In Situ Growth of MOF from Wood Aerogel toward Bromide Ion Adsorption in Simulated Saline Water.

Utilizing metal-organic framework (MOF) materials for the extraction of bromide ions (Br-) from aqueous solutions, as an alternative to chlorine gas oxidation technology, holds promising potential for future applications. However, the limitations of powdered MOFs, such as low utilization efficiency, ease of aggregation in water, and challenging recovery processes, have hindered their practical application. Shaping MOF materials into application-oriented forms represents an effective but challenging approach to address these drawbacks. In this work, a novel Ag-UiO-66-(OH)2@delignified wood cellulose aerogel (CA) adsorbent is synthesized using an oil bath impregnation method, involving the deposition of UiO-66-(OH)2 nanoparticles onto CA and the uniform dispersion of Ag0 nanoparticles across its surface. CA, characterized by the intertwined cellulose nanofiber structure and a highly hydrophilic surface, serves as an ideal substrate for the uniform growth of UiO-66-(OH)2 nanoparticles, which, in turn, spontaneously reduce Ag+ to form distributed Ag0 nanoparticles due to the abundant hydroxyl groups provided. Leveraging the well-defined biological structure of CA, which offers excellent mass transfer channels, and the highly dispersed Ag adsorption sites, Ag-UiO-(OH)2/CA exhibits remarkable adsorption capacity (642 mg/gAg) under optimized conditions. Furthermore, an integrated device is constructed by interconnecting Ag-UiO-(OH)2/CA adsorbents in series, affirming its potential application in the continuous recovery of Br-. This study not only presents an efficient Ag-UiO-(OH)2/CA adsorbent for Br- recovery but also sheds light on the extraction of other valuable elements from various liquid ores.

A capillary electrophoresis method for the determination of soluble monosaccharides in Ginkgo biloba leaves.

A method for the simultaneous determination of six monosaccharides by pre-column derivatization with 1-phenyl-3-methyl-5-pyrazolone and capillary electrophoresis was developed in this work. The derivatization (i.e., reaction temperature, capillary electrophoresis duration, and extraction number) and separation (i.e., pH and buffer concentration) conditions for capillary electrophoresis were optimized. Results showed that the limits of detection under optimal conditions were in the range of 0.036-0.35 mg/L with a mean correlation coefficient >0.99. The recoveries were in the range of 87.3-108.49%, and the relative standard deviations of intra- and inter-day variations were in the ranges of 2.2-3.8 and 3.2-5.0%, respectively. The method was successfully applied to the analysis of six free monosaccharides in three types of Ginkgo biloba leaves.

Small molecule-mediated self-assembly behaviors of Pluronic block copolymers in aqueous solution: impact of hydrogen bonding on the morphological transition of Pluronic micelles.

The influence of hydrogen bonding on the self-assembly behaviors of Pluronic P123 micelles is experimentally and theoretically investigated by introducing three small molecules, i.e. propyl benzoate (PB), propyl paraben (PP) and propyl gallate (PG) into the aqueous solution. It is discovered that the number of phenolic hydroxyl groups and concentration of the tested small molecules exhibit a profound impact on the micellar morphology. Although all the small molecules increase the size and polydispersity of Pluronic micelles in a concentration-dependent manner, the micellar morphologies induced by them vary considerably as demonstrated by DLS and cryo-TEM measurement. PB, without phenolic hydroxyl, cannot bring about the morphological change of P123 micelles, while PP induces a series of morphological transitions from spheres to long worm-like micelles and then to unilamellar vesicles by increasing the PP content. Upon increasing the number of phenolic hydroxyls in small molecules, i.e. PG, the fusion of the intermicellar core takes place, resulting in the formation of large micelles and micellar clusters. A qualitative study by NMR reveals that the different locations of small molecules within the micelles are attributed to the balance of hydrogen bonding and hydrophobic interaction between small molecules and copolymers. In addition, molecular dynamics simulations (MDS) are performed to further confirm the experimental results and provide quantitative information on intermolecular interaction strength. It is supposed that the mechanism of micellar morphological transition mediated by small molecules is ascribed to the hydrogen bonding interactions with varying strengths between the PEO blocks and their phenolic hydroxyls, which governs their locations in micelles, affecting the free energies from different regions of micelles, and consequently leads to the varying micellar morphologies. This study deepens our understanding of the role of hydrgen bonding in the self-assembly behaviors of Pluronic micelles and provides an alternative strategy for manipulating the nanostructure of Pluronic micelles.

