Anisotropic composite aerogel with thermal insulation and flame retardancy from cellulose nanofibers, calcium alginate and boric acid.

With the increasing severity of energy shortages and environmental pollution, there is an urgent need for advanced thermal insulation materials with excellent comprehensive performance, including low thermal conductivity, high flame resistance, and strong compressive strength. Herein, an anisotropic composite aerogel based on cellulose nanofibers (CNF), calcium alginate (CA), and boric acid (BA) is fabricated using a directional freeze-drying strategy. The CA and BA, as double cross-linking agents, associated with oriented porous structure provide the resultant aerogel with good mechanical strength. Additionally, self-flame retardant CA and BA act as synergistic flame retardants that endow the aerogel with excellent flame retardance properties such as a limiting oxygen index value of 44.2 %, UL-94 V-0 rating, and low heat release. Furthermore, this composite aerogel exhibits outstanding thermal insulation performance with a low thermal conductivity of approximately 30 mW m-1 K-1. Therefore, the composite aerogel is expected to have a wide potential application in areas such as construction, automotive industry, batteries, petrochemical pipelines, and high-temperature reaction devices.

Synthesis of terpinyl acetate from α-pinene catalyzed by α-hydroxycarboxylic acid-boric acid composite catalyst.

To enhance the yield of the one-step synthesis of terpinyl acetate from α-pinene and acetic acid, this study evaluated α-hydroxycarboxylic acid (HCA)-boric acid composite catalysts based on orthogonal experimental design. The most important factor affecting the terpinyl acetate content in the product was the HCA content. The catalytic performance of the composite catalyst was related to the pKa1 of HCA. The tartaric acid-boric acid composite catalyst showed the highest catalytic activity. The α-pinene conversion reached 91.8%, and the terpinyl acetate selectivity reached 45.6%. When boric acid was replaced with B2O3, the HCA composite catalyst activity was enhanced, which reduced the use of HCA. When the lactic acid and B2O3 content accounted for 10% and 4% of the α-pinene mass content, respectively, the α-pinene conversion reached 93.2%, and the terpinyl acetate selectivity reached up to 47.1%. In addition, the presence of water was unfavorable to HCA-boric acid composite catalyst. However, a water content less than 1% of the α-pinene mass content improved the catalytic activity of HCA-B2O3. When the tartaric acid-B2O3 was used as catalyst, and the water content was 1% of the α-pinene mass content, the α-pinene conversion was 89.6%, and the terpinyl acetate selectivity was 47.5%.

Boric acid intercepts 80S ribosome migration from AUG-stop by stabilizing eRF1.

In response to environmental changes, cells flexibly and rapidly alter gene expression through translational controls. In plants, the translation of NIP5;1, a boric acid diffusion facilitator, is downregulated in response to an excess amount of boric acid in the environment through upstream open reading frames (uORFs) that consist of only AUG and stop codons. However, the molecular details of how this minimum uORF controls translation of the downstream main ORF in a boric acid-dependent manner have remained unclear. Here, by combining ribosome profiling, translation complex profile sequencing, structural analysis with cryo-electron microscopy and biochemical assays, we show that the 80S ribosome assembled at AUG-stop migrates into the subsequent RNA segment, followed by downstream translation initiation, and that boric acid impedes this process by the stable confinement of eukaryotic release factor 1 on the 80S ribosome on AUG-stop. Our results provide molecular insight into translation regulation by a minimum and environment-responsive uORF.

Boric acid-functionalized silver nanoparticles as SERS substrate for sensitive and rapid detection of fructose in artificial urine.

The accurate detection of fructose in human urine can help prevent and screen for diseases such as fructokinase deficiency and hereditary fructose intolerance. Surface-enhanced Raman spectroscopy (SERS) is an analytical technique with selectivity and high sensitivity, which has been widely applied to the detection of targets with complex backgrounds. In this work, 4-mercaptophenylboronic acid (4-MPBA) was modified on the surface of silver nanoparticles (AgNPs) under mild conditions to obtain a boronic acid-functionalized SERS substrate for the detection of fructose in artificial urine. The detection mechanism was based on the deboronization reaction of 4-MPBA on the surface of AgNPs, which was induced by fructose, and the Raman signal of the generated thiophenol (TP) molecules was significantly enhanced by the silver nanoparticles, with a linear increase in SERS peak intensity at 1570 cm-1. We achieved the detection limits of 0.084 µmol/L in water and 0.535 µmol/L in urine by this method. The relative standard deviation (RSD) in the recovery experiments of urine ranged from 1.01 % to 2.22 %, and the whole detection time was less than 10 min, which indicated that this method is highly reliable for fructose detection and has a good prospect in bioassay and clinical medicine.

