13C Cross-polarization Research Articles

Room-temperature hyperpolarization of polycrystalline samples with optically polarized triplet electrons: pentacene or nitrogen-vacancy center in diamond?

We demonstrate room-temperature C hyperpolarization by dynamic nuclear polarization(DNP) using optically polarized triplet electron spins in two polycrystalline systems: pentacene-doped [carboxyl-C] benzoic acid and microdiamonds containing nitrogen-vacancy (NV) centers. For both samples, the integrated solid effect (ISE) is used to polarize the C spin system in magnetic fields of 350-400 mT. In the benzoic acid sample, the C spin polarization is enhanced by up to 0.12 % through direct electron-to-C polarization transfer without performing dynamic H polarization followed by cross-polarization. In addition, the ISE has been successfully applied to polarize naturally abundant C spins in a microdiamond sample to 0.01 %. To characterize the buildup of the C polarization, we discuss the efficiencies of direct polarization transfer between the electron and C spins as well as that of spin diffusion, examining various parameters which are beneficial or detrimental for successful bulk dynamic C polarization.

Signal Deconvolution and Generative Topographic Mapping Regression for Solid-State NMR of Multi-Component Materials.

Solid-state nuclear magnetic resonance (ssNMR) spectroscopy provides information on native structures and the dynamics for predicting and designing the physical properties of multi-component solid materials. However, such an analysis is difficult because of the broad and overlapping spectra of these materials. Therefore, signal deconvolution and prediction are great challenges for their ssNMR analysis. We examined signal deconvolution methods using a short-time Fourier transform (STFT) and a non-negative tensor/matrix factorization (NTF, NMF), and methods for predicting NMR signals and physical properties using generative topographic mapping regression (GTMR). We demonstrated the applications for macromolecular samples involved in cellulose degradation, plastics, and microalgae such as Euglena gracilis. During cellulose degradation, 13C cross-polarization (CP)–magic angle spinning spectra were separated into signals of cellulose, proteins, and lipids by STFT and NTF. GTMR accurately predicted cellulose degradation for catabolic products such as acetate and CO2. Using these methods, the 1H anisotropic spectrum of poly-ε-caprolactone was separated into the signals of crystalline and amorphous solids. Forward prediction and inverse prediction of GTMR were used to compute STFT-processed NMR signals from the physical properties of polylactic acid. These signal deconvolution and prediction methods for ssNMR spectra of macromolecules can resolve the problem of overlapping spectra and support macromolecular characterization and material design.

Alizarin Grafting onto Ultrasmall ZnO Nanoparticles: Mode of Binding, Stability, and Colorant Studies.

The demand is rising for colorants that are obtained from natural resources, tolerant to industrial processing methods, and meet color quality demands. Herein, we report how relevant properties such as thermal stability and photostability of the natural colorant alizarin can be improved by grafting it onto ZnO nanoparticles (NPs), allowing application in a warm extrusion process for the fabrication of polyamide fibers. For this study, ZnO NPs (diameter 2.0 ± 0.6 nm) were synthesized and subsequently functionalized with alizarin. The alizarin-coated ZnO NPs (i.e., dyed nanoparticles, DNPs) were characterized. Thermogravimetric analysis and ultraviolet–visible (UV–vis) studies revealed that alizarin coating accounts for ∼65% (w/w) of the total mass of the DNPs. A subsequent detailed characterization with Fourier transform infrared (FT-IR), 1H nuclear magnetic resonance (NMR), 13C cross-polarization magic angle spinning (CP-MAS) NMR, X-ray photoelectron spectroscopy (XPS), and quantum chemistry studies using various density functional theory (DFT) functionals and basis sets indicated that binding onto the ZnO NPs occurred predominantly via the catechol moiety of alizarin. Importantly, this grafting increased the thermal stability of alizarin with >100 °C, which allowed the processing of the DNPs into polyamide fibers by warm extrusion at 260 °C. Evaluation of the lightfastness of the DNP-dyed nylon fibers revealed that the changes in color quantified via the distance metric ΔE* of alizarin when embedded in a hybrid material were 2.6-fold better compared to nylon fibers that were directly dyed with alizarin. This reveals that the process of immobilization of a natural dye onto ZnO nanoparticles indeed improves the dye properties significantly and opens the way for a wide range of further studies into surface-immobilized dyes.