High-performance thin-layer chromatography coupled with HPLC-DAD/HPLC-MS/MS for simultaneous determination of bisphenol A and nine brominated analogs in biological samples.

Bisphenol A (BPA) and its brominated analogs exhibiting bioaccumulation potential, endocrine disruption, and reproductive toxicity have been worldwide detected in water, air, soil, and sediments. But few methods have been proposed for simultaneously determining a variety of these compounds in biological matrices, hindering the further study on their biological transformation/degradation and health risks. In this study, a simple, solvent-saving and sensitive method based on high-performance thin-layer chromatography (HPTLC) for sample pretreatment coupled with high-performance liquid chromatography-diode array detector (HPLC-DAD) (UV = 214 nm)/triple quadrupole mass spectrometry (MS/MS) was developed for determining BPA and its nine brominated analogs in biological samples. The method detection limits (MDLs) and method quantification limits (MQLs) for ten BPA analogs ranged from 0.8 to 685.7 ng g-1 dw (S/N = 3) and 2.7 to 2285.7 ng g-1 dw (S/N = 10), respectively. The recoveries were 64-124% with SD less than 10%. The RSD of intermediate precision was less than 11%, and matrix effects were lower than 19%. Compared with traditional purification procedures, HPTLC largely reduced the workload and procedures for complex biological sample cleanup without inducing decomposition of the analytes. The proposed method exhibited good performance when detecting these ten chemicals in chicken samples from a nearby yard of brominated flame retardant plants, indicating its great potential for investigating their environment level, behavior, and fate in organisms. Graphical abstract ᅟ.

Glycopolymer Grafted Silica Gel as Chromatographic Packing Materials.

The modification of the surface of silica gel to prepare hydrophilic chromatographic fillers has recently become a research interest. Most researchers have grafted natural sugar-containing polymers onto chromatographic surfaces. The disadvantage of this approach is that the packing structure is singular and the application scope is limited. In this paper, we explore the innovative technique of grafting a sugar-containing polymer, 2-gluconamidoethyl methacrylamide (GAEMA), onto the surface of silica gel by atom transfer radical polymerization (ATRP). The SiO2-g-GAEMA with ATRP reaction time was characterized by Fourier infrared analysis, Thermogravimetric analysis (TGA), and elemental analysis. As the reaction time lengthened, the amount of GAEMA grafted on the surface of the silica gel gradually increased. The GAEMA is rich in amide bonds and hydroxyl groups and is a typical hydrophilic chromatography filler. Finally, SiO2-g-GAEMA (reaction time = 24 h) was chosen as the stationary phase of the chromatographic packing and evaluated with four polar compounds (uracil, cytosine, guanosine, and cytidine). Compared with unmodified silica gel, modified silica gel produces sharper peaks and better separation efficiency. This novel packing material may have a potential for application with highly isomerized sugar mixtures.

Bare magnetic nanoparticles as fluorescence quenchers for detection of thrombin.

