Integration of wheat straw for a biorefinery-based energy generation process by producing ethanol and biogas together with the production of high-protein fungal biomass (suitable for feed application) was the main focus of the present study. An edible ascomycete fungal strain Neurospora intermedia was used for the ethanol fermentation and subsequent biomass production from dilute phosphoric acid (0.7 to 1.2% w/v) pretreated wheat straw. At optimum pretreatment conditions, an ethanol yield of 84 to 90% of the theoretical maximum, based on glucan content of substrate straw, was observed from fungal fermentation post the enzymatic hydrolysis process. The biogas production from the pretreated straw slurry showed an improved methane yield potential up to 162% increase, as compared to that of the untreated straw. Additional biogas production, using the syrup, a waste stream obtained post the ethanol fermentation, resulted in a combined total energy output of 15.8 MJ/kg wheat straw. Moreover, using thin stillage (a waste stream from the first-generation wheat-based ethanol process) as a co-substrate to the biogas process resulted in an additional increase by about 14 to 27% in the total energy output as compared to using only wheat straw-based substrates.
Rhodococcus sp. has a broad catabolic diversity and unique enzymatic capabilities, and it is able to adapt under extreme conditions. Thereby, the production of this remarkable bacterium has a great biotechnological and industrial importance. In this sense, we sought to improve the R. erythropolis ATCC 4277 growth through a central composite design, by varying the components of nutrient medium (glucose, malt extract, yeast extract, CaCO3), temperature, and agitation. It was found that the concentrations of glucose and malt extract are not statistically significant, being reduced of 4.0 and 10.0 g L-1 to 2.0 and 5.0 g L?1, respectively. The CaCO3 concentration and temperature were also diminished of 2.0 to 1.16 g L?1and 28 to 23.7 °C, respectively. Optimal growth conditions provided a 240% increase in final biomass concentration, an increment in specific growth rate, and a growth yield coefficient about five times greater. Application of the optimal conditions in biodesulfurization and biodenitrogenation processes showed that desulfurization capability is not associated with optimal growth conditions; however, it was achieved a 47% of nitrogen removal in the assay containing 10% (w/w) of heavy gas oil.
Electrophoretic, antioxidant, and FTIR profiles of some varieties of amaranth, quinoa, and buckwheat seeds and their by products were compared. Water extracts of these products were evaluated by the Folin–Ciocalteau method in order to determine total phenolic content. The antioxidant activities were determined by 2,2′-azobis-2-methyl-propanimidamide, ferric-reducing/antioxidant power, and cupric reducing antioxidant capacity radical scavenging assays. FTIR spectra showed the secondary structure of pseudocereals in the ranges of amides I, II, and III shifts. Results of evaluated methods could be used to control several products (seeds, flours, extracts, flakes, roasting) with high phenolic content and antioxidant activity suitable for supplementation in food applications.
The aim of this paper was to evaluate different strategies of chitosan activation using cross-linking reagent like glycidol, epichlorohydrin, and glutaraldehyde for Thermomyces lanuginosus lipase (TLL) immobilization. Operational activity and stability by esterification of oleic acid with ethanol and thermal inactivation using these derivatives were investigated. Derivative obtained by sequentially activation with glycidol, ethylenediamine, and glutaraldehyde and subsequent TLL immobilization showed the best performance, with high hydrolytic activity value. Its stability was 15-fold higher than solubilized TLL in the evaluated inactivation conditions (60 °C, 25 mM sodium phosphate buffer pH 7). After 5 cycles of oleic acid esterification, only a few percentage of its conversion has reduced. On the other hand, glycidol-activated chitosan derivative showed very low hydrolytic activity value. Epichlorohydrin-activated chitosan derivative showed regular hydrolytic activity value. Both derivatives showed low immobilization yields. Operational stability of this last derivative was very low, where after the first cycle of oleic acid esterification, only 56% of its initial conversion was obtained.
