and a sacrificial electrode (copper or zinc) generating metallic ions in electrospray ionization mass spectrometry (ESI-MS). Using peptides containing one, two and three cysteines, we have compared the different chemical and electrochemical oxidation pathways of cysteine (RS(-II)H) to cystine (RS(-I)S(-I)R) and to sulfenic, sulfinic and sulfonic acid (RS(0)OH, RS(II)O(2)H and RS(IV)O(3)H, respectively). In the absence of copper ions, intra-molecular reactions were the most abundant, whereas inter-molecular reactions were found to be enhanced by the presence of copper ions. These cations favor the formation of 2 : 1 (peptide : copper) complexes compared to 1 : 1 complexes, thus enhancing the formation of inter-molecular bridges. This study highlights the importance of the position of cysteine inside a peptide during disulfide bridge formation.

[The weak acids as proton carriers through bilayer lipid membranes].

The ability of the weak inorganic acids (H2S, HCN) and lower carboxylic acids to interact with bilayer lipid membranes (BLMs), change their conductivity, act as the protonophores were investigated. The mechanism of the BLM conductivity change was studied. The factors affecting the acids interaction with model lipid membranes were determined. Maximum conductivity change observes at pH equal dissociation constant of weak acids and depends on the distribution coefficient "octanol(membrane)-water".

A simple and efficient synthesis of puromycin, 2,2'-anhydro-pyrimidine nucleosides, cytidines and 2',3'-anhydroadenosine from 3',5'-O-sulfinyl xylo-nucleosides.

Synthesis of antibiotics, puromycin and 3'-amino-3'-deoxy-N6,N6-dimethyladenosine 11 was achieved by utilizing the cyclic sulfite 6a of the xylo-3',5'-dihydroxy group as a new protective group. The key synthetic step is the deprotection of the sulfite moiety through the intramolecular cyclization of 2-alpha-carbamate 7. In a similar manner 2,2'-anhydro-pyrimidine nucleosides 15, ribo-cytidines 17 and 2',3'-anhydroadenosine 14 were prepared in high yields from the corresponding sulfites 4, 5, and 6b, respectively.

Recycling spent zinc manganese dioxide batteries through synthesizing Zn-Mn ferrite magnetic materials.

A novel process to reclaim spent zinc manganese dioxide batteries (SDBs) through synthesizing Zn-Mn ferrite magnetic materials is present. Firstly, the dismantling, watering, magnetism, baking and griddling steps were consecutively carried out to obtain iron battery shells, zinc grains and manganese compounds using the collected SDBs, and then these separated substances were dissolved with 4 mol L(-1) H(2)SO(4) to prepare FeSO(4), ZnSO(4) and MnSO(4) reactant solutions. Secondly, Zn-Mn ferrites with stoichiometric ratio of Mn(0.26)Zn(0.24)FeO(2) were synthesized using chemical co precipitation process with ammonium oxalate precipitator. The XRD results showed that the obtained Zn-Mn ferrites had spinel structure and high purity at the calcining temperatures of 850-1250 degrees C. With the increase of calcining temperature, the finer crystalline structure could be formed, and their intensity of saturation magnetization reached the highest value at 1150 degrees C. The magnetization performances of Zn-Mn ferrites prepared from the SDBs were similar to that of from analysis reagents, suggesting the feasibility to synthesize Zn-Mn ferrites with high properties from SDBs.

Reactions between the SO4*(-) radical and some common anions in atmospheric aqueous droplets.

The rate constants of reactions between the SO4*(-) radical and some common anions in atmospheric aqueous droplets e.g. Cl-, NO3-, HSO3- and HCO3- were determined using the laser flash photolysis technique. Absorption spectra of SO4*(-) and the product radicals were also reported. The chloride ion was evaluated among all the anions to be the most efficient scavenger of SO4*(-). The results may supply useful information for a better understanding of the vigorous radical-initiated reactions in atmospheric aqueous droplets such as clouds, rains or fogs.

Matrix isolation FTIR spectroscopic and theoretical study of dimethyl sulfite.

The preferred conformations of dimethyl sulfite and their vibrational spectra were studied by matrix-isolation Fourier transform infrared spectroscopy and theoretical methods (density functional theory (DFT) and Moller-Plesset (MP2), with basis sets of different sizes, including the quadruple-zeta, aug-cc-pVQZ basis). Five minima were found at these levels of theory. At the MP2/6-31++G(d,p) and DFT/B3LYP/aug-cc-pVQPZ levels, the GG conformer (where the O-S-O-C dihedral angles are 73.2 and 70.8 degrees ) resulted in the conformational ground state. At the highest level of theory used, the GT conformer (O-S-O-C = +68.5 and -173.2 degrees ) is 0.83 kJ mol(-1) higher in energy than the GG form, while conformer GG' (O-S-O-C = +85.7 and -85.7 degrees ) has a relative energy of 1.18 kJ mol(-1). The remaining two conformers (G'T and TT) are high-energy forms and not experimentally relevant. In consonance with the theoretical predictions, conformer GG was found to be the most stable conformer in the gaseous phase as well as in the low-temperature matrices. Annealing of the argon matrices first promotes the GG'-->GT isomerization, which is followed by conversion of GT into the most stable conformer. There is no evidence of occurrence of GG'-->GG direct conversion in the low-temperature matrices. On the other hand, during deposition of the xenon matrices conformer GG' totally converts to conformer GT. Two observations demonstrated this fact: no evidence of bands corresponding to GG' were observed in xenon matrices and the GG/GT intensity ratio became similar to the GG/(GT + GG') intensity ratio observed in argon matrices. All these results could be explained by taking into account the relative values of the theoretically predicted energy barriers for the different isomerization processes: GG'-->GT, 1.90 kJ mol(-1); GT-->GG, 9.64 kJ mol(-1); and GG'-->GG, 19.46 kJ mol(-1).

[Influence of reagent evaporation on other laboratory reagents and appropriate countermeasures].

When the automated analyzer was first introduced, abnormally high values of urine creatinine and abnormally low values of serum creatinine were seen. It was shown that evaporation of the reducing agent stabilizer(sulfurous acid), which is present in the serum iron measurement kit, was occurring and that the observed low values of serum creatinine were due to consumption of hydrogen peroxide by gasifying sulfurous acid. After the cause was elucidated, the abnormal lowering of creatinine values was prevented. This experience demonstrates that care must be exercised when introducing new analytical method in clinical laboratories because evaporation of reagents can influence in other reagent systems.