Simultaneous quantification and qualification of synacthen in plasma

Tetracosactide (Synacthen), a synthetic analogue of adrenocorticotropic hormone (ACTH), can be used as a doping agent to increase the secretion of glucocorticoids by adrenal glands. The only published method for anti-doping control of this drug in plasma relies on purification by immunoaffinity chromatography and LC/MS/MS analysis. Its limit of detection is 300 pg/mL, which corresponds to the peak value observed 12 h after 1 mg Synacthen IM administration. We report here a more sensitive method based on preparation of plasma by cation exchange chromatography and solid-phase extraction and analysis by LC/MS/MS with positive-mode electrospray ionization using 7–38 ACTH as internal standard. Identification of Synacthen was performed using two product ions, m/z 671.5 and m/z 223.0, from the parent [M?+?5H]⁵⁺ ion, m/z 587.4. The recovery was estimated at 70%. A linear calibration curve was obtained from 25 to 600 pg/mL (R ²?>?0.99). The lower limit of detection was 8 pg/mL (S/N?>?3). The lower limit of quantification was 15 pg/mL (S/N?>?10; CV%?相似文献   

Determination of Congo red in food samples by methyl-β-cyclodextrin/Triton X-100 synergistic sensitized fluorescence quenching method of the derivatives of calix[4]arene

A novel fluorescent chemosensor of the derivatives of calix[4]arene (SAX) for Congo red (CR) in methyl-β-cyclodextrin/Triton X-100 synergistic sensitized system was developed. The results showed that the fluorescence intensity of SAX could be quenched by CR, and the fluorescence quenching (?F?=?F_SAX ? F_CR-SAX) was synergistic sensitized by methyl-β-CD and Triton X-100. Under the conditions of λ_ex/em?=?332/468 nm and pH 7.5, the linear range and the detection limit for CR were found to be 0.040–8.0 μg/mL and 8.9 ng/mL, respectively. The mechanism of determination was discussed by quenching type analysis and sensitizing effect. This method has also been applied for the determination of CR in beef samples with satisfactory results.     

Covalent Immobilization and Characterization of a Novel Pullulanase from <Emphasis Type="Italic">Fontibacillus</Emphasis> sp. Strain DSHK 107 onto Florisil® and Nano-silica for Pullulan Hydrolysis

A novel pullulanase partially purified from Fontibacillus sp. was covalently immobilized on Florisil® and nano-silica through both glutaraldehyde and (3-glycidyloxypropyl)trimethoxysilane spacer arms. The pullulanase immobilized on Florisil® and nano-silica through glutaraldehyde spacer arm showed 85 and 190 % activity of its free form, respectively, whereas no activity was observed when it was immobilized on the same supports through (3-glycidyloxypropyl)trimethoxysilane spacer arm. The maximum working pHs of both the immobilized pullulanases on Florisil® and nano-silica through glutaraldehyde spacer arm were determined as 5.0; however, the maximum working pH of the free pullulanase was pH 6.0. The maximum temperatures of all the pullulanase preparations were determined as 35 °C. The apparent K _m values were 1.49, 1.54, and 0.59 mg/mL pullunan, respectively, for the free and immobilized pullulanases on Florisil® and nano-silica. The corresponding apparent V _max values were 0.59, 1.53, and 1.57 U mg prot.^?1?min.^?1. Thermal stability of pullulanases immobilized on Florisil® and nano-silica was enhanced 6.5- and 15.6-folds, respectively at 35 °C and 6.6- and 16.0-folds, respectively, at 50 °C. The pullulanases immobilized on Florisil® and nano-silica protected 71 and 90 % of their initial activities after 10 reuses.     