An indirect CO2 utilization for the crystallization control of CaCO3 using alkylcarbonate

Carbon mineralization into calcium carbonate (CaCO3) has been widely studied as a promising CO2 resource utilization pathway. In this work, CO2 was fixed to alkylcarbonate through phase change absorption in polyethylene glycol 200 (PEG) plus ethanediamine (EDA) system at ambient conditions. This alkylcarbonate was identified by FTIR and 13C cross-polarization magic-angle spinning (CP-MAS) NMR spectra. It was used as both CO32− source and crystal modifier to induce crystallization of CaCO3 particles. The CaCO3 microsphere with uniform morphology and vaterite crystal phase was acquired by adjusting quality of alkylcarbonate, concentration of Ca2+ concentration, and crystallization period without any additives. Furthermore, a plausible self-assembly formation mechanism toward inducing crystallization of vaterite CaCO3 microsphere also was proposed. This synthesis strategy is environmentally friendly and offers an alternative strategy for indirect utilization of CO2.

Structural changes in cell wall of Japanese radish accompanied by release of rhamnogalacturonan during pressure cooker heating

Changes in the cell wall of Japanese radish due to heating at 100 °C or 117 °C for 3 h were examined. Signals in 13C cross polarization magic angle spinning solid-state NMR (which detects rigid components) showed no differences between heating temperatures. 13C pulse saturation transfer magic angle spinning NMR (which detects flexible components) showed clear temperature-dependent changes in the rhamnose side chains of rhamnogalacturonan. Alcohol-insoluble solids isolated from raw samples were heated in water at 100 °C or 117 °C for 3 h. The concentrations of dissolved sugars and metal ions measured after heating in water at 117 °C were greater than in samples heated at 100 °C, indicating that loosening of cell wall structures increased with temperature, likely via degradation and elution of rhamnogalacturonan followed by β-elimination of homogalacturonan, and fewer interactions between cell wall components, including divalent metal ions. Vegetable shape was retained despite fewer interactions.

Synthesis and chromatographic evaluation of pyrazinedicarboxylic anhydride bonded stationary phase

A silica based hydrophilic stationary phase bonding with 2,3-pyrazinedicarboxylic anhydride and amino groups was synthesized via amino-acid anhydride ring opening reaction. The bonded groups could not only provide hydrophilic interaction, but also electrostatic, π–π and hydrogen bonding interactions, etc. The results of characterization with elemental analysis and solid-state 13C cross-polarization magic-angle-spinning NMR indicated the successful preparation of amino and carboxyl bonded stationary phase named ZAC. The ζ-potential of ZAC stationary phase showed the negatively charge was dominate at pH larger than 3.5. Chromatographic evaluation revealed that ZAC stationary phase behaved well under HILIC mode. It showed different selectivity and retention compared to some typical commercial columns, and it was validated by the separation of chitooligosaccharides, flavonoid glycosides, organic acids and alkaloid samples. Based on the different selectivity between ZAC stationary phase and C18 columns, ZAC stationary phase also showed different selectivity with C18. And it was verified by the separation of Lonicerae Japonicae Flos and Menispermi Rhizoma extracts.

