Total synthesis of 1-(Z)-atractylodinol

The total synthesis of 1-(Z)-atractylodinol, a natural polyacetylenic alcohol with several biological activities, has been achieved using a newly developed telluride synthon and a novel use for the Negishi type coupling reaction employing vinyl tellurides.     

Standard enthalpy of solution and formation of cesium chromate. Derived thermodynamic properties of the aqueous chromate,bichromate, and dichromate ions,alkali metal and alkaline earth chromates,and lead chromate

Calorimetric measurements of the enthalpy of solution of cesium chromate gave ΔH_soln = (7622 ± 24) cal_th mol^?1 for a dilution of Cs₂CrO₄·21128H₂O. This result, along with the enthalpy of dilution gave the standard enthalpy of solution, ΔH_soln^o = (7512 ± 31) cal_th mol^?1, whence the standard enthalpy of formation, ΔH_f⁰(Cs₂CrO₄, c, 298.15 K), was calculated to be ?(341.78 ± 0.46) kcal_th mol^?1. Recomputed thermodynamic data for the formation of the other alkali metal chromates have been tabulated. From their solubilities and enthalpies of solution, the standard entropies, S⁰(298 K), of BaCrO₄ and PbCrO₄ were estimated to be (38.9 ± 0.9) and (43.7 ± 1.2) cal_th K^?1 mol^?1, respectively. There is evidence that ΔH_f⁰(SrCrO₄, c, 298.15 K) may be in error. Thermochemical, solubility, and equilibrium data, have been combined to update the thermodynamic properties of the aqueous chromate (CrO₄^2?), bichromate (HCrO₄^?), and dichromate (Cr₂O₇^2?) ions. The new values at 298.15 K are as follows:

     

3.

Characterization of Sol-gel bioencapsulates for ester hydrolysis and synthesis     

Cleide M. F. Soares  Heizir F. de Castro  Juliana E. Itako  Flavio F. De Moraes  Gisella M. Zanin 《Applied biochemistry and biotechnology》2005,123(1-3):845-859

Candida rugosa lipase was entrapped in silica sol-gel particles prepared by hydrolysis of methyltrimethoxysilane and assayed by p-nitrophenyl palmitate hydrolysis, as a function of pH and temperature, giving pH optima of 7.8 (free enzyme) and 5.0–8.0 (immobilized enzyme). The optimum temperature for the immobilized enzyme (50–55°C) was 19°C higher than for the free enzyme. Thermal, operational, and storage stability were determined with n-butanol and bytyric acid, giving at 45°C a half-life 2.7 times greater for the immobilized enzyme; storage time was 21 d at room temperature. For ester synthesis, the optimum temperature was 47°C, and high esterification conversions were obtained under repeated batch cycles (half-life of 138 h).     

4.

A new polyphenol modified electrode containing an anchored ruthenium complex and its use in electrocatalytic oxidation of organic substrates     

Juliana R. Steter  José O.S. PontólioM.I.C.F. Costa  J.R. Romero 《Polyhedron》2007

This work describes the preparation of a new modified electrode containing a ruthenium complex (cis-aquadimethylbipyridyltriphenylphosphineruthenium II), bonded to a stable polyphenol film. This modified electrode promotes the fast electrocatalytic oxidation of safrol (5-allyl-benzo[1,3]dioxole) and isosafrol (5-propenyl-benzo[1,3]dioxole), giving two interesting products benzo[1,3]dioxole-5-carbaldehyde (piperonal) and 3-benzo[1,3]dioxol-5-yl-propenal respectively, with good yields. The electrode preparation can be carried out at a potential range which does not interfere on the anchored electroactive ruthenium complex, but it allows for the phenol oxidation to occur and therefore polymerize forming the polyphenol film. The catalytic character of this modified electrode is showed by its high turnover numbers. The procedure to isolate the products is very simple.     

5.