Structural improvement of ZnO electrodes through solution-processed routes for enhancing open-circuit voltage in dye-sensitized solar cells

We report herein one of our recent studies on nanostructured ZnO electrodes for application in dye-sensitized solar cells, focusing on achieving a higher open-circuit voltage (V_OC). ZnO films were obtained through solution-processed routes including pyrolytic conversion of layered hydroxide zinc acetate (LHZA) films deposited on a fluorine-doped tin oxide-coated conducting glass substrate by a chemical bath deposition method. The morphology of the initial LHZA and the converted ZnO films was tuned from a thick (approximately 12 μm) flower bed-/lawn-like bilayer structure to a thin (1.2 μm) lawn-like quasi-monolayer structure by decreasing the Zn source concentration in the chemical bath. V_OC was found to be enhanced with this morphological change from 0.692 (the bilayer structure) to 0.735 V (the quasi-monolayer structure). Fine tuning of the quasi-monolayer structure by introducing the grain growth effect led to V_OC of the cell as high as 0.807 V, although a short-circuit photocurrent density (J_SC) remained low. Further attempts were then made to increase J_SC while maintaining the high V_OC. When the thickness of the lawn-like monolayer film was increased up to approximately 5 μm, the resultant cell showed V_OC?=?0.750 V, J_SC?=?6.20 mA cm^?2 and a conversion efficiency (η) of 2.83%. The film with a modified flower bed-/lawn-like bilayer structure approximately 11 μm in thickness finally yielded V_OC?=?0.741 V, J_SC?=?13.6 mA cm^?2, and η?=?5.44%.     

Study of the growth of <Emphasis Type="Italic">Enterococcus faecalis</Emphasis>, <Emphasis Type="Italic">Escherichia coli</Emphasis> and their mixtures by microcalorimetry

In a majority of environments, microbes live as interacting communities. Microbial communities are composed of a mix of microbes with often unknown functions. Polymicrobial diseases represent the clinical and pathological manifestations induced by the presence of multiple infectious agents. These diseases are difficult to diagnose and treat and usually are more severe than monomicrobial infections. The interaction relationship between Enterococcus faecalis and Escherichia coli was researched using a Calvet calorimeter. Three mixtures of both bacteria were prepared in the following proportions: 20 + 80 % (0.2 mL E. faecalis + 0.8 mL E. coli), 50 + 50 % (0.5 mL E. faecalis + 0.5 mL E. coli) and 80 + 20 % (0.8 mL E. faecalis + 0.2 mL E. coli). Experiments were carried out at concentration of 10⁶ CFU mL^?1 and a constant temperature of 309.65 K. The differences in shape of graph of E. faecalis, E. coli and their mixtures were compared. Also, the thermokinetic parameters such as detection time (t _d), growth constant (k), generation time (G) and the amount of heat released (Q) were calculated.     

Synthesis,SAR and in vitro therapeutic potentials of thiazolidine-2,4-diones

Background

Thiazolidinedione is a pentacyclic moiety having five membered unsaturated ring system composed with carbon, oxygen, nitrogen and sulfur molecules at 1 and 3 position of the thiazole ring and widely found throughout nature in various form. They favourably alter concentration of the hormones secreted by adipocytes, particularly adiponectin. They also increase total body fat and have mixed effects on circulating lipids. Thiazolidinedione nucleus is present in numerous biological moieties and has different pharmacological activities likes, e.g. antimalarial, antimicrobial, antimycobacterial, anticonvulsant, antiviral, anticancer, anti-inflammatory, antioxidant, anti-HIV (human immunodeficiency virus) and antituberculosis.

Results and discussion

The synthesized compounds were screened for their in vitro antimicrobial potential against Gram (positive and negative) bacterial and fungal strains by tube dilution technique. In this series, compound 10 exhibited significant antimicrobial activity against B. subtilis and S. aureus with MIC?=?4.2?×?10^?2 µM/ml, compound 15 showed significant activity against K. pneumonia with MIC?=?2.60?×?10^?2 µM/ml and compound 4 displayed potent antibacterial activity against E. coli with MIC?=?4.5?×?10^?2 µM/ml. Compound 10 had most potent antifungal activity against C. albicans and A. niger with MIC?=?4.2?×?10^?2 µM/ml. Compounds 12 and 15 were found as most active antidiabetic agents having IC₅₀?=?27.63 μg/ml and 22.35 μg/ml, respectively, using DPPH assay. Antioxidant activity results indicated that compounds 3 and 9 displayed good antioxidant agent with IC₅₀?=?29.04 μg/ml and 27.66 μg/ml respectively, using α amylase assay.