Structural Evaluation of the Choline and Geranic Acid/Water Complex by SAXS and NMR Analyses

Recently, choline and geranic acid (CAGE), an ionic liquid (IL), has been recognized to be a superior biocompatible material for oral and transdermal drug delivery systems (DDS). When CAGE is administered, CAGE would be exposed to various types of physiological fluids, such as intestinal and intradermal fluids. However, the effect of physiological fluids on the structure of CAGE remains unclear. In the present study, molecular structures of CAGE with different ratios of water were investigated using small-angle X-ray scattering (SAXS) and nuclear magnetic resonance (NMR). The SAXS pattern of CAGE showed an IL-specific broad peak derived from nanoscale aggregation until 17 vol % water. Meanwhile, narrow peaks were observed in samples with 25-50 vol % water, showing a transition to the lamellar phase. With more than 67 vol % water, CAGE was found to exist as micelles in water. The 1H NMR spectra indicated that protons of H2O, OH in choline (CH), and COOH in geranic acid (GA) were observed as only one peak up to 17 vol % water. This peak shifted to a high magnetic field, and the integral values increased with the water content, speculating that water is localized close to the COOH and OH groups to allow proton exchange. The 13C NMR spectra showed that peaks related to the carboxyl group shifted with adding water. Moreover, only GA peaks were observed in the lamellar phase through 13C cross-polarization magic-angle spinning NMR, suggesting that the main rigid component of the lamellar phase was GA. Taken together, this study suggested that CAGE still maintained its IL structure up to 17 vol % water, then transitioned to the lamellar phase with 25-50 vol % water, and finally changed to the micellar phase with more than 67 vol % water. This information would be useful in the formulation and development of DDS using CAGE.

Silica Nanopowder Supported Frustrated Lewis Pairs for CO2 Capture and Conversion to Formic Acid.

Treatment of hydroxylated silica nanopowders S1 and allyl-functionalized silica nanopowders S2 with 3-(diphenylborano)- or 3-bis(pentafluorophenylborano)propyltrimethoxysilane or 2-(diphenylphosphino)- or 2-(dicyclohexylphosphino)ethyltriethoxysilane generates silica nanopowder supported Lewis acids S3 and silica nanopowder supported Lewis bases S4. These surfaces were characterized by 13C, 11B, and 31P cross-polarization magic angle spinning nuclear magnetic resonance (CP MAS NMR), X-ray photoelectron spectroscopy (XPS), and attenuated total reflection Fourier transform infrared (ATR FTIR). When S3 is combined with solution-phase Lewis bases PR3 (R = C6F5, C6H5, mesityl), six associated silica nanopowder supported frustrated Lewis pairs (FLPs) are formed. In another set of six reactions, the interactions between the supported Lewis bases S4 and solution-phase Lewis acids BR3 with R = C6F5, C6H5, mesityl produced six more associated supported FLPs. The capture of CO2 by these FLPs producing FLP-CO2 Lewis pair adducts S5 and S6 were highlighted by ATR FTIR, and it was found that FLP S5e with R = C6H5 on both the supported Lewis acid and solution-phase Lewis base trapped the largest quantities of CO2 on the silica nanopowder supports. Conversion of CO2 to HCOOH was achieved by first activating H2 to generate activated FLP-H2 surfaces S7 and S9. Addition of CO2 then generated HCOOH via the silica nanopowder supported FLP-HCOOH adducts S8 and S10. Qualitative identification of HCOOH generation was achieved by ATR FTIR measurements, and surface 10b with R = C6H5 proved to be the most successful silica nanopowder surface bound FLP in HCOOH generation. In some cases, diborano formates (-BO(CH)OB-) S11 and S12 were also identified as side products during HCOOH formation. Spectroscopic characterization of purposefully synthesized S11 and S12 included 11B and 31P CP MAS NMR.