An enzyme immobilized on a mesoporous silica nanoparticle can serve as a multiple catalyst for the synthesis of industrially useful chemicals. In this work, MCM-41 nanoparticles were coated with polyethylenimine (MCM-41@PEI) and further modified by chelation of divalent metal ions (M = Co2+, Cu2+, or Pd2+) to produce metal-chelated silica nanoparticles (MCM-41@PEI-M). Thermomyces lanuginosa lipase (TLL) was immobilized onto MCM-41, MCM-41@PEI, and MCM-41@PEI-M by physical adsorption. Maximum immobilization yield and efficiency of 75 ± 3.5 and 65 ± 2.7% were obtained for MCM@PEI-Co, respectively. The highest biocatalytic activity at extremely acidic and basic pH (pH = 3 and 10) values were achieved for MCM-PEI-Co and MCM-PEI-Cu, respectively. Optimum enzymatic activity was observed for MCM-41@PEI-Co at 75 °C, while immobilized lipase on the Co-chelated support retained 70% of its initial activity after 14 days of storage at room temperature. Due to its efficient catalytic performance, MCM-41@PEI-Co was selected for the synthesis of ethyl valerate in the presence of valeric acid and ethanol. The enzymatic esterification yield for immobilized lipase onto MCM-41@PEI-Co was 60 and 53%, respectively, after 24 h of incubation in n-hexane and dimethyl sulfoxide media.
Graphical Abstract Divalent metal chelated polyethylenimine coated MCM-41 (MCM-41@PEI-M) was used for immobilization of Thermomyces lanuginosa lipase catalyzing green apple flavor preparation
ε-Poly-l-lysine (ε-PL) is a natural preservative for food processing industry. A thermo-responsive polymer, attached with Cu2+ or Ni2+, was prepared for metal-chelate affinity precipitation for purification of ε-PL. The low critical solution temperatures (LCSTs) of these polymers were close to the room temperature (31.0–35.0 °C). The optimal adsorption conditions were as follows: pH 4.0, 0 mol/L NaCl, ligand density 75.00 μmol/g, and 120 min. The ligand Cu2+ showed a stronger affinity interaction with ε-PL and the highest adsorption amount reached 251.93 mg/g polymer. The elution recovery of ε-PL could be 98.42% with 0.50 mol/L imidazole (pH = 8.0) as the eluent. The method could purify ε-PL from fermentation broth and the final product was proved as electrophoretic pure by SDS-PAGE. Moreover, these affinity polymers could be recycled after the purification of ε-PL and the recoveries were above 95.00%.
A series of collagen hydrolysates (CHs) were prepared from pigskin shavings by using pepsin (PCH), trypsin (TCH), Alcalase (ACH), HCl (HCH), and NaOH (NCH). Their physicochemical properties, including degree of collagen hydrolysis, molecular weight distribution, electric charge, and microstructure, were investigated, and their flocculation performance was evaluated in a kaolin suspension, at varied pHs and concentrations. PCH exhibited high flocculation capability under acidic and neutral conditions, and its efficiency for removing suspended particles was approximately 80% at a concentration of 0.05 g/L. TCH, ACH, HCH, and NCH showed almost no flocculation capability. The flocculation capability of PCH could be mainly due to a combination of optimal molecular weight distribution and electric charge. This study could provide an environment-friendly natural flocculant and also proposes a promising approach for the reuse of collagen wastes.
Currently, the heavy metal pollution is of grave concern, and the part of microorganism for metal bioremediation should take into account as an efficient and economic strategy. On this framework, the heavy metal stress consequences on exopolysaccharide (EPS)-producing agricultural isolate, Pantoea agglomerans, were studied. The EPS production is a protective response to stress to survive and grow in the metal-contaminated environment. P. agglomerans show tolerance and mucoid growth in the presence of heavy metals, i.e., mercury, copper, silver, arsenic, lead, chromium, and cadmium. EDX first confirmed the metal accumulation and further, FTIR determined the functional groups involved in metal binding. The ICP-AES identified the location of cell-bound and intracellular metal accumulation. Metal deposition on cell surface has released more Ca2+. The effect on bacterial morphology investigated with SEM and TEM revealed the sites of metal accumulation, as well as possible structural changes. Each heavy metal caused distinct change and accumulated on cell-bound EPS with some intracellular deposits. The metal stress caused a decrease in total protein content and increased in total carbohydrate with a boost in EPS. Thus, the performance of P. agglomerans under metal stress indicated a potential candidate for metal bioremediation.