Magnetic Torus Microreactor as a Novel Device for Sample Treatment via Solid-Phase Microextraction Coupled to Graphite Furnace Atomic Absorption Spectroscopy: A Route for Arsenic Pre-Concentration     

Sofía Ortegn  Paula Andrea Pearanda  Cristian F. Rodríguez  Mabel Juliana Noguera  Sergio Leonardo Florez  Juan C. Cruz  Ricardo E. Rivas  Johann F. Osma 《Molecules (Basel, Switzerland)》2022,27(19)

This work studied the feasibility of using a novel microreactor based on torus geometry to carry out a sample pretreatment before its analysis by graphite furnace atomic absorption. The miniaturized retention of total arsenic was performed on the surface of a magnetic sorbent material consisting of 6 mg of magnetite (Fe₃O₄) confined in a very small space inside (20.1 µL) a polyacrylate device filling an internal lumen (inside space). Using this geometric design, a simulation theoretical study demonstrated a notable improvement in the analyte adsorption process on the solid extractant surface. Compared to single-layer geometries, the torus microreactor geometry brought on flow turbulence within the liquid along the curvatures inside the device channels, improving the efficiency of analyte–extractant contact and therefore leading to a high preconcentration factor. According to this design, the magnetic solid phase was held internally as a surface bed with the use of an 8 mm-diameter cylindric neodymium magnet, allowing the pass of a fixed volume of an arsenic aqueous standard solution. A preconcentration factor of up to 60 was found to reduce the typical “characteristic mass” (as sensitivity parameter) determined by direct measurement from 53.66 pg to 0.88 pg, showing an essential improvement in the arsenic signal sensitivity by absorption atomic spectrometry. This methodology emulates a miniaturized micro-solid-phase extraction system for flow-through water pretreatment samples in chemical analysis before coupling to techniques that employ reduced sample volumes, such as graphite furnace atomic absorption spectroscopy.     

6.

Development of a Protein-Rich By-Product by 23 Factorial Design: Characterization of Its Nutritional Value and Sensory Analysis     

Thamara R. dos Santos  Jakcline dos Santos Melo  Alysson V. dos Santos  Patrícia Severino  lvaro S. Lima  Eliana B. Souto  Aleksandra Zieli&#x;ska  Juliana C. Cardoso 《Molecules (Basel, Switzerland)》2022,27(24)

The aim of this study was the development of a cereal bar based on bee pollen (BP), honey (H), and flour by-products (peel passion fruit flour—PPFF), generating an innovative product. BP is a protein-rich ingredient and can be used in the composition of cereal bars. PPFF is a by-product rich in fibers. The formulations were developed using a 2³ factorial design with four replicates in the center point, studying the sensory analysis as a response variable. The texture and nutritional parameters were performed for the optimal formulation. BP showed ca. 15% of protein. The final formulation (10.35% BP, 6.8% PPFF, and 25% H) presented 22.2% moisture, 1.8% ash, 0.4% total fat, 3.0% fiber, 63.1% carbohydrates, and 74.0 Kcal/25 g. The sensory analysis presented valued around 7 (typical of a traditional bar). Regarding the possibility of purchasing the product, 51% of the panelists said they would probably buy the developed product. The formulated cereal bar had a similar composition as those already marketed. Moreover, it can be considered a source of fiber and is sensory acceptable. This approach opens up new opportunities for developing nutritional and functional foodstuff with improved sensorial aspects.     

7.

Assessment of pharmacokinetic interaction between piracetam and l‐carnitine in healthy subjects     

Gustavo D. Mendes  Gabriela Traldi Zaffalon  Antonio Sérgio Silveira  Juliana Cama Ramacciato  Rogério Heládio Lopes Motta  Thiago Gagliano‐Jucá  Anibal Gil Lopes  José Cássio de Almeida Magalhães  Gilberto De Nucci 《Biomedical chromatography : BMC》2016,30(4):536-542