Solid state NMR investigation of the roman Acqualadroni rostrum: tenth year assessment of the consolidation treatment of the wooden part

This work follows a previous one dealing with the state of conservation study of the wooden part of the roman Acqualadroni rostrum soon after its finding in the seabed of Acqualadroni (Messina, Italy). The archaeological survey and recovery were particularly relevant since this artefact is one of the two rostrums, nowadays known, found together with its wooden part. Following the recovery, it was consolidated by immersion in a melamine-formaldehyde resin (Kauramin) aqueous solution for eight months at the “Centro di Restauro del Legno Bagnato” (Pisa, Italy). The present investigation is aimed to determine at microscopic scale the wood state of conservation and to highlight interactions of the consolidant with wood components, by using solid-state NMR spectroscopy ten years after the consolidation treatment. Sampling by coring was exceptionally authorized, and the wood core was divided into seven aliquots as a function of depth. 13C cross-polarization magic angle spinning (13C{1H} CP-MAS NMR) spectra and variable contact time (VCT) experiments have been carried out to determine the cellulose crystallinity index, the lignin condensation degree and the holocellulose-lignin ratio. The interactions between the resin and the wood components were highlighted by T1ρH relaxation times determination and two-dimensional 13C–1H correlation (FSLG CP HETCOR) NMR experiments. Findings revealed specific interactions between the aromatic part of the resin and the lignin, as well as a network of hydrogen bonds involving all components of the system.

Unexpected behavior of commercial artists’ acrylic paints under UVA artificial aging

The study of the behavior of acrylic paints after UV-A (400–300 nm, near UV) artificial exposure was further investigated by extending it to more commercially available artists’ acrylic paints. The accelerated aging of eight acrylic-based commercial paints was studied using a combination of analytical techniques including Nuclear Magnetic Resonance (NMR) spectroscopies, Pyrolysis coupled with Gas Chromatography/Mass Spectrometry (Py-GC/MS), Fourier Transform Infrared in ATR mode (FTIR-ATR), Direct Analysis in Real Time coupled to Mass Spectrometry (DART-MS) and microscopic techniques, such as Stereoscopic Microscopy (SM) and Scanning Electron Microscopy coupled with Energy Dispersive X-ray Spectroscopy (SEM-EDS). All the aging process was characterized and monitored to study the signs of decay. During the aging process a gradual loss of the organic surfactant occurred in all the paints, similar to the results contained in a previous study. Interestingly, two of the studied paints presented an unexpected behavior related to the properties of the acrylic binder. In one of such paints solid-state 13C Cross Polarization Magic Angle Spinning (13C CPMAS) NMR spectroscopy was performed. The results obtained by changing the recycled delay and carrying out variable temperature experiments, suggested a change in the internal mobility of the aged sample that could be attributed to the presence of ionomers.According to this study, the aging of acrylic binders may not be the same in all paints and may be affected by the interaction of different components of the formulation. Understanding these processes will give more tools for the preservation of modern art paintings and cultural heritage since this type of commercial paints and other conservation materials of the same composition were extensively used during the 20th century.

Fabrication of Conjugated Porous Polymer Catalysts for Oxygen Reduction Reactions: A Bottom-Up Approach

The present study demonstrates the fabrication of a conjugated porous polymer (CPP-P2) through a Pd-catalyzed Suzuki–Miyaura poly-condensation reaction. 13C cross-polarization solid-state NMR and Fourier transform infrared (FTIR) spectroscopy were used to characterize CPP-P2. Pristine nitrogen-containing CPP was explored as a catalyst for the oxygen reduction reaction in 0.1 M KOH aqueous alkaline media. In the case of CPP-P2,the polymer oxygen reduction reaction occurs via a four-electron transfer mechanism. An understanding of the oxygen reduction at the molecular level and the role of molecular packing in the three-dimensional structure was proposed based on density functional theory (DFT) modeling.