Rapid and sensitive detection of thrombin has very important significance in clinical diagnosis. In this work, bare magnetic iron oxide nanoparticles (magnetic nanoparticles) without any modification were used as fluorescence quenchers. In the absence of thrombin, a fluorescent dye (CY3) labeled thrombin aptamer (named CY3-aptamer) was adsorbed on the surface of magnetic nanoparticles through interaction between a phosphate backbone of the CY3-aptamer and hydroxyl groups on the bare magnetic nanoparticles in binding solution, leading to fluorescence quenching. Once thrombin was introduced, the CY3-aptamer formed a G-quartet structure and combined with thrombin, which resulted in the CY3-aptamer being separated from the magnetic nanoparticles and restoration of fluorescence. This proposed assay took advantage of binding affinity between the CY3-aptamer and thrombin for specificity, and bare magnetic nanoparticles for fluorescence quenching. The fluorescence signal had a good linear relationship with thrombin concentration in the range of 1-60 nM, and the limit of detection for thrombin was estimated as low as 0.5 nM. Furthermore, this method could be applied for other target detection using the corresponding fluorescence labeled aptamer.

Solvent effect on ζ potential at an aqueous/oil interface in surfactant-free emulsion.

The present study prepared a size-controllable, uniform, and surfactant-free emulsification to investigate the ζ potential of the solvent effect. The results showed that the ratio of electrophoretic mobility changed with droplet diameter, and the correct factor of the ζ potential was determined. The effect of functional groups on the ζ potential was further studied in the presence of an organic hydrophilic solvent. The study characterized the effects of pH, ionic strength, and ionic type on the ζ potential and indicated that the solvents were able to modulate the local electrochemical environment, thus leading to the redistribution of interface charges.

Solution-Phase Synthesis of KCl Nanocrystals Templated by PEO-PPO-PEO Triblock Copolymers Micelles.

The current work introduces the synthesis of inorganic salt nano/micro-crystals during the reduction of hydrogen tetrachloroaurate(III) by Pluronic triblock copolymers (P123, PEO20-PPO70-PEO20). The morphologies and component were confirmed using an electron microscope with an electronic differential system (EDS), and the crystal structures were determined with X-ray diffraction (XRD). The morphologies highly depend on the concentrations of Pluronic and pH values. The mean size of the nanocrystal and hollow micro-crystal were controlled typically in the range of 32-150 nm (side length) and 1.4 µm, respectively. Different from the electrospray-ionization (EI) method, a model in which KCl forms a supersaturated solution in the micellar core of Pluronic is used to explain the formation process. This work provides the new insight that inorganic salt nanocrystals could be synthesized with the template of micelles in pure aqueous solutions.

Analysis of Mogroside V in Siraitia grosvenorii with micelle-mediated cloud-point extraction.

INTRODUCTION: Mogroside V is the main effective ingredient of Siraitia grosvenorii used as a natural sweet food as well as a traditional Chinese medicine. The sample pre-treatment prior to chromatographic analysis requires large amounts of toxic organic solvents and is time consuming. OBJECTIVE: To develop an effective and simple method for extracting and determining mogroside V of Siraitia grosvenorii. METHODS: Mogroside V was extracted and preconcentrated by micelle-mediated cloud-point extraction with nonionic surfactant isotridecyl poly (ethylene glycol) ether (Genapol® X-080). The obtained solutions containing mogroside V were analysed by high-performance liquid chromatography (HPLC) with ultraviolet (UV) detection. The chromatographic separation was performed on a C18 -column using gradient elution with acetonitrile and water at 203 nm. RESULTS: The cloud-point extraction yield was 80.7% while the pre-concentration factor was about 10.8. The limit of detection was 0.75 µg/mL and the limit of quantification was 2 µg/mL. The relative standard deviations for intra- and interday precisions of mogroside V were less than 8.68% and 5.78%, respectively, and the recoveries were between 85.1% and 103.6%. CONCLUSION: The HPLC-UV method based on micelle-mediated cloud-point extraction for determination mogroside V in Siraitia grosvenorii was environmentally friendly, simple and sensitive.

Electrodialysis Deacidification of Acid Hydrolysate in Hemicellulose Saccharification Process: Membrane Fouling Identification and Mechanisms.

