Cellular uptake of octaarginine-conjugated tetraarylporphyrin included by per-O-methylated ß-cyclodextrin.

This paper describes the synthesis, structural characterization and cellular uptake of a supramolecular 1 : 2 inclusion complex of meso-tetraphenylporphyrin having an octaarginine peptide chain (R8-TPP) and heptakis(2,3,6-tri-O-methyl)-ß-cyclodextrin (TMe-ß-CD). R8-TPP was synthesized by 2 approaches: (1) on-resin conjugation of the N-terminal of octaarginine with 5-(4-carboxyphenyl)-10,15,20-triphenylporphyrin, followed by cleavage from the resin, and (2) Michael addition reaction between 5-[4-(3-maleimidopropylamido)phenyl]-10,15,20-triphenylporphyrin and cysteine-octaarginine peptide (Cys-Arg8). The R8-TPP obtained from both the approaches formed stable inclusion complexes with TMe-ß-CD by which non-substituted phenyl groups at the 10- and 20-positions were included to form trans-type 1 : 2 inclusion complexes. The complexation prevented the self-aggregation of R8-TPP, which resulted in the solubilisation of R8-TPP in aqueous media. A cellular uptake study using HeLa cells showed that R8-TPP complexed with TMe-ß-CD in a serum-free medium was efficiently taken up by the cells and uniformly dispersed in the cytosol. In the serum-containing medium, the R8-TPP-TMe-ß-CD complex dissociated, and the serum protein bound R8-TPP. The R8-TPP-protein complex was localized in the endosomes of the cells. The cytosol-dispersed R8-TPP showed a higher photo-induced cytotoxicity than its endosome-trapped counterpart.

Bio-diesel Fuel Material Supply in Vietnam and Its Current and Future Potentiality with a Focus on Rubber Seed Oil.

Diesel fuel usage in Vietnam is increasing rapidly, but most of it is imported from overseas. In this study, we investigated the possibility of popularizing bio-diesel fuel (BDF) made from Vietnamese origin resources as a sustainable energy solution. The world's energy cost fluctuates significantly depending on economic or political movements, especially after the Russian invasion of Ukraine began in 2022. This caused energy prices soar, attacking the global economy in a short period and requiring a wide range of energy supply sources. We aim to promote commercial BDF production in Vietnam for future energy security and contribution to the Vietnamese economy. Eight necessary factors were investigated to choose suitable material for BDF production. The factors are as follows: 1) material with Vietnamese origin, 2) sufficient and continuous supply volume, 3) sufficient quality to run diesel engines, including common-rail diesel engines, 4) inedibility, 5) low enough freezing point, 6) ease of collection, 7) affordability, and 8) availability of valuable elements in the material. If a suitable material candidate is not stable, it may be changed over time. In this study, the focus material was rubber seed oil. Because rubber production in Vietnam is quite stable with over 900,000 ha plantation area, and there is a potentiality to collect seeds and produce about 50,000 tons of BDF annually. In addition, the quality of rubber seeds based BDF is very high, such as low enough freezing point, etc. However, most of those rubber seeds are currently not collected and used.

Preparation of High-quality Oil from Vegetable Oil with High-free Fatty Acid (FFA) Content Using an Ammonia/Methanol Solution.

There are significant concerns regarding the quality of vegetable oils in the food and biofuel industries. In this study, we explored the preparation of high- quality oil from high-free fatty acid (FFA) vegetable oil using an ammonia/MeOH solvent as an alkali base. Among the six tested solvents, MeOH was the most suitable for the separation of the oil and FFAs. Among the three alkali bases, ammonia enhanced the miscibility of FFAs in MeOH by forming ammonium salts. The amounts of FFAs in the upper layer and oil in the lower layer were positively correlated (r = 0.9348 and 0.9617, respectively) with MeOH. With increasing MeOH concentration, the amount of oil in the lower layer increased along with the FFAs in the upper layer. Using the molar ratio of ammonia to FFA 1:1 and the ratio (v/w) of MeOH to oil 4:3, 91.6% FFAs and 97.8% oil in the upper and lower layers, respectively, were produced from 50% FFA oil. Using a relational expression of FFAs and oil in the upper layer, 97.1% FFAs and 99.6% oil in each layer was obtained from 10% FFA oil. The oil in the lower layer was further purified by extraction with MeOH. This method is easy and efficient for the separation and purification of oil, accompanied by the reuse of reagents with almost no loss of raw materials.

Optimization of Procedure for Determining Dissolved Oxygen in Surface Water and Seawater Exploiting the UV-vis Absorption of Mn(III) Species.

