A new amperometric biosensor for fructose determination based on epoxy-graphite-TTF-TCNQ-FDH-biocomposite

In this work a novel amperometric biosensor for fructose determination in solutions was developed. The device was constructed by the incorporation of a tetrathiofulvalene-tetracyanoquinodimethane organic conducting salt and fructose dehydrogenase enzyme, include in a polymeric matrix of epoxy resin and graphite powder. Because of the electrocatalytic function of the salt, the direct transfer of the electron between the reduced prosthetic group (PQQH₂) of the enzyme and the transducing material, was verified at a low working potential (150 mV vs. Ag/AgCl), where the interfering reactions were minimized. The response time at 90% of the steady state value was less than 20 s. The current response was directly proportional to the D-fructose concentration from 0.01 to 0.3 mmol/l with a detection limit of 0.005 mmol/l (signal/noise of 3) and a sensitivity of 1.9985 μA/mmol. The biosensor sensitivity diminishes when its surface is not polished between successive determinations, and remains constant (rsd=1.85, n=10) when the surface is polished between determinations. The effects of temperature and pH on the biosensor response were studied and analyzed; also the properties of the enzyme (Km _ap, I _max, Q₁₀) were determinate in this work. The biosensor was used to determine fructose in high fructose syrups and there were not significant differences between these results and those obtained by HPLC (p≤0.05). During 4 months, in intermittent determinations the biosensor kept 100% of its original sensitivity and after 18 months stored at 4°C, it only lost 32% of its sensitivity. The simplicity, low working potential, high stability and good performance of this biosensor shows a great potential for its use in the fructose determination.     

Functionalized metal–organic frameworks with strong acidity and hydrophobicity as an efficient catalyst for the production of 5-hydroxymethylfurfural

In the dehydration of fructose to 5-hydroxymethyl furfural(HMF), in situ produced water weakens the acid strength of the catalyst and causes the rehydration of HMF, causing unsatisfactory catalytic activity and selectivity. In this work, a class of benzenesulfonic acid-grafted metal–organic frameworks with strong acidity and hydrophobicity is obtained by the direct sulfonation method using 4-chlorobenzenesulfonic acid as sulfonating agent. The resultant MOFs have a specific surface area of greater than 250 m~2·g~(-1), acid density above 1.0 mmol·g~(-1), and water contact angle up to 129°. The hydrophobic MOF-Ph SO_3 H exhibits both higher catalytic activity and selectivity than MOF-SO_3 H in the HMF synthesis due to its better hydrophobicity and olephilicity. Moreover, the catalyst has a high recycled stability. At last, fructose is completely converted, and 98.0% yield of HMF is obtained under 120 °C in a DMSO solvent system. The successful preparation of the hydrophobic acidic MOF provides a novel hydrophobic catalyst for the synthesis of HMF.     

A carboxyalkanethiol monolayer modified electrode for blocking of ascorbic acid oxidation and its application to a biosensor

Upon the application of amperometric biosensor to the biological fluid, ascorbic acid interferes the amperometric determination of analytes, because the oxidative potential of ascorbic acid is lower than that of electro active substances such as H₂O₂ produced by the enzymatic reaction. In this study we propose a method to block ascorbic acid based on the electrostatic interaction with self-assembled monolayer (SAM) and its application of the surface modified electrode to biosensor. In order to form SAM on the gold electrode with carboxyl group, 7-carboxy-heptanethiol (7-CHT) was used. The 7-CHT modified electrode did not show anodic response to ascorbic acid, but oxidized phenanthroline cobalt complex [Co(phen)₃²⁺], which can be used as a mediator of biosensor. Thus, the 7CHT-modified electrode was applied to biosensor mediated with Co(phen)₃²⁺. Fructose dehydrogenase (FDH) was immobilized to the 7-CHT modified electrode. Fructose was determined selectively with the FDH/7-CHT modified electrode at the range of 0.2-2 mM.     

Rapid and direct determination of fructose in food: A new osmium-polymer mediated biosensor

This paper describes the development and performance of a new rapid amperometric biosensor for fructose monitoring in food analysis. The biosensor is based on the activity of fructose dehydrogenase (FDH) immobilised into a carbon nanotube paste electrode according to two different procedures. The direct wiring of the FDH in a highly original osmium-polymer hydrogel was found to offer a better enzyme entrapment compared to the immobilisation of the enzyme in an albumin hydrogel. The optimised biosensor required only 5 U of FDH and kept the 80% of its initial sensitivity after 4 months. During this time, the biosensor showed a detection limit for fructose of 1 μM, a large linear range between 0.1 and 5 mM, a high sensitivity (1.95 μA cm⁻² mM), good reproducibility (RSD = 2.1%) and a fast response time (4 s).     