Acid saccharification of hemicelluloses offers promising pathways to sustainably diversify the revenue of the lignocellulose biorefinery industry. Electrodialysis to separate inorganic acids from acid hydrolysate in the hemicellulose saccharification process could realize the recovery of sulfuric acid, and significantly reduced the chemical consumption than the traditional ion exchange resins method. In this work, the deacidification of corncob acid hydrolysate was conducted by a homemade electrodialysis apparatus. The results showed that: (1) more than 99% of acid can be removed through the electrodialysis process; (2) A non-negligible membrane fouling occurred during the electrodialysis process, which aggravated with the repeated batch running The final global system resistance rose from 15.8 Ω (1st batch) to 43.9 Ω (10th batch), and the treatment ending time was delayed from 120 min (1st batch) to 162 min (10th batch); (4) About 90% of protein, 70% of ferulate acid, and 80% of p-coumarate acid precipitated from the corncob acid hydrolysate during the electrodialysis process. The zeta potential of corncob acid hydrolysate changed from a positive value to a negative value, and an isoelectric point around pH 2.3 was reached. HSQC, FTTR, and GPC, along with SEM and EDS analysis, revealed that the fouling layers mostly consisted of hydrolysates of protein and lignin. The result of HSQC indicated that the membrane foulant may exist in the form of lignin-carbohydrate complexes, as the lignin component of the membrane foulant is in the form of p-coumarate and ferulate. From the result of FTIR, a strong chemical bonding, such as a covalent linkage, existed between the lignin and protein in the membrane foulant. Throughout the electrodialysis process, the increased pH decreased the stability of colloidal particles, including lignin and proteins. Destabilized colloidal particles started to self-aggregate and form deposits on the anion exchange membrane's surface. Over time, these deposits covered the entire membrane surface and the spaces between the membranes. Eventually, they attached to the surface of the cation exchange membrane. In the end, a suggestion to control and minimize membrane fouling in this process was discussed: lower pH as a process endpoint and a post-treatment method.

Structural elucidation and targeted valorization of untractable lignin from pre-hydrolysis liquor of xylose production via a simple and robust separation approach.

Effective separation of lignin macromolecules from the xylose pre-hydrolysates (XPH) during the xylose production, thus optimizing the separation and purification process of xylose, is of great significance for reducing the production costs, achieving the high value-added utilization of lignin and increasing the industrial revenue. In this study, a simple and robust method (pH adjustment) for the separation of lignin from XPH was proposed and systematically compared with the conventional acid-promoted lignin precipitation method. The results showed that the lignin removal ratio (up to 60.34 %) of this simple method was higher than that of the conventional method, and the proposed method eliminated the necessity of heating and specialized equipment, which greatly reduced the separation cost. Meanwhile, this simple method does not destroy the components in XPH (especially xylose), ensuring the yield of the target product. On the other hand, the obtained lignin was nano-scale with less condensed structures, which also possessed small molecular weights with narrow distribution, excellent antioxidant activity (8-14 times higher than commercial antioxidants) and UV protection properties. In conclusion, the proposed simple separation method could effectively separate lignin from XPH at low cost, and the obtained lignin had potential commercial applications, which would further enhance the overall profitability of industrial production.

Spontaneous vesicle formation of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer.

A novel method has been developed to prepare vesicles from aqueous solutions of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer, by adding anionic surfactant sodium dodecyl sulfate (SDS) and inorganic salt NaF. As determined by TEM and dynamic light scattering (DLS) measurements, the average diameter of vesicles is about 800 nm having 50 nm outer shell thickness. Identifying hydrophobic interactions between the block copolymers and the microenvironments around the vesicles using FTIR, 1H NMR, and fluorescence spectroscopy techniques revealed the vesicle formation mechanism. The spontaneously formed vesicles were further cross-linked by converting the terminal hydroxyl groups of block copolymers into aldehydes, and then chemically bridging the polymer chains by the reaction between aldehydes and diamine compounds. The cross-linked vesicles are proved much more stable than free vesicles even at higher dilutions. The obtained vesicles with good stability and biocompatibility are promising candidates for widespread applications.

Simultaneous detection of anions and cations in mineral water by two dimensional ion chromatography.