A rapid, sensitive and specific method for quantifying piracetam in human plasma using Piracetam d‐8 as the internal standard (IS) is described. The analyte and the IS were extracted from plasma by one‐step precipitation of protein using an acetonitrile (100%). The extracts were analyzed by high‐performance liquid chromatography coupled with electrospray tandem mass spectrometry (HPLC‐MS/MS). The method had a chromatographic run time of 3.8 min and a linear calibration curve over the range 0.5–50 µg/mL (r > 0.99). This LC‐MS‐MS procedure was used to assess the bioavailability of two piracetam formulations: piracetam + l‐carnitine (Piracar®; 270/330 mg tablet) and piracetam (Nootropil®; 800 mg tablet) in healthy volunteers of both sexes. The geometric means with corresponding 90% confidence interval (CI) for test/reference percentage ratios were 88.49% (90% CI = 81.19 – 96.46) for peak concentration/dose and 102.55% (90% CI = 100.62 – 104.51) for AUC_inf/dose. The limit of quantitation of 0.5 µg/mL is well suited for pharmacokinetic studies in healthy volunteers. It was concluded that piracetam (Piracar®; 270/330 mg tablet) has a bioavailability equivalent to the piracetam (Nootropil®; 800 mg tablet) formulation with regard to both the rate and the extent of absorption. Copyright © 2015 John Wiley & Sons, Ltd.     

8.

Separation and Immobilization of Lipase from Penicillium simplicissimum by Selective Adsorption on Hydrophobic Supports     

Aline G. Cunha  Gloria Fernández-Lorente  Melissa L. E. Gutarra  Juliana V. Bevilaqua  Rodrigo V. Almeida  Lúcia M. C. Paiva  Roberto Fernández-Lafuente  Jose M. Guisán  Denise M. G. Freire 《Applied biochemistry and biotechnology》2009,156(1-3):133-145

Lipases are an enzyme class of a great importance as biocatalysts applied to organic chemistry. However, it is still necessary to search for new enzymes with special characteristics such as good stability towards high temperatures, organic solvents, and high stereoselectivity presence. The present work’s aim was to immobilize the lipases pool produced by Penicillium simplissicimum, a filamentous fungi strain isolated from Brazilian babassu cake residue. P. simplissicimum lipases were separated into three different fractions using selective adsorption method on different hydrophobic supports (butyl-, phenyl-, and octyl-agarose) at low ionic strength. After immobilization, it was observed that these fractions’ hyperactivation is in the range of 131% to 1133%. This phenomenon probably occurs due to enzyme open form stabilization when immobilized onto hydrophobic supports. Those fractions showed different thermal stability, specificity, and enantioselectivity towards some substrates. Enantiomeric ratio for the hydrolysis of (R,S) 2-O-butyryl-2-phenylacetic acid ranged from 1 to 7.9 for different immobilized P. simplissicimum lipase fractions. Asymmetry factor for diethyl 2-phenylmalonate hydrolysis ranged from 11.8 to 16.4 according to the immobilized P. simplissicimum lipase fractions. Those results showed that sequential adsorption methodology was an efficient strategy to obtain new biocatalysts with different enantioselectivity degrees, thermostability, and specificity prepared with a crude extract produced by a simple and low-cost technology.     

9.

Experimental Evidence of CO2 Photoreduction Activity of SnO2 Nanoparticles     

Dr. Juliana Arriel Torres  Dr. Gelson T. S. T. Da Silva  Dr. Fernando Barbosa de Freitas Silva  Dr. Caue Ribeiro 《Chemphyschem》2020,21(21):2392-2396

Tin dioxide (SnO₂) has intrinsic characteristics that do not favor its photocatalytic activity. However, we evidenced that surface modification can positively influence its performance for CO₂ photoreduction in the gas phase. The hydroxylation of the SnO₂ surface played a role in the CO₂ affinity decreasing its reduction potential. The results showed that a certain selectivity for methane (CH₄), carbon monoxide (CO), and ethylene (C₂H₄) is related to different SnO₂ hydrothermal annealing. The best performance was seen for SnO₂ annealed at 150 °C, with a production of 20.4 μmol g⁻¹ for CH₄ and 16.45 μmol g⁻¹ for CO, while for SnO₂ at 200 °C the system produced more C₂H₄, probably due to a decrease of surface −OH groups.     

