Design and evaluation of semicarbazide-embeddedd stationary phases for liquid chromatography.

Semicarbazide, as a derivative of urea, constitutes a great variety of functional molecules for different needs. Herein, novel stationary phases with an incorporated semicarbazide group were proposed. Using aliphatic (docosanoyl, C22) and aromatic (benzoyl, Bz) hydrazides, the semicarbazide-embedded ligands were synthesized before chemical modification of the silica gel, allowing for an accurate interpretation of the chromatographic properties of the corresponding packings. The new stationary phases were water-wettable, due to the presence of highly polar groups. In particular, Bz-semicarbazide (Bz-SCD) stationary phase was sufficiently hydrophilic to run in hydrophilic interaction (HILIC) mode, whilst the C22 (C22-SCD) equivalent, in spite of its reversed-phase nature, was markedly less hydrophobic than the referenced polar-embedded ones. The versatility of C22-SCD was demonstrated with a large selection of analytes, including geometric isomers and standard mixtures of polycyclic aromatic hydrocarbons, sulfonamides, sulfonylurea, substituted ureas, pyridines and carbamates, fat-soluble colorants, antifungal metabolites, angiotensin II receptor blockers and calcium channel blockers.

Facile Preparation of Hydrogel-Coated Surfaces with Antifouling and Salt Resistance for Efficient Solar-Driven Water Evaporation.

Hydrogel-based evaporators are a promising strategy to obtain freshwater from seawater and sewage. However, the time-consuming and energy-consuming methods used in hydrogel preparation, as well as their limited scalability, are major factors that hinder the development of a hydrogel-based evaporator. Herein, a facile and scalable strategy was designed to prepare a hydrogel-coated evaporator to realize efficient solar-driven water evaporation. The hydrogel coating layer is composed of a robust 3D network formed by tannic acid (TA) and poly(vinyl alcohol) (PVA) through a hydrogen bond. With the assistance of TA surface modifier, carbon black (CB) is uniformly distributed within the hydrogel matrix, endowing the coating with remarkable photothermal properties. In addition, Fe3+ is deposited on the surface of the hydrogel coating through metal coordination with TA, further improving the light absorption of the coating. Due to the synergistic effect of CB and Fe3+, the hydrogel-coated foam exhibited excellent photothermal properties. The water evaporation rate reached 3.64 kg m-2 h-1 under 1 sun irradiation. Because of the hydration ability of PVA hydrogel and the large porous structure of the foam, the hydrogel-coated foam demonstrated excellent antifouling performance and salt resistance. This study provides a facile method for designing and manufacturing high-performance solar-driven water evaporation materials.

Plant Leaf-Inspired Separators with Hierarchical Structure and Exquisite Fluidic Channels for Dendrite-Free Lithium Metal Batteries.

Lithium (Li) metal batteries are among the most promising devices for high energy storage applications but suffer from severe and irregular Li dendrite growth. Here, it is demonstrated that the issue can be well tackled by precisely designing the leaf-like membrane with hierarchical structure and exquisite fluidic channels. As a proof of concept, plant leaf-inspired membrane (PLIM) separators are prepared using natural attapulgite nanorods. The PLIM separators feature super-electrolyte-philicity, high thermal stability and high ion-selectivity. Thus, the separators can guide uniform and directed Li growth on the Li anode. The Li//PLIM//Li cell with limited Li anode shows high Coulombic efficiency and cycling stability over 1500 h with small overpotential and interface impedance. The Li//PLIM//S battery exhibits high initial capacity (1352 mAh g-1 ), cycling stability (0.019% capacity decay per cycle at 1 C over 500 cycles), rate performance (673 mAh g-1 at 4 C), and high operating temperature (65 °C). The separators can also effectively improve reversibility and cycling stability of the Li/Li cell and Li//LFP battery with carbonate-based electrolyte. As such, this work provides fresh insights into the design of bioinspired separators for dendrite-free metal batteries.

Recent advances in perovskite oxides for non-enzymatic electrochemical sensors: A review.