Multiwalled carbon nanotubes (MWNTs) were modified by imidazole-based ionic liquids with different alkyl groups. The modified support samples were characterized by scanning transmission electron microscopy, Raman spectra, thermogravimetric analyses, and X-ray photoelectron spectroscopy. The samples were used to immobilize Candida antarctic lipase (CALB) and the influence of alkyl chain length of ionic liquids on enzymatic properties was investigated by the hydrolysis reaction of triacetin. The results revealed that functionalized ionic liquids modification did not destroy the structure of MWNTs. Compared with the immobilized CALB on MWNTs, the immobilized CALB on novel carriers all exhibited higher activity, thermal stability, and reusability. Especially, the activity of MWNTs-IL (8C)-CALB improved 15.23-folds than MWNTs-CALB, meanwhile, after incubation at 70 °C for 20 min, residual enzyme activity of MWNTs-IL (8C)-CALB was 46% of the initial activity, while MWNTs-CALB already lost all activity. Besides, MWNTs-IL (8C)-CALB retained 64.5% of its initial activity after 4 cycles, while MWNTs-CALB retained only 2.12%.
Porcine pancreatic lipase (PPL) was immobilized onto functionalized ionic liquid-modified silica carrier using gelatinization and physical adsorption. The immobilized lipase was characterized with N2 adsorption–desorption, X-ray diffraction (XRD), scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FT-IR) before and after modification and immobilization. The results showed that the modification of the ionic liquid and the introduction of lipase had been successfully approved. The rate of enzymatic reaction and its influencing factors was primarily studied by enzymatic reaction kinetics. Km values of PPL-SiO2@CA and PPL-IM/BF4-SiO2@CA were 4.9 and 3.7 mg/ml, respectively. It indicated that the modification of the functionalized ionic liquid enhanced the affinity between the immobilized enzyme and the substrate. The immobilization efficiency, specific activity, optimum temperature, optimum pH, thermal stability, reusability, and storage stability of the immobilized enzyme were investigated. We found that the stability of the immobilized enzyme was significantly higher than that of the unmodified immobilized enzyme. Specially, PPL-IM/BF4-SiO2@CA maintained good thermal stability and retained more than 92% of its activity at 65 °C after preheating 3 h.
A new method is described for the determination of the pesticide λ-cyhalothrin (LC). It combines SERS detection with molecular imprinting and largely improves selectivity. A multilayer surface imprinted nanocomposite was synthesized in two steps on a nanostructure of type SiO2@rGO@Ag acting as a substrates. Firstly, the surface of the SiO2@rGO@Ag composite was modified with self-polymerized dopamine. Secondly, surface-initiated polymerization was carried out to prepare a molecularly imprinted polymer (MIP) using LC as the template. The use of this SiO2@rGO@Ag-MIP allows for excellent SERS based detection and has high selectivity for LC. The Raman intensity and LC concentration present perfect linear relationship between 10?5 to 10?9 mol L?1 and the detection limit is 3.8×10?10 mol L?1. All the procedures are conducted in aqueous or ethanol solution.
Graphical abstract Schematic of a new method for determination of the pesticide λ-cyhalothrin. It combines SERS detection with molecular imprinting and largely improves selectivity. A multilayer surface imprinted nanocomposite was synthesized in two steps on a nanostructure of type SiO2@rGO@Ag acting as a substrates.
A nonresonant, femtosecond (fs) laser is employed to desorb samples of Victoria blue deposited on stainless steel or indium tin oxide (ITO) slides using either electrospray deposition (ESD) or dried droplet deposition. The use of ESD resulted in uniform films of Victoria blue whereas the dried droplet method resulted in the formation of a ring pattern of the dye. Laser electrospray mass spectrometry (LEMS) measurements of the ESD-prepared films on either substrate were similar and revealed lower average relative standard deviations for measurements within-film (20.9%) and between-films (8.7%) in comparison to dried droplet (75.5% and 40.2%, respectively). The mass spectral response for ESD samples on both substrates was linear (R2?>?0.99), enabling quantitative measurements over the selected range of 7.0?×?10?11 to 2.8?×?10?9 mol, as opposed to the dried droplet samples where quantitation was not possible (R2?=?0.56). The limit of detection was measured to be 210 fmol.
A potassium-containing hexaazamacrocyclic dication, [M?H?K]2+, is able to add in the gas phase mono- and dicarboxylate anions as well as inorganic anions by forming the corresponding monocharged adducts, the structure of which markedly depends on the basicity of the anion. With anions, such as acetate or fluoride, the neutral hexaazamacrocycle M acts as an acceptor of monosolvated K+ ion. With less basic anions, such as trifluoroacetate or chloride, the protonated hexaazamacrocycle [M?H]+ performs the unusual functions of an acceptor of contact K+/anion pairs.