We present an analytical method for dissolved oxygen based on the quantification of Mn(III) absorbance in a water sample. After Mn(II) reacts with the oxygen molecules in water, Mn(III) is formed and stabilized by hexa-metaphosphate under acidic conditions. The UV visible absorbance of Mn(III) is proportional to the oxygen concentration in the water sample. Compared to the Winkler method, the proposed method has the same accuracy (R = 0.9992 at 0 - 52 mg dm-3) but requires fewer reagents; furthermore, it does not involve titration. Interferences from nitrite and iodate were not observed. This procedure can be used to accurately and quickly determine the oxygen concentrations in different natural water sources, including seawater.

Development of a Photometric Method to Measure Molecular Oxygen in Water.

A photometric method to determine molecular oxygen in water was developed. When manganese(II) is oxidized by oxygen under alkaline conditions, the presence of polyphosphate can prevent precipitation due to a coacervate reaction. The oxidized manganese later dissolves in acid to form a pink Mn(III) species, which has a stable UV/vis spectrum. Monitoring of the oxygen concentration based on the absorbance of the pink Mn(III) species at 517 nm showed a strong correlation with both the Winkler method and an optical sensor. As a result, the present method can measure not only dissolved oxygen, but also fine bubbles oxygen in in the water sample with high reliability (0 - 26 mg dm-3, r2 = 0.9995). During this process, no significant interference from nitrite or metal ions was observed. The accuracy of the measurement was steady at high temperatures of the water samples (≤ 363 K).

Ultrasound Assisted Cascade Extraction of Oil, Vitamin E, and Saccharides from Roselle (Hibiscus Sabdariffa L.) Seeds.

Roselle seeds, a waste biomass of the roselle calyx processing industry, were utilized to recover valuable compounds of oil, vitamin E, and water-soluble saccharides. Firstly, ultrasound-assisted extraction (UAE) and conventional stirring extraction were conducted for saccharide extraction, and the advantage of UAE was confirmed. Secondly, oil, vitamin E, and saccharides extracted from Vietnamese roselle seeds by UAE were analyzed for the first time. Oil of tri-, di-, and mono-glycerides, fatty acids of linoleic-, oleic-, palmitic-, and stearic-acids, vitamin E of γ- and α-tocopherol, and saccharides of sucrose, raffinose, stachyose, etc. were identified, and the amounts of these components were compared with those in other country's roselle seeds. Thirdly, cascade extraction of oil, vitamin E, and saccharides by UAE was investigated with solvents of hexane, hexane:ethyl acetate binary solvent, and water. The results indicated that the order of using solvents was very important for high and selective extraction: the best order to recover oil (almost 100%), vitamin E (95.7%), and saccharides (86.2%) was hexane, and then water.

The chemistry of drying an aqueous solution of salts.

The fate of salts in drying aqueous solution was investigated. In the drying of acidic solutions, weak acid ions and chloride ions combine with protons and evaporate, depending on the proton concentration. In the drying of alkaline solutions, weak acid ions evaporate or remain as salts depending on the ratio of the concentrations of excess nonvolatile cations (the difference between concentrations of nonvolatile cation and nonvolatile anion) to volatile anions defined as DeltaCA. Under neutral and alkaline conditions, the fate of nitrite depends not only on DeltaCA but also on the drying speed. Nitrite is converted to N2, which is formed by reacting nitrite with ammonium (denitrification), NO and NO2, HONO and salts. In urban areas, nitrite and ammonium can appear in high concentrations in dew. HONO in the atmosphere affects the ozone concentration, but dew formation decreases the concentration of HONO. If chemical denitrification occurs, nitrogen species will decrease in the environment, and as a result, the ozone concentration could decrease. Ozone levels show an ozone depression when dew formed, and a Box model simulation showed an ozone depression by decreasing HONO levels.

Sonochemical reduction of permanganate to manganese dioxide: the effects of H2O2 formed in the sonolysis of water on the rates of reduction.

Chemical effects of ultrasound have been actively researched in the field of the synthesis of various metal nanoparticles and nanostructured materials. It is very important to understand the reduction mechanism of metal ions, because the reduction processes can be often applied to the synthesis of various materials. In this study, the sonochemical reduction of MnO4- to MnO2 in water under Ar atmosphere was investigated to discuss the reduction mechanism. It has been reported that H, OH, H2 and H2O2 are formed from the sonolysis of water. To understand the roles of H2O2 on the reduction, the reaction of MnO4- with H2O2 without ultrasonic irradiation was investigated. The obtained results suggested the progress of the following reaction: 2MnO4-+3H2O2-->2MnO2+3O2+2OH-+2H2O. In addition, the rates of the sonochemical reduction of MnO4- were investigated in the presence of 1-propanol, where 1-propanol acted as an OH radical scavenger so that the amounts of the sonochemically formed H2O2 molecules were able to be controlled. The results clearly indicated that the sonochemically formed H2O2 molecules as well as H2 molecules and H atoms play an important role for MnO4- reduction. This mechanism was also supported by the analysis of pH changes during ultrasonic irradiation: the pH value increased as the sonochemical reduction of MnO4- proceeded.