Non-enzymatic electrochemical sensors with significant advantages of high sensitivity, long-term stability, and excellent reproducibility, are one promising technology to solve many challenges, such as the detection of toxic substances and viruses. Among various materials, perovskite oxides have become a promising candidate for use in non-enzymatic electrochemical sensors because of their low cost, flexible structure, and high intrinsic catalytic activity. A comprehensive overview of the recent advances in perovskite oxides for non-enzymatic electrochemical sensors is provided, which includes the synthesis methods of nanostructured perovskites and the electrocatalytic mechanisms of perovskite catalysts. The better sensing performance of perovskite oxides is mainly due to the lattice O vacancies and superoxide oxygen ions (O22-/O-), which are generated by the transfer of lattice oxygen to adsorbed -OH and have performed excellent properties suitable for electrooxidation of analytes. However, the limited electron transfer kinetics, stability, and selectivity of perovskite oxides alone make perovskite oxides far from ready for scientific development. Therefore, composites of perovskite oxides with other materials like graphitic carbon, metals, metal compounds, conducting organics, and biomolecules are summarized. Furthermore, a brief section describing the future challenges and the corresponding recommendation is presented in this review.

Participation of Lattice Oxygen in Perovskite Oxide as a Highly Sensitive Sensor for p-Phenylenediamine Detection.

The harmful effects on the human body from p-phenylenediamine (PPD) in hair dyes can cause allergies and even cancer. Therefore, it is particularly important to accurately control and detect the content of PPD in our daily products and environment. Here, a small amount of non-metallic elemental P doped in perovskite oxide of SrCoO3-δ (SC) forms a good catalytic material, SrCo0.95P0.05O3-δ (SCP), for PPD detection. The improved performance compared with that of the parent SC can be attributed to three contributing factors, including a larger amount of highly oxidative oxygen species O22-/O-, better electrical conductivity, and more active sites on the P5+-oxygen bonds of SCP. Moreover, the lattice oxygen mechanism (LOM) with highly active species of lattice O vacancies and adsorbed -OO for electrocatalytic oxidation of PPD by the SCP/GCE (glass carbon electrode) sensor is proposed in our work. More importantly, the SCP/GCE sensor exhibits good stability, a low limit of detection, and high reliability (error < 5.78%) towards PPD determination in real samples of hair dyes, suggesting the substantial research potential for practical applications.

p-Terphenyl-based rigid stationary phases with embedded polar groups for liquid chromatography.

Terphenyls are important building blocks for a wide range of functional molecules. Among the three isomers, p-terphenyl (C18H14) is particularly useful for the construction of optical devices on account of its unique structure. Herein, two rigid stationary phases bearing p-terphenyl as an external moiety and variable embedded carbamate groups (p-TerC with one embedded carbamate group and p-TerC2 with two embedded carbamate group) were presented. The proposed stationary phases were characterized by various means and evaluated in reversed-phase (RP) mode, using different classes of analytes, including polycyclic aromatic hydrocarbons (PAHs), alkylbenzenes, 4-alkylbiphenyls, substituted ureas, sulfonylureas, substituted sulfanilamides and aromatic acids. The comparison with conventional C18, several other polar-embedded aromatic and C18 equivalents indicated p-terphenyl-based stationary phases were featured by multiple retention mechanisms, involving π-π interaction, charge-transfer interaction, hydrogen-bonding and hydrophobic interaction in RP mode. A unusually high specificity to the analytes with linear structures was observed, as exemplified by an irreversible adsorption of tetracene and a readily separation of tetraphene and chrysene. The aliphatic linker used in the proposed stationary phases was an influential factor for retentivity, selectivity and column efficiency. Interestingly, p-TerC2 was operable in normal-phase mode for the separation of certain PAHs through polar-related interactions. The linear, rigid polyphenyl structure of p-terphenyl endowed the new stationary phase with distinctive chromatographic properties, in contrast to those of the preceding counterparts bonded with alkyl and/or polynuclear aromatic moieties.

A carbonylative coupling approach to alkyl stationary phases with variable embedded carbamate groups for high-performance liquid chromatography.