Conclusion

All the synthesized derivatives exhibited good antimicrobial, antidiabetic and antioxidant activities using specific methods then compared with mentioned standard drugs. Especially, compounds 3, 4, 9, 10, 12 and 15 displayed highest activity. Structure activity relationship demonstrated that presence of electron withdrawing group (o-NO₂, p-Cl, p-Br) enhanced the antibacterial activity against E. coli as well as increased the antioxidant activity while the presence of electron releasing group (o/p-OCH₃, 3,4,5-trimethoxy) enhanced the antibacterial activity against S. aureus, B. subtilis, S. typhi, K. pneumonia, C. albicans and A. niger as well as the antidiabetic activity.

     

Increased enzymatic hydrolysis of sugarcane bagasse by a novel glucose- and xylose-stimulated β-glucosidase from <Emphasis Type="Italic">Anoxybacillus flavithermus</Emphasis> subsp. <Emphasis Type="Italic">yunnanensis</Emphasis> E13<Superscript>T</Superscript>

Background

β-Glucosidase is claimed as a key enzyme in cellulose hydrolysis. The cellulosic fibers are usually entrapped with hemicelluloses containing xylose. So there is ongoing interest in searching for glucose- and xylose-stimulated β-glucosidases to increase the efficiency of hydrolysis of cellulosic biomass.

Results

A thermostable β-glucosidase gene (Bglp) was cloned from Anoxybacillus flavithermus subsp. yunnanensis E13^T and characterized. Optimal enzyme activity was observed at 60 °C and pH 7.0. Bglp was relatively stable at 60 °C with a 10-h half-life. The kinetic parameters V _max and K _m for p-nitrophenyl-β-D-glucopyranoside (pNPG) were 771?±?39 μmol/min/mg and 0.29?±?0.01 mM, respectively. The activity of Bglp is dramatically stimulated by glucose or xylose at concentrations up to 1.4 M. After Bglp was added to Celluclast® 1.5 L, the conversion of sugarcane bagasse was 48.4?±?0.8%, which was much higher than of Celluclast® 1.5 L alone. Furthermore, Bglp showed obvious advantages in the hydrolysis when initial concentrations of glucose and xylose are high.

Conclusions

The supplementation of BglP significantly enhanced the glucose yield from sugarcane bagasse, especially in the presence of high concentrations of glucose or xylose. Bglp should be a promising candidate for industrial applications.

     

Production of <Emphasis Type="Italic">R</Emphasis>-Mandelic Acid Using Nitrilase from Recombinant <Emphasis Type="Italic">E. coli</Emphasis> Cells Immobilized with Tris(Hydroxymethyl)Phosphine

Recombinant Escherichia coli cells harboring nitrilase from Alcaligenes faecalis were immobilized using tris(hydroxymethyl)phosphine (THP) as the coupling agent. The optimal pH and temperature of the THP-immobilized cells were determined at pH 8.0 and 55 °C. The half-lives of THP-immobilized cells measured at 35, 40, and 50 °C were 1800, 965, and 163 h, respectively. The concentration of R-mandelic acid (R-MA) reached 358 mM after merely 1-h conversion by the immobilized cells with 500 mM R,S-mandelonitrile (R,S-MN), affording the highest productivity of 1307 g L^?1 day^?1 and the space-time productivity of 143.2 mmol L^?1 h^?1 g^?1. The immobilized cells with granular shape were successfully recycled for 60 batches using 100 mM R,S-MN as substrate at 40 °C with 64% of relative activity, suggesting that the immobilized E. coli cells obtained in this study are promising for the production of R-MA.     

Theoretical and experimental study of the catalytic cathodic stripping square-wave voltammetry of chromium species