Influence of adding salt on ultrasonic atomization in an ethanol-water solution.

Ethanol was enriched by ultrasonic atomization. Enrichment ratios were increased by adding salt to the ethanol solution. Different enrichment ratios were observed for different types of salts in a range of low ethanol concentrations. The enrichment ratio was significantly improved by adding K(2)CO(3) or (NH(4))(2)SO(4). It is concluded that this is due to enhanced interfacial adsorption of the ethanol. Addition of Na(2)CO(3) to the ethanol solution also enhanced the interfacial adsorption of the ethanol, but the effect was relatively small. Addition of NaCl to the ethanol solution did not enhance the interfacial adsorption of the ethanol.

Effect of reaction vessel diameter on sonochemical efficiency and cavitation dynamics.

The influence of reaction vessel diameter on the sonochemical yield was investigated by using reaction vessels with five different diameters. It was revealed that the formation of H(2)O(2) and chloride ion, from the sonolysis of pure water and 1,2,4-trichlorobenzene aqueous solution, was affected by the reaction vessel diameter. That is, these yields increased as the reaction vessel diameter increased up to ø 90 mm and then decreased over ø 90 mm. From the analyses of the measurement of sonochemiluminescence and the calorimetry, it was suggested that active cavitation bubbles were formed at certain zones. In the case of a larger diameter reaction vessel, it was suggested that bubble nuclei that have not grown up to the resonance size, escaped from the sonication zone to the non-sonication zone and dissolved away. As a result, the number of active cavitation bubbles and the yields of H(2)O(2) and chloride ion would decrease in the case of a larger diameter reaction vessel.

Comparison between the effects of ultrasound and gamma-rays on the inactivation of Saccharomyces cerevisiae: analyses of cell membrane permeability and DNA or RNA synthesis by flow cytometry.

The effects of 200 kHz ultrasonic irradiation on DNA or RNA formation and membrane permeability of yeast cells were investigated by flow cytometry and compared with those of (60)Co gamma-ray radiation. Colony counting analyses were also performed for comparison. It was observed that the colony-forming activity of yeast cells was not affected by small doses of ultrasonic irradiation, but was closely related to the amounts of sonolytically formed hydrogen peroxide at concentrations of more than 80 microM. On the other hand, gamma-rays directly retarded colony-forming ability in addition to the effects of radiolytically formed hydrogen peroxide. The results obtained by flow cytometry also indicated that the amounts of DNA or RNA formed decreased with an increase in ultrasonic irradiation time without any threshold. These results indicated that flow cytometry can show early growth activities, but that colony counting analyses are insufficient to evaluate continuous and quantitative changes in these activities. In addition, by analyzing the amounts of DNA or RNA formed in the presence of the same amount of hydrogen peroxide, it was found that DNA or RNA formation behavior in the presence of hydrogen peroxide with no irradiation was similar to that following ultrasonic irradiation. These results suggested that similar chemical effects due to the formation of hydrogen peroxide were produced during ultrasonic irradiation. In addition, physical effects of ultrasound, such as shock wave, hardly contributed to cell inactivation and cell membrane damage, because relatively high frequency ultrasound was used here. In the case of gamma-ray radiation, direct physical effects on the cells were clearly observed.

Seasonal change in the atmospheric concentration of particulate polycyclic aromatic hydrocarbons in Ho Chi Minh City, Vietnam.

We analyzed atmospheric particulate polycyclic aromatic hydrocarbons (PAHs) in Ho Chi Minh City, Vietnam, for 19 months. The average concentrations of total PAHs at dry and rainy seasons were 4.28 +/- 2.83 and 15.71 +/- 8.21 ng m(-3), respectively. The use of motorcycles without catalytic converters, estimated to be main emission sources of PAHs, would be higher during the dry season. PAH concentrations show a negative correlation with sunshine duration (r = -0.51). Furthermore, the ratio of average PAH concentration in the dry season to that in the rainy season shows a positive correlation with photolytic half-life (r = 0.94). Thus, seasonal changes in PAH concentrations are attributable to their photolytic degradation.