A highly efficient carbonylative coupling method for the preparation of alkyl stationary phases with variable numbers of carbamate groups was established. The effectiveness of such method was verified through elemental analysis, X-ray photoelectron spectroscopy and solid-state 13C nuclear magnetic resonance spectroscopy of three as-synthesized stationary phases bearing different alkyl chains and different numbers of carbamate groups (octadecyl/one carbamate group, C18C; docosyl/three carbamate groups, C22C3; triacontyl/two carbamate groups, C30C2). The comparative evaluation of these stationary phases using a great variety of analytes, including three sets of isomers of alkylbenzenes, two sets of standard mixtures of polycyclic aromatic hydrocarbons (SRM 1647e and 869b), nine polychlorinated biphenyls, fiveteen N-substituted ureas, ten sulfonylureas, five xanthines and some other phytonutrients, revealed their remarkable applicability in reversed-phase liquid chromatography. Notably, the intercalated carbamate groups rendered the resultant stationary phases compatible with 100% aqueous mobile phase. The suppression of silanol activity was positively related to the number of polar groups embedded in the bonded selector, and the smallest peak tailing factor (1.14) for amitriptyline was obtained by C22C3. The molecular shape-related selectivity was found to be more closely related to the length of the selector's aliphatic chain, as supported by the lowest αTBN/BaP value (0.31) by C30C2. These carbamate-embedded alkyl stationary phases constituted another class of polar-embedded stationary phases possessing a single type of functional ligand.

A docosyl-terminated polyamine amphiphile-bonded stationary phase for multimodal separations in liquid chromatography.

A convenient synthetic approach to a linear alkyl-polyamine amphiphilic chromatographic selector was proposed. Successive immobilization of the amphiphile onto silica gel afforded a multimodal stationary phase for high-performance liquid chromatography (HPLC). The as-prepared silica material was studied comparatively with a conventional octadecyl (C18) and an amide-embedded C18 stationary phase. The new uniform docosyl-triamine tandem was featured by an enhanced shape selectivity towards geometric isomers, and a low silanol activity towards alkaline solutes. The presence of multiple amino groups rendered the new adsorbent operable in different modes, such as hydrophilic interaction and ion-exchange modes. The satisfactory performance of the said stationary phase in separating different classes of analytes, including polycyclic aromatic hydrocarbons, flavonoids, tricyclic antidepressants, calcium channel blockers, aromatic acids, inorganic anions, nucleosides and estrogens, revealed its great potential and high adaptability for multipurpose LC utility.

Evaluation of hydroxyapatite derived from flue gas desulphurization gypsum on simultaneous immobilization of lead and cadmium in contaminated soil.

Flue gas desulphurization gypsum (FGD) is a major solid waste in coal-fired energy plants, and the appropriate reuse of this resources is still a major challenge. In this study, the feasibility of FGD as a calcium source to produce hydroxyapatite (FGD-HAP) for the immobilization of lead (Pb) and cadmium (Cd) in spiked soil was investigated. The effects of FGD and FGD-HAP on soil properties and redistribution, bioaccessibility and plant uptake of Pb and Cd were examined. Results showed that application of FGD and FGD-HAP could significantly improve the enzymes activities of contaminated soils, but the effectiveness was more pronounced with FGD-HAP. Addition of only 1% FGD-HAP could effectively reduce bioavailable Pb and Cd concentration in soil as measured by CaCl2 extraction by 60.6% and 65.4%, respectively. On the other hand, plant available Pb and Cd could significantly decrease by 93.8% and 73.2% after amendment of 5% FGD-HAP. Significant changes in the micro-scale distribution of heavy metals before and after FGD-HAP treatment demonstrated that while heavy metals were predominantly associated with iron/manganese oxides in untreated soil, high correlation between heavy metals and phosphorus/sulfur was observed in FGD-HAP treated soil. In addition, results of the leaching tests showed that incorporation of FGD-HAP enhanced the retention capacity of heavy metals in soil, indicating that application of FGD-HAP could diminish the environmental risk of leachable heavy metals to groundwater. Overall, this study highlighted the potential value of FGD-HAP as a low-cost and high-efficient amendment for remediation of Pb and Cd contaminated soils.

Redox-Switchable Biocatalyst for Controllable Oxidation or Reduction of 5-Hydroxymethylfurfural into High-Value Derivatives.