10.

Statistical Experimental Design for Obtaining Nanocellulose from Curaua Fiber     

Juliana N. Lunz  Suellem B. Cordeiro  José Carlos F. Mota  Maria F. V. Marques 《Macromolecular Symposia》2012,319(1):99-107

Summary: This study focuses on the methodology to obtain nanocellulose from vegetal fibers. An experimental planning was carried out for the treatment of curaua fibers and parameters were estimated, having the concentration of H₂SO₄, hydrolysis time, reaction temperature and time of applied sonication as independent variables for further statistical analysis. According to the estimated parameters, the statistically significant effects were determined for the process of obtaining nanocellulose. With the results obtained from the thermogravimetric analysis (TGA) it was observed that certain conditions led to cellulose with degradation temperatures near or even above that of the untreated cellulose fibers. The crystallinity index (I_C) obtained after fiber treatment (by X-ray diffraction technique) was higher than that of the pure fiber. Treatments with high acid concentrations led to higher IC. After the statistical experimental design, mixtures of polypropylene with fibers prepared after different treatments were performed in a mini-extruder. It was possible to observe a sharp increase in the mechanical properties through the dynamic mechanical thermal analysis (DMTA).     

1 [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] 下一页 » 末  页»

	$\text{S}{}^0\text{/}\text{cal}{}_{\mathrm{th}}\text{K}{}^{\mathrm{?1}}\text{mol}{}^{\mathrm{?1}}$	$\text{ΔH}{}_{\mathrm{f}}{}^0\text{/kcal}{}_{\mathrm{th}}\text{mol}{}^{\mathrm{?1}}$	$\text{ΔG}{}_{\mathrm{f}}{}^0\text{/kcal}{}_{\mathrm{th}}\text{mol}{}^{\mathrm{?1}}$
CrO42?(aq)	(13.8 ± 0.5)	?(210.93 ± 0.45)	?(174.8 ± 0.5)
HCrO4?(aq)	(46.6 ± 1.8)	?(210.0 ± 0.7)	?(183.7 ± 0.5)
Cr2O72?(aq)	(67.4 ± 3.9)	?(356.5 ± 1.5)	?(312.8 ± 1.0)

Characterization of Sol-gel bioencapsulates for ester hydrolysis and synthesis

Candida rugosa lipase was entrapped in silica sol-gel particles prepared by hydrolysis of methyltrimethoxysilane and assayed by p-nitrophenyl palmitate hydrolysis, as a function of pH and temperature, giving pH optima of 7.8 (free enzyme) and 5.0–8.0 (immobilized enzyme). The optimum temperature for the immobilized enzyme (50–55°C) was 19°C higher than for the free enzyme. Thermal, operational, and storage stability were determined with n-butanol and bytyric acid, giving at 45°C a half-life 2.7 times greater for the immobilized enzyme; storage time was 21 d at room temperature. For ester synthesis, the optimum temperature was 47°C, and high esterification conversions were obtained under repeated batch cycles (half-life of 138 h).     

A new polyphenol modified electrode containing an anchored ruthenium complex and its use in electrocatalytic oxidation of organic substrates

This work describes the preparation of a new modified electrode containing a ruthenium complex (cis-aquadimethylbipyridyltriphenylphosphineruthenium II), bonded to a stable polyphenol film. This modified electrode promotes the fast electrocatalytic oxidation of safrol (5-allyl-benzo[1,3]dioxole) and isosafrol (5-propenyl-benzo[1,3]dioxole), giving two interesting products benzo[1,3]dioxole-5-carbaldehyde (piperonal) and 3-benzo[1,3]dioxol-5-yl-propenal respectively, with good yields. The electrode preparation can be carried out at a potential range which does not interfere on the anchored electroactive ruthenium complex, but it allows for the phenol oxidation to occur and therefore polymerize forming the polyphenol film. The catalytic character of this modified electrode is showed by its high turnover numbers. The procedure to isolate the products is very simple.     