Evaluation of benchtop versus portable near-infrared spectroscopic method combined with multivariate approaches for the fast and simultaneous quantitative analysis of main sugars in syrup formulations

In this work a total of 116 syrup samples was investigated in order to establish predictive models for glucose, fructose and sucrose of sufficient accuracy based on partial least squares regression. The samples are divided into two main groups a) standard syrups b) reformulated syrups. The latter products can be distinguished via the very low amount of glucose and sucrose and a high amount of fructose which makes them suitable for special nutrition. Near-infrared spectroscopy was applied together with Multivariate Analysis to develop a new method for quality control of syrups. Comparison between a portable spectrometer and the benchtop device showed that the reduced wavelength range and reduced resolution of the portable device is sufficient to receive calibrations with R² ≥ 0.96 for standard syrups with comparable SEP values of 1.30 g/100 g vs. 1.19 g/100 g, 0.94 g/100 g vs. 0.99 g/100 g and 2.04 g/100 g vs. 2.46 g/100 g for glucose, fructose and sucrose respectively using the handheld device. The SEP values led to high RPD values of 5.56 vs. 5.26, 4.30 vs. 4.72, 5.06 vs. 4.20 for fructose, glucose and sucrose respectively. The R² values for reformulated syrups were 0.94 with a SEP of 1.04 g/100 g and a RPD value of 2.58 for the portable spectrometer and 0.92 with a SEP of 0.92 g/100 g and a resulting RPD value of 2.84 for the benchtop spectrometer. The method is suitable to be implemented for quality control in the producing industry as well as in grocery stores.     

Conversion of fructose and glucose into 5-hydroxymethylfurfural catalyzed by a solid heteropolyacid salt

A solid heteropolyacid salt Ag₃PW₁₂O₄₀ has been used as a heterogeneous catalyst for the production of 5-hydroxymethylfurfural (HMF) from fructose and glucose. The fructose was selectively dehydrated into HMF with the HMF yield as high as 77.7% and selectivity of 93.8% within 60 min at 120 °C. In addition, Ag₃PW₁₂O₄₀ also exhibited catalytic activity for conversion of glucose into HMF. Moreover, the catalyst is tolerant to high concentration feedstock and can be recycled. The results illustrate that the Ag₃PW₁₂O₄₀ is an excellent acid and environmentally benign solid catalyst for the production of HMF from fructose and glucose.     

Fructose decomposition kinetics in organic acids-enriched high temperature liquid water

Biomass continues to be an important candidate as a renewable resource for energy, chemicals, and feedstock. Decomposition of biomass in high temperature liquid water is a promising technique for producing industrially important chemicals such as 5-hydroxymethylfurfural (5-HMF), furfural, levulinic acid with high efficiency. Hexose, which is the hydrolysis product of cellulose, will be one of the most important starting chemicals in the coming society that is highly dependent on biomass. Taking fructose as a model compound, its decomposition kinetics in organic acids-enriched high temperature liquid water was studied in the temperature range from 180 °C to 220 °C under the pressure of 10 MPa to further improve reaction rate and selectivity of the decomposition reactions. The results showed that the reaction rate is greatly enhanced with the addition of organic acids, especially formic acid. The effects of temperature, residence time, organic acids and their concentrations on the conversion of fructose and yield of 5-HMF were investigated. The evaluated apparent activation energies of fructose decomposition are 126.8 ± 3.3 kJ mol⁻¹ without any catalyst, 112.0 ± 13.7 kJ mol⁻¹ catalyzed with formic acid, and 125.6 ± 3.8 kJ mol⁻¹ catalyzed with acetic acid, respectively, which shows no significant difference.     

H-Y/β双微孔沸石分子筛催化果糖脱水生成5-羟甲基糠醛的研究

研究了以H-Y/β双微孔沸石分子筛为催化剂,果糖脱水转化为5-羟甲基糠醛(HMF)的反应,考察不同催化剂、溶剂、助剂用量、反应温度和反应时间,以确定H-Y/Beta双微孔沸石分子筛催化剂催化果糖脱水转化为HMF的最佳反应条件。研究发现,以1 g果糖为原料,最佳反应条件为:催化剂0.05 g、溶剂二甲基亚砜(DMSO)30 mL、助剂聚乙烯吡咯烷酮(PVP)0.03 g、反应温度160℃、反应时间1.5 h,利用紫外分光光度法测定产物,并计算其产率为64.6%。