Molecular characterization of ombrotrophic peats by humeomics

BackgroundAn insight into the molecular composition of ombrotrophic peats of different geographical origin and collected at different depths was achieved by the humeomics method. The humeomic fractionation allowed the separation of molecular components in either organic solvents or water on the basis of their progressive binding strength to the humic matrix. The solubilized matter in fractions was analyzed by gas chromatography–mass spectrometry (GC–MS) or by proton nuclear magnetic resonance (1H NMR) spectroscopy, while the residues depleted of the extracted material were observed by 13C cross-polarization magic-angle-spinning nuclear magnetic resonance (13C-CPMAS-NMR) spectroscopy.ResultsThe analytical characterization of fractions and residues differentiated peats not only on the basis of the different classes of extracted molecules, but also on their binding strength to the complex peat matrix. Aromatic, lipidic, and sugar compounds were the most representative molecular classes extracted in the humeomic fractions and their abundance varied with depth. The distribution and abundance of extracted compounds provided an indication of the extent of organic matter accumulation in peat. The NMR spectra of solid residues supported the interpretation of the characteristics of the various extracts.ConclusionsOur findings proved that the humeomic approach allows to provide important information on both the molecular composition of peats and its variation with depth.

Chain-folded lamellar structure and dynamics of the crystalline fraction of Bombyx mori silk fibroin and of (Ala-Gly-Ser-Gly-Ala-Gly)n model peptides

Solid-state NMR is a powerful analytical technique to determine the composite structure of Bombyx mori silk fibroin (SF). In our previous paper, we proposed a lamellar structure for Ala-Gly copolypeptides as a model of the crystalline fraction in Silk II. In this paper, the structure and dynamics of the crystalline fraction and of a better mimic of the crystalline fraction, (Ala-Gly-Ser-Gly-Ala-Gly)n (n = 2–5, 8), and 13C selectively labeled [3-13C]Ala-(AGSGAG)5 in Silk II forms, were studied using structural and dynamical analyses of the Ala Cβ peaks in 13C cross polarization/ magic angle spinning NMR and 13C solid-state spin-lattice relaxation time (T1) measurements, respectively. Like Ala-Gly copolypeptides, these materials have lamellar structures with two kinds of Ala residues in β-sheet, A and B, plus one distorted β-turn, t, formed by repetitive folding using β-turns every eighth amino acid in an antipolar arrangement. However, because of the presence of Ser residues at every sixth residue in (AGSGAG)n, the T1 values and mobilities of B decreased significantly. We conclude that the Ser hydroxyls hydrogen bond to adjacent lamellar layers and fix them together in a similar way to Velcro®.

Molecular Crystal Forms of Antitubercular Ethionamide with Dicarboxylic Acids: Solid-State Properties and a Combined Structural and Spectroscopic Study.

We report on the preparation, characterization, and bioavailability properties of three new crystal forms of ethionamide, an antitubercular agent used in the treatment of drug-resistant tuberculosis. The new adducts were obtained by combining the active pharmaceutical ingredient with three dicarboxylic acids, namely glutaric, malonic and tartaric acid, in equimolar ratios. Crystal structures were obtained for all three adducts and were compared with two previously reported multicomponent systems of ethionamide with maleic and fumaric acid. The ethionamide-glutaric acid and the ethionamide-malonic acid adducts were thoroughly characterized by means of solid-state NMR (13C and 15N Cross-Polarization Magic Angle Spinning or CPMAS) to confirm the position of the carboxylic proton, and they were found to be a cocrystal and a salt, respectively; they were compared with two previously reported multicomponent systems of ethionamide with maleic and fumaric acid. Ethionamide-tartaric acid was found to be a rare example of kryptoracemic cocrystal. In vitro bioavailability enhancements up to a factor 3 compared to pure ethionamide were assessed for all obtained adducts.

Component Quantification in Solids with the Mixture Analysis Using References Method.