Aesculetin Exhibits Strong Fluorescent Photoacid Character.

Coumarins are bioactive molecules that often serve as defenses in plant and animal systems, and understanding their fundamental behavior is essential for understanding their bioactivity. Aesculetin (6,7-dihydroxycoumarin) has recently attracted attention due to its ability to act as an antioxidant, but little is known about its photophysical properties. The fluorescence lifetimes of its neutral and anion form in water are 19 ± 2 ps and 2.3 ± 0.1 ns, respectively. Assuming the short lifetime of the neutral is determined by ESPT, we estimate kPT ~ 5 × 1010 s-1. Using steady-state and time-resolved fluorescence spectroscopy, we determine its ground and excited-state [Formula: see text] to be 7.3 and -1, respectively, making it one of the strongest photoacids of the natural coumarins. Aesculetin exhibits a strong pH dependence of the relative fluorescence quantum yield becoming much more fluorescent above [Formula: see text]. The aesculetin anion [Formula: see text] slightly photobasic character. We also report that aesculetin forms a fluorescent catechol-like complex with boric acid, and this complex has a [Formula: see text] of 5.6.

B- and N-doped carbon dots by one-step microwave hydrothermal synthesis: tracking yeast status and imaging mechanism.

BACKGROUND: Carbon dots (CDs) are widely used in cell imaging due to their excellent optical properties, biocompatibility and low toxicity. At present, most of the research on CDs focuses on biomedical application, while there are few studies on the application of microbial imaging. RESULTS: In this study, B- and N-doped carbon dots (BN-CDs) were prepared from citric acid, ethylenediamine, and boric acid by microwave hydrothermal method. Based on BN-CDs labeling yeast, the dead or living of yeast cell could be quickly identified, and their growth status could also be clearly observed. In order to further observe the morphology of yeast cell under different lethal methods, six methods were used to kill the cells and then used BN-CDs to label the cells for imaging. More remarkably, imaging of yeast cell with ultrasound and antibiotics was significantly different from other imaging due to the overflow of cell contents. In addition, the endocytosis mechanism of BN-CDs was investigated. The cellular uptake of BN-CDs is dose, time and partially energy-dependent along with the involvement of passive diffusion. The main mechanism of endocytosis is caveolae-mediated. CONCLUSION: BN-CDs can be used for long-term stable imaging of yeast, and the study provides basic research for applying CDs to microbiol imaging.

Chitosan-based hydrogel crosslinked through an aza-Michael addition catalyzed by boric acid.

Polysaccharide-based hydrogels are particularly attractive materials for biomedical applications. However, their use is restricted due to their brittleness and poor mechanical properties. Here, to overcome such limitations, we report an original, green, simple, and efficient strategy to synthesize a polysaccharide-based hydrogel of chitosan (Cht) and a vinyl-functionalized PVA (PVA-MA), a non-toxic synthetic polymer that is widely known to improve the mechanical properties and stability of materials containing polysaccharides. The hydrogel was crosslinked through an aza-Michael addition among the amino groups of Cht with the vinyl moieties of PVA-MA catalyzed by boric acid (B(OH)3), an eco-friendly inorganic compound. Characterization analyses revealed that the prepared hydrogel has a porous-like morphology, an outstanding liquid uptake capacity (>665%), and improved stability in a physiological fluid for long periods. In summary, this original and simple strategy showed to be efficient in the synthesis of hydrogels with attractive properties for the biomedical field application.

Development and Characterization of Ulvan Polysaccharides-Based Hydrogel Films for Potential Wound Dressing Applications.