Evaporation loss of dissolved volatile substances from ice surfaces.

Volatile acidic solutes were used to make dilute solutions, which were frozen by various methods. The concentration of solutes and the pH of the samples were measured before and after being frozen. When the sample solution is frozen from the bottom to the top, solutes are concentrated into the unfrozen solution (i.e., the upper part of the sample) due to the freeze concentration effect. Thereafter, concentrated anions combine with protons to form acids, and the amount of acids in the unfrozen solution increase as the ice formation progresses. At the end of freezing, the acid is saturated at the ice surface, and if the formed acid is volatile, then evaporation occurs. Frozen solutions were allowed to stand below 0 degrees C, where evaporation rates were obtained in the following order: formate > acetate > propionate > n-butyrate > chloride >> nitrate. Except for nitrate, evaporation rates were enough to take place in frozen water of the natural environment (e.g., ice crystal, graupel, snow crystal, and frozen droplets). The relationship between the evaporation rate of volatile acids and their physical properties demonstrate that the evaporation rates of weak acids are faster than those of strong acids, and the evaporation rates among weak acids are the same as the volatility of weak acids.

Sonochemical degradation of various monocyclic aromatic compounds: relation between hydrophobicities of organic compounds and the decomposition rates.

Various aromatic compounds, i.e., nitrobenzene, aniline, phenol, benzoic acid, salicylic acid, 2-chlorophenol, 4-chlorophenol, styrene, chlorobenzene, toluene, ethylbenzene and n-propylbenzene were decomposed under identical ultrasonic irradiation conditions. The relationships between the initial rates of degradation of these aromatic compounds and their physicochemical parameters were systematically investigated. It was revealed that some correlations between the degradation rates and parameters of volatility, Henry's law constant and vapor pressure, were observed only in the limited high range of parameters. It was suggested that the Henry's law constant and vapor pressure had influenced on the rate of degradation for some of the tested aromatic compounds. In contrast, better correlations between the initial rates of degradation and hydrophobic parameters, water solubility and LogP (water-octanol partition coefficient), were observed over the wide range of chosen parameters. These results meant that the hydrophobicity of the compounds significantly affected their accumulation at the gas-liquid interface of the bubbles and it was the most important factor for the sonochemical degradation of aromatic compounds. In particular, for the sonolysis of water-insoluble organic compounds, LogP was found to be the representative parameter for understanding the hydrophobic properties of water-insoluble compounds.

Screening of fatty acids, saccharides, and phytochemicals in Jatropha curcas seed kernel as their trimethylsilyl derivatives using gas chromatography/mass spectrometry.

Jatropha curcas is a multipurpose plant, of which the seed kernel oil (up to 60% content) has been exploited for BDF production. In this report, we explored the various kinds of minor compounds of saccharides, phytochemicals, fatty acids (FAs), and amino acids in the seed kernel using gas chromatography/mass spectrometry (GC/MS) as their trimethylsilyl (TMS) derivatives. The homogenized seed kernels were extracted with methanol, and the extract was distributed into ethyl acetate/water phase. The components of each layer were derivatized with N, O-bis (trimethylsilyl) trifluoroacetamide (BSTFA) and their TMS derivatives were screened by GC/MS analysis. In ethyl acetate layer, the four FAs of palmitic acid, oleic acid, linoleic acid, and stearic acid were identified with total content of 12 wt% in kernel. In addition, the two tocochromanols of γ-tocopherol and γ-tocotrienol, and three phytosterols of campesterol, stigmasterol, and ß-sitosterol were also identified. Meanwhile, as the main saccharide components, di-saccharide of sucrose with content of 3 wt% in kernel, tri-saccharide of raffinose, and sugar alcohol of sorbitol and myo-inositol, were identified in aqueous layer. Furthermore, metabolites of amino acid, and a series of metabolite were also identified. These results suggested that the Jatropha curcas seed kernel can be applied to cascade use for metallic soap, liquid fuel, food and medical supplement, and cosmetics in addition to biodiesel production.

Production of Biodiesel from Candlenut Oil Using a Two-step Co-solvent Method and Evaluation of Its Gaseous Emissions.