Magnetic Torus Microreactor as a Novel Device for Sample Treatment via Solid-Phase Microextraction Coupled to Graphite Furnace Atomic Absorption Spectroscopy: A Route for Arsenic Pre-Concentration

This work studied the feasibility of using a novel microreactor based on torus geometry to carry out a sample pretreatment before its analysis by graphite furnace atomic absorption. The miniaturized retention of total arsenic was performed on the surface of a magnetic sorbent material consisting of 6 mg of magnetite (Fe₃O₄) confined in a very small space inside (20.1 µL) a polyacrylate device filling an internal lumen (inside space). Using this geometric design, a simulation theoretical study demonstrated a notable improvement in the analyte adsorption process on the solid extractant surface. Compared to single-layer geometries, the torus microreactor geometry brought on flow turbulence within the liquid along the curvatures inside the device channels, improving the efficiency of analyte–extractant contact and therefore leading to a high preconcentration factor. According to this design, the magnetic solid phase was held internally as a surface bed with the use of an 8 mm-diameter cylindric neodymium magnet, allowing the pass of a fixed volume of an arsenic aqueous standard solution. A preconcentration factor of up to 60 was found to reduce the typical “characteristic mass” (as sensitivity parameter) determined by direct measurement from 53.66 pg to 0.88 pg, showing an essential improvement in the arsenic signal sensitivity by absorption atomic spectrometry. This methodology emulates a miniaturized micro-solid-phase extraction system for flow-through water pretreatment samples in chemical analysis before coupling to techniques that employ reduced sample volumes, such as graphite furnace atomic absorption spectroscopy.     

Development of a Protein-Rich By-Product by 23 Factorial Design: Characterization of Its Nutritional Value and Sensory Analysis

The aim of this study was the development of a cereal bar based on bee pollen (BP), honey (H), and flour by-products (peel passion fruit flour—PPFF), generating an innovative product. BP is a protein-rich ingredient and can be used in the composition of cereal bars. PPFF is a by-product rich in fibers. The formulations were developed using a 2³ factorial design with four replicates in the center point, studying the sensory analysis as a response variable. The texture and nutritional parameters were performed for the optimal formulation. BP showed ca. 15% of protein. The final formulation (10.35% BP, 6.8% PPFF, and 25% H) presented 22.2% moisture, 1.8% ash, 0.4% total fat, 3.0% fiber, 63.1% carbohydrates, and 74.0 Kcal/25 g. The sensory analysis presented valued around 7 (typical of a traditional bar). Regarding the possibility of purchasing the product, 51% of the panelists said they would probably buy the developed product. The formulated cereal bar had a similar composition as those already marketed. Moreover, it can be considered a source of fiber and is sensory acceptable. This approach opens up new opportunities for developing nutritional and functional foodstuff with improved sensorial aspects.     

Assessment of pharmacokinetic interaction between piracetam and l‐carnitine in healthy subjects

A rapid, sensitive and specific method for quantifying piracetam in human plasma using Piracetam d‐8 as the internal standard (IS) is described. The analyte and the IS were extracted from plasma by one‐step precipitation of protein using an acetonitrile (100%). The extracts were analyzed by high‐performance liquid chromatography coupled with electrospray tandem mass spectrometry (HPLC‐MS/MS). The method had a chromatographic run time of 3.8 min and a linear calibration curve over the range 0.5–50 µg/mL (r > 0.99). This LC‐MS‐MS procedure was used to assess the bioavailability of two piracetam formulations: piracetam + l‐carnitine (Piracar®; 270/330 mg tablet) and piracetam (Nootropil®; 800 mg tablet) in healthy volunteers of both sexes. The geometric means with corresponding 90% confidence interval (CI) for test/reference percentage ratios were 88.49% (90% CI = 81.19 – 96.46) for peak concentration/dose and 102.55% (90% CI = 100.62 – 104.51) for AUC_inf/dose. The limit of quantitation of 0.5 µg/mL is well suited for pharmacokinetic studies in healthy volunteers. It was concluded that piracetam (Piracar®; 270/330 mg tablet) has a bioavailability equivalent to the piracetam (Nootropil®; 800 mg tablet) formulation with regard to both the rate and the extent of absorption. Copyright © 2015 John Wiley & Sons, Ltd.     