BACKGROUND: Ulvan is a natural polymer and type of sulfated polysaccharides from green seaweed that could have potential as a candidate for wound dressing material based on the support of its biopolymer characteristics such as antioxidant and antimicrobial activities. OBJECTIVE: In this study, we developed and prepared three different hydrogel films to explore the potency of ulvan for wound dressing application. METHODS: Ulvan hydrogel films were prepared by the facile method through ionic crosslinking with boric acid and added glycerol as a plasticizer. The films were evaluated in regard to swelling degree, water vapor transmission (WVTR), Fourier transform infrared (FTIR), powder x-ray diffractometry (P-XRD), scanning electron microscopy (SEM), mechanical properties, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), antimicrobial, and antioxidant activity. RESULTS: The hydrogel films showed that the different concentration of ulvan in the formula affects the characteristics of the hydrogel film. The higher the concentration of ulvan in UHF, the higher the value of viscosity (201±13.45 to 689±62.23 cps for UHF5 to UHF10), swelling degree (82% to 130% for UHF5 to UHF10 at 1 h), moisture content (24%±1.94% to 18.4%±0.51 for UHF5 to UHF10), and the WVTR were obtained in the range 1856-2590g/m2/24h. Meanwhile, the SEM showed porous hydrogel film. Besides, all hydrogel films can reduce hydroxyl radicals and inhibit gram-positive and negative bacteria (Staphylococcus aureus, Pseudomonas aeruginosa, Escherichia coli, and Streptococcus epidermidis). CONCLUSION: The swelling behavior and WVTR of these films are great and could have potential as a wound dressing biomaterial, supported by their antimicrobial and antioxidant properties.

Post-synthesis of boric acid-functionalized magnetic covalent organic framework as an affinity probe for the enrichment of N-glycopeptides.

A novel type of boric acid-functionalized magnetic covalent organic framework (mCOF) with polyethyleneimine (PEI) as a linker (denoted as mCOF@PEI@B(OH)2) has been prepared through a post-synthesis strategy, which points out an achievable path for the construction of boronic acid-functionalized COFs. Based on the boric acid chemistry, the obtained core-shell structured mCOF@PEI@B(OH)2 can selectively isolate glycopeptides through the modified boronic acid groups. The mCOF@PEI@B(OH)2 exhibits excellent performance with good reusability (ten cycles), low detection limit (0.5 fmol·µL-1), size-exclusion effect, and relatively high loading capacity (80 µg·mg-1), recovery yield (94.9 ± 2.8%), and selectivity (HRP digests:BSA digests = 1:500). Detection is done by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). In addition, 37 endogenous glycopeptides are captured from human saliva with mCOF@PEI@B(OH)2, providing effective proofs for its capability to capture low-abundance glycopeptides from actual biological samples.

[Preparation of branched polyethyleneimine-assisted boric acid-functionalized magnetic nanoparticles and its application to selective enrichment of ginsenoside Re].

Panax ginseng has a 5000-year-long history as a traditional herbal medicine in Eastern Asia and North America. It is also known as crown jewel in traditional Chinese herbs because of its wide pharmacological properties. Ginsenosides, a class of saponins containing triterpene aglycones and various sugar moieties, are the main active components of ginseng. Considering the low abundance of ginsenosides and other abundant interferences, separation of ginsenosides is essential prior to further analysis. Recently, our group demonstrated the potential of a boronate affinity material for the selective enrichment of ginsenosides. However, conventional boronate affinity materials suffer from an apparent drawback. The binding strength of boronic acids toward cis-diol-containing compounds is low, with dissociation constants (Kd) ranging from 10-1 to 10-3mol/L. Thus, it is necessary to develop boronate affinity materials with high binding strength. In this study, we developed polyethyleneimine (PEI)-functionalized boronate affinity magnetic nanoparticles (BA-MNPs) for the selective enrichment of ginsenosides. Branched PEI was applied as a scaffold to amplify the number of boronic acid moieties, while 3-formylphenylboronic acid, which shows high affinity toward cis-diol-containing molecules, was used as the affinity ligand. In addition, the presence of the multi-glycan structure of ginsenoside leads to higher binding affinity between the PEI-BA-MNPs due to the synergistic multivalent binding effect. Combining with high performance liquid chromatography, a method for the selective analysis of ginsenosides was established. With ginsenoside Re as the representative and under the optimized conditions for magnetic solid-phase extraction, the developed method showed good linearity in the range of 50-800 µg/L, with a linear correlation coefficient (R2) of 0.9681. At different spiked levels (0.1-10 mg/L), the recoveries were in the range of 91.5%-117.3%, and the relative standard deviations (RSDs) ranged from 7.2% to 13.4%. Since the PEI-BA-MNPs exhibited significantly improved binding strength toward ginsenosides, they could extract trace glycoproteins. After enrichment, a 50-fold improvement in the sensitivity was achieved. In addition, the PEI-BA-MNPs maintained at least 72% of their original binding capacity after five consecutive uses. Finally, the developed method was applied to the determination of ginsenoside Re in commercial medicine (Qipi oral liquid). As opposed to the tedious and time-consuming sample preparation in the standard method (Pharmacopoeia of the People's Republic of China, 2015; ChP2015), the present protocol allowed for direct enrichment of the diluted commercial medicine with PEI-BA-MNPs. The magnetic separation made the overall experiment much simpler than the standard ChP2015 method. After washing and elution, the enriched ginsenoside Re was eluted and subjected to HPLC-UV analysis. The results obtained with the developed method (0.27%) were similar to those of ChP2015 (0.31%). We have experimentally demonstrated that PEI-BA-MNPs are ideal affinity sorbents for the selective enrichment of ginsenosides owing to their significant advantages, including high affinity, excellent selectivity, easy manipulation, high binding capacity, and fast binding equilibrium. As many saponins contain sugar side chains, we foresee a promising prospect for the proposed method in real-world applications.