CdSe:Eu nanocrystals were successfully synthesized and characterized by transmission electron microscopy, X-ray powder diffraction, and X-ray photoelectric spectroscopy. The CdSe:Eu nanocrystals showed enhanced green electrochemiluminescence (ECL) intensity when compared to pure CdSe nanocrystals. Further, the nanocrystals were used to design an ECL immunosensor for the detection of carcinoembryonic antigen (CEA) that has a linear response over the 1.0 fg·mL?1 to 100 ng·mL?1 CEA concentration range with a 0.4 fg·mL?1 detection limit. The assay was applied to the determination of CEA in human serum samples.
Graphical abstract Schematic of the assay: GCE-glassy-carbon electrode, Ab- Antibody, BSA- Bovine serum albumin, Ag- Antigen. CdSe:Eu nanocrystals were used to design an ECL immunosensor for the detection of carcinoembryonic antigen.
Imidazole ring is a known structure in many natural or synthetic drug molecules and its metal complexes can interact with DNA and do the cleavage. Hence, to study the influence of the structure and size of the ligand on biological behavior of metal complexes, two water-soluble Pd(II) complexes of phen and FIP ligands (where phen is 1,10-phenanthroline and FIP is 2-(Furan-2-yl)-1H–Imidazo[4,5-f][1, 10]phenanthroline) with the formula of [Pd(phen)(FIP)](NO3)2 and [Pd(FIP)2]Cl2, that were activated against chronic myelogenous leukemia cell line, K562, were selected. Also, the interaction of these anticancer Pd(II) complexes with highly polymerized calf thymus DNA was extensively studied by means of electronic absorption, fluorescence, and circular dichroism in Tris-buffer. The results showed that the binding was positive cooperation and [Pd(phen)(FIP)](NO3)2 (Kf = 127 M-1G = 1.2) exhibited higher binding constant and number of binding sites than [Pd(FIP)2]Cl2 (Kf = 13 M-1G = 1.03) upon binding to DNA. The fluorescence data indicates that quenching effect for [Pd(phen)(FIP)](NO3)2 (KSV = 58 mM?1) was higher than [Pd(FIP)2]Cl2 (KSV = 12 mM?1). Also, [Pd(FIP)2]Cl2 interacts with ethidium bromide-DNA, as non-competitive inhibition, and can bind to DNA via groove binding and [Pd(phen)(FIP)](NO3)2 can intercalate in DNA. These results were confirmed by circular dichroism spectra. Docking data revealed that longer complexes have higher interaction energy and bind to DNA via groove binding.
Graphical Abstract Two anticancer Pd(II) complexes of imidazole derivative have been synthesized and interacted with calf thymus DNA. Modes of binding have been studied by electronic absorption, fluorescence, and CD measurements. [Pd(FIP)2]Cl2 can bind to DNA via groove binding while intercalation mode of binding is observed for [Pd(phen)(FIP)](NO3)2.
A novel polyhedral oligomeric silsesquioxane (POSS) composite polyacrylonitrile (PAN)-based porous structure gel polymer electrolyte (GPE) is prepared by phase inversion method. The POSS additive filler is firstly obtained in the dehydration condensation reaction of vinyltrimethoxysilane (VTMS) and 3-methacryloxypropyltrimethoxysilane (MPTMS). The composition and structure of synthetic POSS and the prepared POSS composite PAN-based GPEs are investigated. It is found that compared with pure PAN-based GPE, the POSS composite PAN-based GPE with 8 wt.% POSS presents the homogeneous pore distribution and abundant electrolyte uptake (540.4 wt.%), which endows GPE-8% with the excellent comprehensive performances: the highest ionic conductivity of 2.62?×?10?3 S cm?1 at room temperature, the higher lithium ion transference number of 0.38, the good compatibility with lithium anode, and the higher electrochemical stability window of 5.7 V (vs. Li/Li+). At 0.2 C, the GPE-8%-based lithium ion battery produces a satisfactory discharge capacity of 140 mAh g?1.