The electrocatalytic mechanism of Cr(III) reduction in the presence of diethylenetriaminepentaacetic acid (DTPA) and nitrate ions is studied theoretically and experimentally by using stripping square-wave voltammetry (SWV). Experimental curves are in excellent agreement with theoretical profiles corresponding to a catalytic reaction of second kind. This type of mechanism is equivalent to a CE mechanism, where the chemical reaction produces the electroactive species. Accordingly, the reaction of Cr(III)–H₂O–DTPA and \( {\mathrm{NO}}_3^{-} \) would produce the electroactive species Cr(III)–NO₃–DTPA and this last species would release \( {\mathrm{NO}}_2^{-} \) to the solution during the electrochemical step. In this regard, the complex of Cr(III)–DTPA would work as the catalyzer that allows the reduction of \( {\mathrm{NO}}_3^{-} \) to \( {\mathrm{NO}}_2^{-} \). Furthermore, it was found that the electrochemical reaction is quite irreversible, with a constant of k _s?=?9.4?×?10^?5 cm s^?1, while the constant for the chemical step has been estimated to be k _chem?=?1.3?×?10⁴ s^?1. Considering that the equilibrium constant is K?=?0.01, it is possible to estimate the kinetic constants of the chemical reaction as k ₁?=?1?×?10² s^?1 and k _?1?=?1.29?×?10⁴ s^?1. These values of k ₁ and k _?1 indicate that the exchange of water molecules by nitrate is fast and that the equilibrium favors the complex with water. Also, a value for the formal potential E°’?≈??1.1 V was obtained. The model used for simulating experimental curves does not consider the adsorption of reactants yet. Accordingly, weak adsorption of reagents should be expected.     

Association of LIM Domain 7 Gene Polymorphisms and Plasma Levels of LIM Domain 7 with Dilated Cardiomyopathy in a Chinese Population

The aim of our study was to investigate the potential association of mRNA expression and plasma levels of the LIM domain 7 (LMO7) gene with the pathogenesis of dilated cardiomyopathy (DCM). Two SNPs of the LMO7 gene were genotyped in 310 patients with DCM and 415 controls. Our results showed that SNP rs7986131 (p = 0.002, OR = 1.38, 95% CI = 1.12–1.71), but not SNP rs4884021, was associated with DCM in the Han Chinese population. Haplotype analysis showed that the haplotype GT was associated with increased DCM susceptibility while AC was a protective haplotype. The Cox multivariate survival analysis indicated that the rs7986131 TT genotype (HR 1.659, 95% CI = 1.122–2.454, p = 0.011) was an independent multivariate predictor for shorter overall survival in patients with DCM. LMO7 mRNA expression and plasma LMO7 levels were significantly decreased in DCM (p < 0.0001). Spearman correlation test revealed that the plasma LMO7 level was negatively associated with left ventricular end-diastolic diameter (r = ?0.384, p = 0.01), left ventricular end-diastolic volume (r = ?0.375, p = 0.012), and brain natriuretic peptide (r = ?0.482, p = 0.001). Our study suggested that the LMO7 gene may play an important role in the pathogenesis of DCM in the Han Chinese population.     

Analytical characteristics and determination of major novel brominated flame retardants (NBFRs) in indoor dust

A new method was developed and optimized for the detection of major “novel” brominated flame retardants (NBFRs), which included decabromodiphenyl ethane (DBDPE), 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), tetrabromobisphenol A-bis(2,3-dibromopropylether) (TBBPA-DBPE), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (TBB), bis(2-ethylhexyl)-3,4,5,6-tetrabromophthalate (TBPH) and hexachlorocyclopentadienyl-dibromocyclooctane (HCDBCO). Several solid phase sorbents were tested, and finally, a two-step cleanup procedure was established. The first step on activated silica was used to fractionate the dust extracts, while the second step on acidified silica (silica gel impregnated with sulphuric acid 44% w/w) and on Florisil®, respectively, was essential for advanced cleanup. High recoveries for NBFRs (range, 75–94%) were achieved. Analysis was performed by gas chromatography coupled with mass spectrometry in electron capture negative ionization using a DB-5ms (15 m?×?0.25 mm?×?0.1 μm) capillary column. Quantification of DBDPE, BTBPE and TBBPA-DBPE was based on ion m/z 79, while characteristic ions were used for quantification of TBB (m/z 359), HCDBCO (m/z 310) and TBPH (m/z 384). The method provided good repeatability; within- and between-day precision were ≤14% for all NBFRs. Method limits of quantification ranged between 1 and 20 ng g^?1; dust and NBFRs were not detected in blanks. The method was further applied to indoor dust (n?=?21) collected from e-waste facilities in Thailand. Except for HCDBCO, all NBFRs were detected in the e-waste dust with concentrations up to 44,000 and 22,600 ng g^?1 DBDPE and BTBPE, respectively. The dust profile was dominated by DBDPE (50%)?>?BTBPE (45%)?>?TBBPA-DBPE (3%)?>?TBPH (1.9%)?>?TBB (0.1%). Significant correlations (p?相似文献   