Synthesis of dextrin-polyacrylamide and boric acid based tough and transparent, self-healing, superabsorbent film.

Stretchabiliy, transparency and self-healing ability of bio-based materials are some of the important features for their utilization in the biomedical field. Recently, robust self-healing super porous materials possessing multifunctional nature have raised enormous interest among the researchers in order to design different materials which can be used in industrial, biomedical and pharmaceutical fields. Herein, a novel self-healing, stretchable and transparent superabsorbent film based on Dextrin-polyacrylamide and Boric Acid (DEX-cl-polyAAm) was synthesized using a free radical reaction mechanism. In distilled water, the maximum water absorptivity of the synthesized film was reported to be 3156% after the optimization of various reaction parameters. The film was also found to show structural integrity in urea solution, phosphate buffer and solutions of different pH. Lastly, the viscoelastic and self-healing analysis of the film suggested its utility towards biomedical field.

Rapid capillary gel electrophoresis analysis of human milk oligosaccharides for food additive manufacturing in-process control.

Industrial production of human milk oligosaccharides (HMOs) represents a recently growing interest since they serve as key ingredients in baby formulas and are also utilized as dietary supplements for all age groups. Despite their short oligosaccharide chain lengths, HMO analysis is challenging due to extensive positional and linkage variations. Capillary gel electrophoresis primarily separates analyte molecules based on their hydrodynamic volume to charge ratios, thus, offers excellent resolution for most of such otherwise difficult-to-separate isomers. In this work, two commercially available gel compositions were evaluated on the analysis of a mixture of ten synthetic HMOs. The relevant respective separation matrices were then applied to selected analytical in-process control examples. The conventionally used carbohydrate separation matrix was applied for the in-process analysis of bacteria-mediated production of 3-fucosyllactose, lacto-N-tetraose, and lacto-N-neotetraose. The other example showed the suitability of the method for the in vivo in-process control of a shake flask and fermentation approach of 2'-fucosyllactose production. In this latter instance, borate complexation was utilized to efficiently separate the 2'- and 3-fucosylated lactose positional isomers. In all instances, the analysis of the HMOs of interest required only a couple of minutes with high resolution and excellent migration time and peak area reproducibility (average RSD 0.26% and 3.56%, respectively), features representing high importance in food additive manufacturing in-process control.

First Characterization of the Formation of Anthocyanin-Ge and Anthocyanin-B Complexes through UV-Vis Spectroscopy and Density Functional Theory Quantum Chemical Calculations.