Quantifying components in solid mixtures composed of the same chemical species exhibiting different physical forms represents a difficult challenge in many areas of chemistry. The development of small-molecule active pharmaceutical ingredients (APIs) is a classic example. APIs predominantly exhibit polymorphism and the propensity to form solvates and hydrates. The various API phases typically display different physical properties affecting chemical stability, processability, and bioperformance. Accordingly, API development critically relies on characterizing and quantifying the relevant API forms in complex mixtures in the presence of each other and in the presence of excipients. Presented here is a new solid-state-NMR-based quantification method for components in solid mixtures: mixture analysis using references (MAR). The method utilizes weighted pure component reference spectra in a linear combination fitting procedure to reproduce the corresponding mixture spectrum. The results yield the respective component contributions to the mixture composition. Using several model systems of varying complexity, the applicability and performance of the MAR analysis utilizing 13C and 19F cross-polarization magic-angle-spinning data are evaluated. Finally, the MAR method is compared to one of the most commonly applied traditional quantification methods. The results demonstrate that MAR performs with the same high accuracy as conventional methods. However, MAR exhibits clear efficiency advantages over conventional methods by requiring significantly less overall time (experimental and computational) and displaying remarkable robustness and general applicability. The MAR quantification protocol as presented here can easily be applied to nonpharmaceutical molecular systems in other branches of chemistry.

Improving the compatibility, surface strength, and dimensional stability of cellulosic fibers using glycidyl methacrylate grafting

The graft copolymerization of lignocellulosic fibers with glycidyl methacrylate (GMA) using a Fe2+–thiourea dioxide–H2O2 redox system (Fe2+–TD–H2O2) was studied to overcome the problems of poor compatibility and low surface strength when cellulosic fibers are composited with synthetic polymers. The results show that cellulose–poly(GMA) (CPGMA) was successfully synthesized from GMA and bleached Eucalyptus cellulosic fibers by Fe2+–TD–H2O2 in a mild aqueous solution. CPGMA had high graft rate (244%), high content of epoxy group, and high stability in water. X-ray diffraction patterns and 13C cross-polarization magic angle spinning nuclear magnetic resonance spectra analyses showed that graft copolymerization did not change the crystalline structure of the CPGMA fiber backbone cellulose, but the crystallinity of the CPGMA fiber decreased with an increase in amorphous PGMA grafting. Scanning electron microscopy confirmed that the grafting reaction occurred both inside and outside the fiber. The specific surface area and pore diameter of the grafted fibers were significantly affected by the grafting. The hydrophobicity of the fibers was significantly enhanced by graft copolymerization. PGMA grafting can enhance the compatibility between the modified fiber and synthetic polymer matrix, improving the processing runnability and product properties of composite materials. A high intensity focused ultrasound method was used to analyze the fiber surface strength. It was confirmed that graft copolymerization significantly improved the surface strength of the grafted fibers. Graft copolymerization can significantly improve the dimensional stability of cellulosic fibers.

Synthesis and Solid-State Dynamics of a Crystalline Steroid Molecular Rotor without the Alkyne Axle: Steroid Dimers Based on a 1,4-Di(1,3-dioxan-2-yl)benzene Moiety.

Two diastereomeric crystalline steroid dimers were obtained by acid-catalyzed double acetalization of (20S)-5α-pregnan-3β,16β,20-triol 3-monoacetate with terephtalaldehyde. These compounds were characterized by NMR in solution, MS, single-crystal X-ray diffraction, and variable-temperature solid-state NMR by 13C cross-polarization magic angle spinning (CPMAS). While the phenylene rotator in the SR diastereomer remains static even at 373 K, the RR isomer shows a slow rotational process of the phenylene ring at temperatures above room temperature and thus may be considered the first crystalline steroid molecular rotor without the alkyne axle.