Candlenut oil (CNO) is a potentially new feedstock for biodiesel (BDF) production. In this paper, a two-step co-solvent method for BDF production from CNO was examined. Firstly, esterification of free fatty acids (FFAs) (7 wt%) present in CNO was carried out using a co-solvent of acetonitrile (30 wt%) and H2SO4 as a catalyst. The content of FFAs was reduced to 0.8 wt% in 1 h at 65°C. Subsequent transesterification of the crude oil produced was carried out using a co-solvent of acetone (20 wt%) and 1 wt% potassium hydroxide (KOH). Ester content of 99.3% was obtained at 40°C in 45 min. The water content in BDF was 0.023% upon purification using vacuum distillation at 5 kPa. The components of CNO BDF were characterized using a Fourier-transform infrared spectrometry and gas chromatography-flame ionization detector. The physicochemical properties of BDF satisfied the ASTM D6751-02 standard. The gaseous exhaust emissions from the diesel engine upon combustion of the BDF blends (B0-B100) with petrodiesel were examined. The emissions of carbon monoxide and hydrocarbons were clearly lower, but that of nitrogen oxides was higher in comparison to those from petro-diesel.

Hydrazine degradation by ultrasonic irradiation.

The influence of pH on the degradation of hydrazine with a concentration of 0.1mmol/L was investigated under the stirring (300rpm) and ultrasonic irradiation conditions (200kHz, 200W) in the pH range of 1-9. It was found that the hydrazine degradation depended greatly upon pH under the ultrasonic irradiation condition, while it did not take place over the whole pH range under the stirring condition. Although it has been known that OH radicals and hydrogen peroxide are sonochemically formed from water, it was considered that the OH radicals played an important role of the hydrazine degradation, but not hydrogen peroxide. The pH dependence of the hydrazine degradation was discussed in terms of the relationship between the chemical structure and the basic dissociation constants of hydrazine.

A 3-Step Chemiluminescence Method for Chemical Oxygen Demand Measurement.

Direct chemiluminescence emission from the reaction of acidic permanganate and organic compounds was employed for determining the chemical oxygen demand (COD) in water (1-step CL COD). Due to the diversity of organic pollutants in water, there are no standards for COD measurements, and many compounds do not show any chemiluminescence signal in the 1-step CL COD method. As a result, this method shows a low correlation with the conventional CODMn method. In this study, a new 3-step CL COD method was developed to overcome these drawbacks. The basic principle of the 3-step CL COD method is based on the principle of "back titration" in the CODMn method: (i) the sample is treated with permanganate under heating, (ii) the excess permanganate is treated with pyrogallol, and (iii) the excess pyrogallol is measured by the chemiluminescence reaction with permanganate. The reagent concentration, sample volume, and heating temperature were optimized, and the 3-step CL COD method successfully obtained the signal from some samples that cannot be detected by 1-step CL COD method. The calibration graph is linear in the range of 0 - 12.86 mg/L with a detection limit of 0.082 mg/L. This method is continuous, sensitive and low cost compared with the conventional method, and is applicable for on-site monitoring. The effect of the chloride ion was investigated, and showed an insignificant effect after two-times dilution of high-salinity samples. The correlation with the CODMn method for various organic compounds showed a good coefficient of determination, R2 = 0.9773 (n = 16).

Binary Solvent Extraction of Tocols, γ-Oryzanol, and Ferulic Acid from Rice Bran Using Alkaline Treatment Combined with Ultrasonication.

Alkaline treatment (Alk) combined with ultrasound-assisted extraction (UAE) (Alk+UAE) was examined as a means of extracting tocols and γ-oryzanol from rice bran into an organic phase while simultaneously recovering ferulic acid into an aqueous phase. The tocols and γ-oryzanol/ferulic acid yields were determined using high-performance liquid chromatography with fluorescence and UV detection. The effects of extraction conditions were evaluated by varying the Alk treatment temperature and extraction duration. The maximum yields of tocols and γ-oryzanol were obtained at 25 °C over a time span of 30 min. When the temperature was increased to 80 °C, the yield of ferulic acid increased dramatically, whereas the recovery of γ-oryzanol slightly decreased. Employing the Alk+UAE procedure, the recovered concentrations of tocols, γ-oryzanol, and ferulic acid were in the ranges of 146-518, 1591-3629, and 352-970 µg/g, respectively. These results are in good agreement with those reported for rice bran samples from Thailand.

Acoustic multibubble cavitation in water: A new aspect of the effect of a rare gas atmosphere on bubble temperature and its relevance to sonochemistry.

Acoustic cavitation generates transient microbubbles with extremely high temperatures and high pressures, which can provide unique reaction routes. The maximum bubble temperature attained is widely known to be dependent on the polytropic index and thermal conductivity of the dissolved gas. Here, we show for the first time experimental evidence that the bubble temperature induced by a high frequency ultrasound is almost the same among different rare gases and the chemical efficiency is in proportion to the gas solubility of rare gases, which would be closely related to the number of active bubbles.