The occurrence of anthocyanin (ACN) and metal (Me) complexes has been widely supported by many research works while the possibility that ACNs bind to metalloids (Mds) is yet to be proven. Here, metalloids (H3BO3 for B; GeO2 for Ge) were added to cyanidin-based solutions at pH 5, 6, and 7 and ACN-Md stoichiometric ratios of 1:1, 1:10, 1:100, and 1:500, and UV-vis transmittance spectroscopy as well as density functional theory (DFT) calculations were performed to test this hypothesis. Ge and B addition caused bathochromic and hyperchromic shifts on ACN UV-vis spectra, particularly pronounced at pH 5 and a 1:500 (ACN:Md) ratio. ACN-Me complexation reactions have been evaluated where Ge showed a higher capability to bind to ACNs than B. Among the complexes envisioned, those labeled as b1, b2, and b3 feature UV-vis spectra compatible with experiments. The combination of experimental and computational data offers for the first time evidence of the formation of ACN-Md complexes.

Polymers Based on Phenyl Boric Acid in Tumor-Targeted Therapy.

BACKGROUND: Tumors are still among the major challenges to human health. Tumor-targeted therapy is an effective way to treat tumors based on precise medical models. Sialic acid (SA) is overexpressed on the surface of tumor cells, and Phenyl Boric Acid (PBA) can specifically bind to SA. However, studies on the use of PBA in tumor-targeted therapy are few. OBJECTIVE: To summarize and analyze the characteristics and influencing factors of tumor targeted therapy in recent years, and the influencing factors of phenyl boric acid modified polymers in tumor targeted therapy, such as hydrogen ion concentration (pH), Adenosine Triphosphate (ATP), and sugars. This paper describes the application of phenyl boric acid partially functionalized nano-polymers in various types of targeted tumors, such as breast cancer, lung adenocarcinoma, liver cancer, and so forth. In order to further improve the basic research and clinical workers' understanding of nano-preparations and tumor targeted therapy. At the same time, it is also expected to promote the development value of phenyl boric acid. METHODS: The findings on tumor-targeted therapy and the role of partially functionalized polymers with PBA in different tumors at home and abroad has been analyzed and summarized in recent years. RESULTS: Tumor-targeted therapy is a promising treatment for tumors. PBA promotes the treatment of tumors using SA, which is highly expressed on the surface of tumor cells. CONCLUSION: Tumor-targeted therapy has shown great prospects for clinical application in recent years. PBA is beneficial as a member of the drug loading system. Further studies are still needed to promote its development and application.

Effects of boric acid on urea-N transformation and 3,4-dimethylpyrazole phosphate efficiency.

BACKGROUND: 3,4-Dimethylpyrazole phosphate (DMPP) is a nitrification inhibitor which can restrict nitrate (NO3 - ) production. Boric acid is a substance which inhibits urease activity. However, few studies have focused on the inhibitory effect of boric acid on urea hydrolysis and the possible synergistic effect with DMPP. Thus, an incubation trial was conducted to determine the impact of boric acid and DMPP addition on urea-N transformation, and their synergistic effects, in chernozem soil (Che) and red soil (RS). Four treatments were set up in each soil: urea only (U); urea combined with DMPP (UD); urea combined with boric acid (UB); and urea combined with both DMPP and boric acid (UDB). RESULTS: Compared to U, adding DMPP (UD) increased NH3 emissions by 11% and 13% and decreased soil NO3 - -N concentration by 38% and 13% in Che and RS, respectively. Boric acid addition (UB) effectively prolonged the half-life time of urea by 0.8 and 0.4 days, reduced NH3 volatilizations by 11% and 16% and delayed the occurrence of NH3 emission peaks for 3 and 4 days in contrast to U treatment in Che and RS, respectively. UDB treatment mitigated the NH3 volatilizations caused by the addition of DMPP (UD) by 16% and 29% in Che and RS, respectively. Additionally, a better nitrification inhibition rate was found in the UDB treatment compared to other treatments in both soils. CONCLUSIONS: There is potential to develop a new N transformation inhibition strategy with the use of a combination of boric acid and DMPP. © 2020 Society of Chemical Industry.

Sensitive and selective detection of glycoprotein based on dual-signal and dual-recognition electrochemical sensing platform.