Physical aspects of the biopolymer matrix in wheat bran and its dissected layers

The objectives of this work were to 1) determine the physical structure of untreated wheat bran and the differences in physical structure between its dissected layers; 2) evaluate how bran hydration affected bran crystallinity and polymer order; and 3) determine how enzymatic treatment of wheat bran affected its physical structure. For the first time, X-ray diffraction (XRD), small angle X-ray scattering (SAXS), solid-state 13C cross-polarization magic-angle spinning nuclear magnetic resonance (13C CP/MAS NMR), and polarized light microscopy with a waveplate were used to study the physical structure of wheat bran and its dissected layers. The XRD and solid-state 13C CP/MAS NMR both confirmed the presence of crystalline cellulose in untreated bran, enzymatically treated bran, and dissected bran layers. The outer pericarp had the highest crystallinity of the dissected bran layers and showed negative birefringence. The aleurone layer was low in cellulose content and completely amorphous, yet the cell walls in the aleurone layer showed strong positive birefringence. The treatment of destarched and deproteinated bran with the Updegraff reagent removed amorphous material, leaving its crystalline cellulose structure intact. Hydration of the outer pericarp increased its crystallinity index and CP/MAS NMR resonance intensity, which indicated a possible increase in polymer order. The SAXS also confirmed that cell wall polymers, possibly aggregated cellulose microfibrils, increased in order as a result of hydration.

Carboxylated Cellulose Nanocrystals Developed by Cu-Assisted H2O2 Oxidation as Green Nanocarriers for Efficient Lysozyme Immobilization.

Cellulose nanocrystals (CNCs), having a high specific surface area and versatile surface chemistry, provide considerable potential to interact by various mechanisms with enzymes for nano-immobilization purposes. However, engineering chemically safe CNCs, suitable for edible administrations, presents a significant challenge. A reliable carboxylate form of H-CNCs was formed using H2O2 oxidation of softwood pulp under mild thermal conditions. Negatively charged carboxyl groups (∼0.9 mmol g-1) played a key role in lysozyme immobilization via electrostatic interactions and covalent linkages, as evidenced by Fourier transform infrared and 13C cross-polarization magic angle spinning nuclear magnetic resonance spectroscopies. Adsorption isotherms showed a high loading capacity of H-CNCs (∼240 mg g-1), and fitting the data to the Langmuir model confirmed monolayer coverage of lysozyme on their surface. Using a non-toxic coupling agent, 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride, lysozyme-conjugated H-CNCs were developed with an immobilization yield of ∼65% and relative catalytic activity of ∼60%, similar to lysozyme adsorption on H-CNCs. These H-CNC-lysozyme nanohybrids, rationally processed via safe and green strategies, are specifically exploitable as catalytically active emulsifiers in food and pharmaceutical sectors.

2-Mercaptopyrimidine-functionalized mesostructured silicas to develop electrochemical sensors for a rapid control of scopolamine in tea and herbal tea infusions

Mesostructured silicas were synthesized and chemically functionalized with a 2-mercaptopyrimidine (MPY)-derivative. Bare and functionalized silicas (MSU-2, HMS, SBA-15, MSU-2-MPY, HMS-MPY and SBA-15-MPY) were characterized by powder X-ray diffraction, nitrogen adsorption-desorption isotherms, transmission electron and scanning electron microscopy, 29Si and 13C cross-polarization magic-angle spinning NMR spectroscopy and elemental analysis, and used to prepare modified carbon paste electrodes (CPEs). The electrodes properties were studied using potassium ferrocyanide and scopolamine as probes employing cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Results proved that MPY groups on the silica surface were necessary to improve the sensitivity in the voltammetric determination of scopolamine. CPE modified with HMS-MPY exhibited higher peak current toward the oxidation of scopolamine, with a well-defined oxidation peak at + 1.1 V (vs. Ag/AgCl) in DPV. This fact can be attributed to the high electroactive area of this material, with 3 D wormhole-like channel structure that favored the scopolamine diffusion. Under optimum conditions, HMS-MPY-CPE exhibited a wider linearity range, from 0.9 to 200 μM, with a detection limit of 0.3 μM and good reproducibility by DPV. The developed sensor was successfully applied for a rapid determination of scopolamine in spiked tea and herbal tea infusion samples with good recoveries (between 83 ± 5 and 101 ± 1%).