Ro-vibrating energy states of a diatomic molecule in an empirical potential

An approximate analytical solution of the Schrödinger equation is obtained to represent the rotational–vibrational (ro-vibrating) motion of a diatomic molecule. The ro-vibrating energy states arise from a systematical solution of the Schrödinger equation for an empirical potential (EP) V _±(r) = D _e {1 ? (?/δ)[coth (ηr)]^±1/1 ? (?/δ)}² are determined by means of a mathematical method so-called the Nikiforov–Uvarov (NU). The effect of the potential parameters on the ro-vibrating energy states is discussed in several values of the vibrational and rotational quantum numbers. Moreover, the validity of the method is tested with previous models called the semiclassical (SC) procedure and the quantum mechanical (QM) method. The obtained results are applied to the molecules H₂ and Ar₂.     

Enzymatic Hydrolysis of Black Liquor Xylan by a Novel Xylose-Tolerant,Thermostable β-Xylosidase from a Tropical Strain of <Emphasis Type="Italic">Aureobasidium pullulans</Emphasis> CBS 135684

From three cell-associated β-xylosidases produced by Aureobasidium pullulans CBS 135684, the principal enzyme was enriched to apparent homogeneity and found to be active at high temperatures (60–70 °C) over a pH range of 5–9 with a specific activity of 163.3 units (U) mg^?1. The enzyme was thermostable, retaining over 80% of its initial activity after a 12-h incubation at 60 °C, with half-lives of 38, 22, and 10 h at 60, 65, and 70 °C, respectively. Moreover, it was tolerant to xylose inhibition with a K _i value of 18 mM. The K _m and V _max values against p-nitrophenyl-β-d-xylopyranoside were 5.57 ± 0.27 mM and 137.0 ± 4.8 μmol min^?1 mg^?1 protein, respectively. When combining this β-xylosidase with xylanase from the same A. pullulans strain, the rate of black liquor xylan hydrolysis was significantly improved by up to 1.6-fold. The maximum xylose yield (0.812 ± 0.015 g g^?1 dry weight) was obtained from a reaction mixture containing 10% (w/v) black liquor xylan, 6 U g^?1 β-xylosidase and 16 U g^?1 xylanase after incubation for 4 h at 70 °C and pH 6.0.     

Orchids as Sources of Novel Nanoinsecticides? Efficacy of <Emphasis Type="Italic">Bacillus sphaericus</Emphasis> and <Emphasis Type="Italic">Zeuxine gracilis</Emphasis>-Fabricated Silver Nanoparticles Against Dengue,Malaria and Filariasis Mosquito Vectors

Mosquitoes are the most critical group of insects in the context of public health, since they transmit key parasites and pathogens, causing millions of deaths annually. Insecticides from natural products may boost the effectiveness of vector control programs. In this study, we tested silver nanoparticles (AgNPs) fabricated using the leaf extract of the orchid Zeuxine gracilis as reducing agent, and the microbial pesticide Bacillus sphaericus, against the mosquitoes Anopheles stephensi, Aedes aegypti and Culex quinquefasciatus. The synthesis of AgNP was confirmed analyzing the excitation of surface Plasmon resonance using ultraviolet–visible (UV–Vis) spectrophotometry. SEM and TEM showed the irregular shapes of AgNPs. EDX spectroscopy, FTIR spectroscopy, X-ray diffraction and dynamic light scattering analysis were carried out. AgNPs were highly effective against the larvae of An. stephensi (LC₅₀ = 8.48 µg/mL), Ae. aegypti (LC₅₀ = 10.39 µg/mL) and Cx. quinquefasciatus (LC₅₀ = 13.21 µg/mL), respectively. Combined treatments testing B. sphaericus with AgNPs were also effective against An. stephensi (LC₅₀ = 12.32 µg/mL), Ae. aegypti (LC₅₀ = 14.78 µg/mL) and Cx. quinquefasciatus (LC₅₀ = 19.19 µg/mL). Overall, this study suggests that the orchid-synthesized AgNPs can be a rapid, environmentally safer bio-pesticide to be used in synergy with B. sphaericus to control mosquito vectors.     