Glycoproteins play extraordinary roles in biology and clinic. The specifically sensitive detection of glycoproteins by electrochemical methods is still a challenging task due to their poor electro-activity and sensitive nature to environment. In this work, ovalbumin (OVA), a model glycoprotein, was sensitively detected by a molecularly imprinted polymer (MIP) based electrochemical sensor, which was prepared by electropolymerizing 3-thiophene boric acid in the presence of OVA. Due to boronate affinity, the rebound OVA interacted with ferrocene boric acid (Fc-BA) to construct a sandwich structural sensing platform. Dual-recognition elements, imprinted effect and the boronate affinity, enabled the sensor to recognize OVA from other proteins. The rebinding of OVA caused the current changes of thionine and Fc-BA, which were combined as a dual-signal for OVA sensitive detection with a low limit of detection of 0.82 pg/mL (S/N = 3). The good performances of sensor indicated its potential applications in clinical diagnosis and other related fields.

Boric Acid-Fueled ATP Synthesis by Fo F1 ATP Synthase Reconstituted in a Supramolecular Architecture.

Significant strides toward producing biochemical fuels have been achieved by mimicking natural oxidative and photosynthetic phosphorylation. Here, different from these strategies, we explore boric acid as a fuel for tuneable synthesis of energy-storing molecules in a cell-like supramolecular architecture. Specifically, a proton locked in boric acid is released in a modulated fashion by the choice of polyols. As a consequence, controlled proton gradients across the lipid membrane are established to drive ATP synthase embedded in the biomimetic architecture, which facilitates tuneable ATP production. This strategy paves a unique route to achieve highly efficient bioenergy conversion, holding broad applications in synthesis and devices that require biochemical fuels.

Borate-modified carbon dots as a probe for quercetin in plants.

Quercetin has been proved to have high medicinal value, and as a type of flavonol, has been found in many plants. A simple, fast and effective detection of quercetin was developed according to the fluorescence enhancement by modified carbon dots (PBA-CDs). PBA-CDs were prepared by connecting phenylboronic acids (PBA) on the surface of carbon dots rich in amino groups. Due to the selective interactions of PBA with the cis-diol groups of quercetin and the additional hydrogen bonds, the intermolecular rotation of quercetin was inhibited, and then the fluorescence significantly increased. The selectivity of this method was proved and the linear ranges were estimated to be 0-28.5 µM with a limit of detection at 28.8 nM. Using this method, the quercetin content in the Ginkgo biloba leaf was measured as 42.28 mg·g-1. In addition, the PBA-CDs hold excellent biocompatibility and have demonstrated their ability to detect quercetin in living cells.

A Facile Strategy for Immobilizing GOD and HRP onto Pollen Grain and Its Application to Visual Detection of Glucose.

Pollen grain was explored as a new carrier for enzyme immobilization. After being modified with boric acid-functionalized titania, the pollen grain was able to covalently immobilize glycosylated enzymes by boronate affinity interaction under very mild experimental conditions (e.g., pH 7.0, ambient temperature and free of organic solvent). The glucose oxidase and horse radish peroxidase-immobilized pollen grain became a bienzyme system. The pollen grain also worked as an indicator of the cascade reaction by changing its color. A rapid, simple and cost-effective approach for the visual detection of glucose was then developed. When the glucose concentration exceeded 0.5 mM, the color change was observable by the naked eye. The assay of glucose in body fluid samples exhibited its great potential for practical application.

Boric-acid-modified Fe3O4@PDA@UiO-66 for enrichment and detection of glucose by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

Herein, boric-acid-modified multifunctional Zr-based metal-organic frameworks (denoted as Fe3O4@PDA@B-UiO-66) were synthesized by hydrothermal reaction and surface modification. Compared to traditional matrix, Fe3O4@PDA@B-UiO-66 has the advantages of high ionization efficiency, high surface area, low matrix background, porous structure, and numerous boric-acid-active sites. By combining matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS), Fe3O4@PDA@B-UiO-66 was used as an adsorbent and matrix for enrichment and detection of glucose, based on a specific reaction between boric acid and glucose. The limit of detection was 58.5 nM. The proposed method provides a simple and efficient approach for the sensitive and quantitative detection of glucose in complex samples based on MALDI-TOF MS. Design and synthesis of boric-acid-modified multifunctional magnetic metal-organic frameworks (designated as Fe3O4@PDA@B-UiO-66) applied as adsorbent and matrix for the matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) analysis of glucose in complex biosamples.