Separation and Immobilization of Lipase from Penicillium simplicissimum by Selective Adsorption on Hydrophobic Supports

Lipases are an enzyme class of a great importance as biocatalysts applied to organic chemistry. However, it is still necessary to search for new enzymes with special characteristics such as good stability towards high temperatures, organic solvents, and high stereoselectivity presence. The present work’s aim was to immobilize the lipases pool produced by Penicillium simplissicimum, a filamentous fungi strain isolated from Brazilian babassu cake residue. P. simplissicimum lipases were separated into three different fractions using selective adsorption method on different hydrophobic supports (butyl-, phenyl-, and octyl-agarose) at low ionic strength. After immobilization, it was observed that these fractions’ hyperactivation is in the range of 131% to 1133%. This phenomenon probably occurs due to enzyme open form stabilization when immobilized onto hydrophobic supports. Those fractions showed different thermal stability, specificity, and enantioselectivity towards some substrates. Enantiomeric ratio for the hydrolysis of (R,S) 2-O-butyryl-2-phenylacetic acid ranged from 1 to 7.9 for different immobilized P. simplissicimum lipase fractions. Asymmetry factor for diethyl 2-phenylmalonate hydrolysis ranged from 11.8 to 16.4 according to the immobilized P. simplissicimum lipase fractions. Those results showed that sequential adsorption methodology was an efficient strategy to obtain new biocatalysts with different enantioselectivity degrees, thermostability, and specificity prepared with a crude extract produced by a simple and low-cost technology.     

Experimental Evidence of CO2 Photoreduction Activity of SnO2 Nanoparticles

Tin dioxide (SnO₂) has intrinsic characteristics that do not favor its photocatalytic activity. However, we evidenced that surface modification can positively influence its performance for CO₂ photoreduction in the gas phase. The hydroxylation of the SnO₂ surface played a role in the CO₂ affinity decreasing its reduction potential. The results showed that a certain selectivity for methane (CH₄), carbon monoxide (CO), and ethylene (C₂H₄) is related to different SnO₂ hydrothermal annealing. The best performance was seen for SnO₂ annealed at 150 °C, with a production of 20.4 μmol g⁻¹ for CH₄ and 16.45 μmol g⁻¹ for CO, while for SnO₂ at 200 °C the system produced more C₂H₄, probably due to a decrease of surface −OH groups.     

Statistical Experimental Design for Obtaining Nanocellulose from Curaua Fiber

Summary: This study focuses on the methodology to obtain nanocellulose from vegetal fibers. An experimental planning was carried out for the treatment of curaua fibers and parameters were estimated, having the concentration of H₂SO₄, hydrolysis time, reaction temperature and time of applied sonication as independent variables for further statistical analysis. According to the estimated parameters, the statistically significant effects were determined for the process of obtaining nanocellulose. With the results obtained from the thermogravimetric analysis (TGA) it was observed that certain conditions led to cellulose with degradation temperatures near or even above that of the untreated cellulose fibers. The crystallinity index (I_C) obtained after fiber treatment (by X-ray diffraction technique) was higher than that of the pure fiber. Treatments with high acid concentrations led to higher IC. After the statistical experimental design, mixtures of polypropylene with fibers prepared after different treatments were performed in a mini-extruder. It was possible to observe a sharp increase in the mechanical properties through the dynamic mechanical thermal analysis (DMTA).