A two dimensional ion chromatography (2D-IC) method was improved for the simultaneous determination of six cations and seven anions using one-valve switching after injection and conductivity detector. The trap conditions and valve-switch timing were optimized. The method has good accuracy and sensitivity for the simultaneous separation of inorganic anions and cations with a mean correlation coefficient of >0.99, repeatability of 0.60%-3.0% for eight replicates, reproducibility of 0.78%-3.1%, and spiked recovery rate of 88.7%-110%. The method was successfully applied to the analysis of inorganic anions and cations in four kinds of mineral water and can completely satisfy the demand of water quality monitoring.

Temperature-dependent aggregation and disaggregation of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymer in aqueous solution.

Aggregation and disaggregation of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) block copolymers, Pluronics P103 and P104, in aqueous solutions during a heating and cooling cycle were investigated by dynamic laser scattering (DLS) and 1H NMR spectroscopy. Temperature hysteresis was observed by DLS when cooling the copolymer aqueous solutions because larger aggregates existed at temperatures lower than critical micellization temperature (CMT), but no temperature differences were observed by NMR. This phenomenon was explained as the forming of water-swollen micelles at temperatures lower than CMT during the cooling process.

Effect of ionic liquids on the aggregation behavior of PEO-PPO-PEO block copolymers in aqueous solution.

Effect of 1-butyl-3-methyl-imidazolium bromide (BmimBr) on the aggregation behavior of PEO-PPO-PEO Pluronic P104 aqueous solution was studied by Fourier transform infrared (FTIR) spectroscopy, freeze fracture transmission electron microscopy (FF-TEM), dynamic light scattering (DLS), and NMR spectroscopy. When the BmimBr concentration was below 1.232 mol/L, the critical micelle temperature (CMT) of Pluronic P104 remained constant, while the size of micelles increased with increasing the BmimBr concentration; above this concentration, the CMT of Pluronic P104 decreased abruptly, and bigger clusters of BmimBr were formed. The selective nuclear Overhauser effect (NOE) spectrum indicates that the PO block of the P104 interacts with the butyl group of the Bmim+ cation by hydrophobic interaction. It suggests that when the concentration of BmimBr is below 1.232 mol/L, there are P104 micelles in the aqueous solution with BmimBr embedding to the micellar core, while above this concentration, P104 micelles and BmimBr clusters coexist in the system.

Effect of acid on the aggregation of poly(ethylene xide)-poly(propylene oxide)-poly(ethylene oxide) block copolymers.

The acid effect on the aggregation of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymers EO(20)PO(70)EO(20) has been investigated by transmission electron microscopy (TEM), particle size analyzer (PSA), Fourier transformed infrared, and fluorescence spectroscopy. The critical micellization temperature for Pluronic P123 in different HCl aqueous solutions increases with the increase of acid concentration. Additionally, the hydrolysis degradation of PEO blocks is observed in strong acid concentrations at higher temperatures. When the acid concentration is low, TEM and PSA show the increase of the micelle mean diameter and the decrease of the micelle polydispersity at room temperature, which demonstrate the extension of EO corona and tendency of uniform micelle size because of the charge repulsion. When under strong acid conditions, the aggregation of micelles through the protonated water bridges was observed.

Microenvironmental and conformational structure of triblock copolymers in aqueous solution by 1H and 13C NMR spectroscopy.