Acetone–Butanol–Ethanol Production from Waste Seaweed Collected from Gwangalli Beach,Busan, Korea,Based on pH-Controlled and Sequential Fermentation Using Two Strains

The optimal conditions for acetone–butanol–ethanol (ABE) production were evaluated using waste seaweed from Gwangalli Beach, Busan, Korea. The waste seaweed had a fiber and carbohydrate, content of 48.34%; these are the main resources for ABE production. The optimal conditions for obtaining monosaccharides based on hyper thermal (HT) acid hydrolysis of waste seaweed were slurry contents of 8%, sulfuric acid concentration of 138 mM, and treatment time of 10 min. Enzymatic saccharification was performed using 16 unit/mL Viscozyme L, which showed the highest affinity (K_m?=?1.81 g/L). After pretreatment, 34.0 g/L monosaccharides were obtained. ABE fermentation was performed with single and sequential fermentation of Clostridium acetobutylicum and Clostridium tyrobutyricum; this was controlled for pH. A maximum ABE concentration of 12.5 g/L with Y_ABE 0.37 was achieved using sequential fermentation with C. tyrobutyricum and C. acetobutylicum. Efficient ABE production from waste seaweed performed using pH-controlled culture broth and sequential cell culture.     

Apparent Molar Volumes of Aqueous Solutions of Magnesium Tetraborate from 283.15 to 363.15 K and 0.1 MPa

Densities for aqueous solutions of magnesium tetraborate MgB₄O₇(aq) at the molalities of (0.00556–0.03341) mol·kg^?1 were measured with an Anton Paar Digital vibrating-tube densimeter at temperature intervals of 5 K from 283.15 to 363.15 K and 0.1 MPa. Apparent molar volumes were obtained based on the experimental density data, and the 3D diagrams of the apparent molar volume (V _? ) of MgB₄O₇(aq) against temperature (T) and molality (m) were plotted. On the basis of the Vogel–Tamman–Fulcher equation, the coefficients of the correlation equation for densities of MgB₄O₇(aq) against temperature and molality were parameterized. According to the Pitzer ion-interaction model of the apparent molar volume, the temperature correlation equations of Pitzer single-salt parameters F(i,p,T)?=?a₀?+?a₁?×?T?+?a₂?×?T ²?+?a₃/T?+?a₄?×?ln(T)?+?a₅?×?T ³ (where T is temperature in Kelvin, a _i are model parameters) for MgB₄O₇ were obtained for the first time.     

Development and Validation of Stability-Indicating UPLC Method for 9-Desmethyl-<Emphasis Type="Italic">α</Emphasis>-dihydrotetrabenazine

A stability-indicating UPLC method was developed for quantitative determination of 9-desmethyl-α-dihydrotetrabenazine (9-DM-α-DTBZ), the precursor for preparing a widely used vesicular monoamine transporter 2 imaging agent ¹¹C-α-DTBZ. Compound 9-DM-α-DTBZ was subjected to various stress conditions consisting of acidic, alkaline, oxidative, thermal and photolytic forced degradation. The decomposition of 9-DM-α-DTBZ was observed under oxidative condition, whereas no obvious degradation was shown under the other stress conditions. For chromatographic separation of 9-DM-α-DTBZ and its degradation products, an Acquity UPLC BEH C18 column (2.1 × 100 mm, 1.7 μm) and a mobile phase of 20:80 (v/v) methanol/ammonium acetate buffer (pH 4.5, 10 mM) were used. Quantitative determination of 9-DM-α-DTBZ was performed using a PDA detector at a flow rate of 0.30 mL min^?1. UPLC–MS analysis was further utilized to characterize the two degradation products. The proposed method was fully validated as per USP guidelines with respect to linearity, accuracy, precision, robustness, limit of detection (LOD) and limit of quantification (LOQ). The linear regression analysis showed a good linear relationship (r ²  = 0.9995) in the concentration range of 0.001–1.00 mg mL^?1 (n = 6). The assay method was found to have good precision (1.14–1.35% RSD) and recovery (98.91–101.23%). Additionally, the LOD and LOQ of 9-DM-α-DTBZ were 0.30 and 1.00 μg mL^?1, respectively. These results indicated that the present method could be used to evaluate the quality of regular production samples and also used in stability assays.     