A highly selective electrochemical sensor was fabricated based on a modified carbon paste electrode with zinc ferrite nanoparticles (ZnFe2O4 NPs). The nanocomposite has attractive properties such as high surface-to-volume ratio and good electrocatalytic activity towards the drugs acetaminophen (AC), epinephrine (EP), and melatonin (MT), best at working voltages of 0.35, 0.09 and 0.55 V (vs. Ag/AgCl), respectively. The linear ranges (and detection limits) are 6.5–135 (0.4) μmol L?1 for AC, 5–100 (0.7) μmol L?1 for EP, and 6.5–145 (3) μmol L?1 for MT.
Graphical abstract A novel electrochemical sensor based on a modified carbon paste electrode with zinc ferrite nanoparticles (ZnFe2O4) for the simultaneous detection of the acetaminophen, epinephrine and melatonin was fabricated
A new zinc-layered hydroxide-L-phenylalanate (ZLH-LP)-modified multiwalled carbon nanotube (MWCNT) was prepared as a new material of paste electrode for the detection of paracetamol (PCM) in 1.0?×?10?1 M phosphate buffer solution and at pH 7.5. The electrochemical characterization of the MWCNTs/ZLH-LP paste electrode was characterized by square wave voltammetry, electrochemical impedance spectroscopy, and cyclic voltammetry while the morphology properties of the MWCNTs, ZLH-LP, and MWCNTs/ZLH-LP were investigated using transmission electron microscopy and scanning electron microscopy. Under optimized conditions, the MWCNTs/ZLH-LP paste electrode demonstrated an excellent electrocatalytic activity towards oxidation of PCM in the linear responses’ ranges from 7.0?×?10?7 M to 1.0?×?10?4 M (correlation coefficient, 0.996) with the limit of detection obtained at 8.3?×?10?8 M. As a conclusion, the MWCNTs/ZLH-LP paste electrode revealed good repeatability, reproducibility, and stability, and was found to be applicable for use in pharmaceutical tablet samples.
The authors describe a cataluminescence (CTL) based sensing method via signals generated at the surface of In3LaTi2O10 nanoparticles for simultaneous determination of trimethylamine, formaldehyde and benzene in air. The analytical wavelengths are 340 nm, 440 nm and 600 nm, and the best surface temperature of the catalytic material is 275 °C. The limits of detection of this method are 0.3 mg?m?3 for trimethylamine, 0.07 mg?m?3 for formaldehyde, and 0.2 mg?m?3 for benzene. The linear ranges of CTL intensity versus gas/vapor concentration are from 1.0 to 65.1 mg?m?3 for trimethylamine, from 0.2 to 72.5 mg?m?3 for formaldehyde, and from 0.5 to 77.5 mg?m?3 for benzene. The recoveries after testing 10 standard samples ranged from 98.1% to 102.6% for trimethylamine, from 98.1% to 102.6% for formaldehyde, and from 97.7% to 103.8% for benzene. Gaseous ammonia, acetaldehyde, toluene, ethylbenzene, ethanol, sulfur dioxide and carbon dioxide do not interfere. The relative deviation of the CTL signals after 200 h of continuous detection of trimethylamine, formaldehyde and benzene is <3%.
Graphical abstract Schematic of a cataluminescence (CTL) based method for simultaneous determination of trimethylamine (TMA), formaldehyde (HCHO) and benzene (C6H6) in air. The linear ranges of CTL intensity versus gas/vapor concentration are from 1.0 to 65.1 mg?m?3 for TMA, from 0.2 to 72.5 mg?m?3 for HCHO, and from 0.5 to 77.5 mg?m?3 for C6H6.
The authors describe an ethylene glycol assisted precipitation method for synthesis of Er(III)/Yb(III)-doped BiF3 nanoparticles (NPs) at room temperature. Under 980-nm light irradiation, the NPs emit upconversion (UC) emission of Er(III) ions as a result of a two-photon absorption process. The temperature-dependent green emissions (peaking at 525 and 545 nm) are used to establish an unambiguous relationship between the ratio of fluorescence intensities and temperature. The NPs have a maximum sensitivity of 6.5?×?10?3 K?1 at 619 K and can be applied over the 291–691 K temperature range. The results indicate that these NPs are a promising candidate for optical thermometry.
Graphical abstract Schematic of the room-temperature preparation of Er(III)/Yb(III)-doped BiF3 nanoparticles with strongly temperature-dependent upconversion emission.