1H and 13C nuclear magnetic resonance (NMR) spectra of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymers in D2O solutions have been systematically investigated. The detailed assignments of various 1H and 13C NMR signals are presented. The hyperfine structure of PO -CH2- protons was clearly assigned, the arising reason of this hyperfine structure was attributed to the influence of the chiral center of -CHCH3- groups and the direct coupling between the PO -CH2- and -CH3 protons. The external standard 2,2-dimethyl-2-silapentane-5-sulfonate sodium salt (DSS) was firstly applied in this system. Accurate chemical shift values referenced to the external standard DSS were obtained. 1H NMR chemical shift of PO -CH2- and -CH3 signals shows a larger decrease in ppm values than that of EO -CH2- signal with the increase of PPO/PEO ratio or temperature indicating that PO segments exist in a more hydrophobic microenvironment. A new resonance signal assigned to the PO -CH2- protons appeared when the temperature is above the CMT, which is attributed to the breakdown of the intra-molecular (C-H)...O hydrogen bond between the PO -CH2- protons and the ester oxygens. The breakdown of this intra-molecular hydrogen bond may result in a decrease of gauche conformers of the PPO chain. The increase of 13C NMR chemical shift of block copolymers validates this conformational change assumption. It can be inferred that the amount of gauche conformers decreases whereas that of trans conformers increases in both PO and EO chains when elevating the PPO/PEO ratio or temperature. The observed 13C NMR chemical shifts of PO segments show a bigger increase than those of EO segments, supporting the formation of a nonpolar microenvironment around PO segments.

[Study on interaction of anionic surfactant SDS and bovine serum albumin by fourier transform infrared spectroscopy].

FTIR spectroscopy was applied to investigate the interaction of anionic surfactant Sodium Dodecyl Sulfate (SDS) and Bovine Serum Albumin (BSA). Amide band I of BSA was analyzed to obtain the change in secondary structure of BSA when different concentration of SDS was added and during different interaction period. In short interaction period and at low concentration of SDS, the alpha-helixes increased and the random coil decreased. In long interaction period or at high concentration of SDS, SDS unfolded the protein by decreasing the alpha-helix structure and increasing the random coil.

Aptamer and PNIPAAm co-conjugated nanoparticles regulate activity of enzyme with different temperature.

In this paper, we described a temperature responsive nano-system that can regulate activity of enzyme with different temperature. Temperature responsive polymer poly(N-isopropylacrylamide) (PNIPAAm), with low critical solution temperature of 32°C, was synthesized with thiol modification. PNIPAAm and thrombin aptamer were co-functionalized on the surface of gold nanoparticles for effective regulation of thrombin activity with different temperature. On the one hand, we studied the thermal responsive properties of this inhibitor via UV-visible spectroscopy. On the other hand, we investigated the regulation of thrombin activity by this platform with different temperature. The PNIPAAm chains could extend and shrink with different temperature, which suggested that PNIPAAm on the surface of gold nanoparticles could regulate interaction between thrombin and aptamer according to temperature changing. At 25°C, PNIPAAm was hydrophilic extended state, which blocked the interaction between thrombin and aptamer on the surface of gold nanoparticles, therefore thrombin activity had no change. On the contrary, at 37°C, PNIPAAm transformed from hydrophilic extended state to hydrophobic shrank state, allowing the aptamer to capture thrombin, inhibiting the activity of thrombin. More interestingly, this regulation was reverse to normal condition, where 37°C was always the optimum reaction temperature for most of human enzymes. This system we prepared was opposite, which was capable of inhibiting the thrombin activity at 37°C. Furthermore, this was the first report of regulation of thrombin activity using this temperature responsive platform.

Reversible regulation of thrombin adsorption and desorption based on photoresponsive-aptamer modified gold nanoparticles.

In the protein separation, adsorption and desorption of target protein have been using different buffer condition. Different buffer will change the structure and activity of target protein in some cases. This work describes the use of different wavelength light for remote regulation of adsorption and desorption of target protein in the same buffer solutions. A dynamic system that captured and released protein in response to light is reported. Matrix gold nanoparticles and light-responsive affinity ligand comprising thrombin aptamer (APT15), polyethylene glycol linker, and azobenzene-modified complementary sequence were used. UV light induced a trans-cis isomerization of the azobenzene that destabilized the duplex of aptamer and azobenzene-modified complementary sequence, resulting in thrombin binding to aptamer sequence. Visible light irradiation resulted in DNA duplex rehybridization and thrombin released. Our work demonstrates that different light wavelengths effectively regulated the adsorption and desorption of thrombin in the same buffer, and this system also can capture and release prothrombin from plasma with different wavelength light. Furthermore, this method can be widely applied to a variety of different protein separation process.