Ethanol Production from Starch Hydrolyzates using <Emphasis Type="Italic">Zymomonas mobilis</Emphasis> and Glucoamylase Entrapped in Polyvinylalcohol Hydrogel

The glucoamylase from Aspergillus niger, immobilized into poly(vinylalcohol) hydrogel lens-shaped capsules LentiKats®, was used for simultaneous saccharification and fermentation (SSF) with Zymomonas mobilis in free form. This system was stable in both the repeated batch and continuous mode of SSF. The microorganism was found to adsorb on the capsules with immobilized enzyme. This increased the ethanol productivity of the repeated batch system with 5% w/v of immobilized glucoamylase almost 2.1 times (7.2 g l^?1 h^?1) compared to free enzyme–free microorganism system (3.5 g l^?1 h^?1). The continuous SSF with the immobilized glucoamylase (11.5% w/v) tested for 15 days had productivity 10 g l^?1 h^?1, which is comparable to continuous experiments on semi-defined glucose medium (10 g l^?1 h^?1). These two systems were stable in both glucoamylase activity and microorganism productivity.     

The response electron–electron repulsion energy and energy component analysis in CC/MBPT methods

Molecular properties are computed as responses to perturbations (energy derivatives) in coupled-cluster (CC)/many-body perturbation theory (MBPT) models. Here, the CC/MBPT energy derivative with respect to a general two-electron (2-e) perturbation is assembled from gradient theory for 2-e property evaluation, including the electron repulsion energy. The correlation energy (?E) is shown to be the sum of response kinetic (?T), electron–nuclear attraction (?V), and electron repulsion (?V _ee ) energies. Thus, evaluation of total V _ee for energy component analysis is simple: For total energy (E), total 1-e responses T and V, and nuclear–nuclear repulsion energy (V _NN ), V _ee  = E ? V _NN  ? T ? V is the true 2-e response value. Component energy analysis is illustrated in an assessment of steric repulsion in ethane’s rotational barrier. Earlier SCF-based results (Bader et al. in J Am Chem Soc 112:6530, 1990) are corroborated: The higher-energy eclipsed geometry is favored versus staggered in the two repulsion energies (V _NN and V _ee ), while decisively disfavored in electron–nuclear attraction energy (V). Our best quality calculations (CCSD/cc-pVQZ) attain practical Virial Theorem compliance (i.e., agreement among the kinetic energy, potential energy, and total energy representations) in assigning 2.70 ± 0.06 to the barrier height; ?195.80 kcal/mol is assigned to the drop in “steric” repulsion upon going to the eclipsed geometry. Steric repulsion is not responsible for any fraction of the ~3 kcal/mol barrier.     

Highly sensitive electrocatalytic determination of pyrazinamide using a modified poly(glycine) glassy carbon electrode by square-wave voltammetry

A new voltammetric sensor based on electropolymerization of glycine at glassy carbon electrode (GCE) was developed and applied to determine of pyrazinamide (PZA) by square-wave voltammetry (SWV). The initial cyclic voltammetric studies showed an electrocatalytic activity of poly(Gly)/GCE on redox system of pyrazinamide in 0.1 mol L^?1 phosphate buffer solution pH 7.5, with E _Pc and E _Pa in ?0.85 and ?0.8 V (versus E _Ag/AgCl), respectively. Studies at different scan rates suggest that the redox system of pyrazinamide at poly(Gly)/GCE is a process controlled by diffusion in the interval from 10 to 100 mV s^?1. Square-wave voltammetry-optimized conditions showed a linear response of PZA concentrations in the range from 0.47 to 6.15 μmol L^?1 (R?=?0.998) with a limit of detection (LOD) of 0.035 μmol L^?1 and a limit of quantification (LOQ) of 0.12 μmol L^?1. The developed SWV-poly(Gly)/GCE method provided a good intra-day (RSD?=?3.75 %) and inter-day repeatability (RSD?=?4.96 %) at 4.06 μmol L^?1 PZA (n?=?10). No interference of matrix of real samples was observed in the voltammetric response of PZA, and the method was considered to be highly selective for the compound. In the accuracy test, the recovery was found in the range of 98.2 and 104.0 % for human urine samples and pharmaceutical formulation (tablets). The PZA quantification results in pharmaceutical tablets obtained by the proposed SWV-poly(Gly)/GCE method were comparable to those found by official analytical protocols.