Biocatalytic upgrading of biomass-derived 5-hydroxymethylfurfural (HMF) into high-value derivatives is of great significance in green chemistry. In this study, we disclosed the successful utilization of whole-cell Paraburkholderia azotifigens F18 for its switchable catalytic performance in the on-demand catalysis of HMF to different value-added derivatives, namely, selective reduction to 2,5-bis(hydroxymethyl)furan (BHMF) or oxidation to 5-hydroxymethyl-2-furancarboxylic acid (HMFCA). Based on the fine-tuning of biochemical properties, the biocatalyst can proceed an efficient hydrogenation reaction toward HMF with a good selectivity of 97.6% to yield the BHMF at 92.2%. Noteworthily, BHMF could be further oxidized to HMFCA and 2,5-furandicarboxylic acid (FDCA) by the whole cell. To realize the on-demand syntheses of HMFCA, the genes encoding HMF oxidoreductase/oxidase of whole-cell F18 were then deleted to prevent the further conversion of HMFCA to FDCA, which led to a 10-fold decrease of FDCA. Thus, an HMF conversion of 100% with an HMFCA yield of 98.3% was finally achieved by the engineered whole cell at a substrate concentration of 150 mM. Moreover, HMFCA synthesis was efficiently prepared with an excellent selectivity of 96.3% and a yield of 85.1% even at a high substrate concentration of up to 200 mM.

A highly efficient acyl-transfer approach to urea-functionalized silanes and their immobilization onto silica gel as stationary phases for liquid chromatography.

An alternative method for efficient synthesis of urea-functionalized silanes was proposed on the basis of an N, N'-carbonyldiimidazole-mediated acyl-transfer reaction between various amino-containing building blocks. The employment of different parent aminosilanes and alkylamines afforded an array of urea-containing silanes, which were subsequently immobilized onto silica gel to form corresponding urea-embedded alkyl stationary phases for high-performance liquid chromatography. The different substituents on the silicon core of the derivatized silane were found to significantly influence the final chromatographic behaviors. The comparative chromatographic characterization of thus-prepared silica packings with conventional octadecyl (C18) stationary phases revealed that the urea group was beneficial to suppress silanol activity towards basic probes, as well as to increase the water-compatibility of the alkyl stationary phases. The combination of a polar urea moiety and a non-polar long alkyl chain was favorable for an enhanced steric selectivity towards shape-constrained isomers. The polarizability-sensitive feature of such stationary phases made them good candidates for efficient separation of nitro-containing polar substances.

Design and evaluation of polar-embedded stationary phases containing triacontyl group for liquid chromatography.

The present work described two triacontyl-bonded silica adsorbents containing different polar embedded groups (i.e. amide- and carbamate-type) for high performance liquid chromatography, which were prepared by covalent surface modification of silica gel with respective pre-synthesized polar-embedded triacontyl (C30) silane. The acylimidazole-mediated method was used for the first time for the synthesis of amide-type alkyl silane, while the carbamate-type silane was obtained via an improved solvent-free procedure. A conventional C30 stationary phase was also developed on the same silica substrate in the similar manner, which was used as a reference column for comparison of the unique mechanisms facilitated and/or furnished by the polar groups. The successful immobilization of the designed C30 species was confirmed by infrared spectroscopy and elemental analysis. In further comparison with an amide-embedded octadecyl (C18) two other conventional C18 stationary phases of different surface chemistry, detailed chromatographic characterization of the C30 series stationary phases was performed in terms of surface density, hydrophobicity, aromatic selectivity, shape selectivity and water tolerance using a diversified range of analytes, including homologous alkylbenzenes, isomeric polycyclic aromatic hydrocarbons, carotenes, congeners of polychlorobiphenyls, aromatic amines, phenolic compounds, estrogens and nucleosides. A high resemblance between the chromatographic behaviors of the two polar-modified C30 stationary phases was observed, meanwhile they demonstrated noticeable differences from non-polar C30 stationary phase. The polar-embedded C30 phases showed satisfactory performance towards the solutes of interest in the studied conditions. The beneficial synergy of the polar groups and the triacontyl chains enabled these polar-enhanced C30 stationary phases to address challenging separation tasks with high selectivity.

A new low-cost hydroxyapatite for efficient immobilization of lead.

Distiller waste (DW), a common by-product of soda ash plants, was used as the unique calcium source to produce low-cost hydroxyapatites (HAPs) for the first time. The DW-derived HAPs were characterized by SEM, TEM, XRD and BET methods and investigated as amendments for soil Pb immobilization. The DW-derived HAPs displayed relatively smaller particle size (30-80 nm) and larger BET specific surface areas (60.00-64.06 m2/g) compared with two selected commercial HAPs (technical grade HAP and biological reagent HAP designated as HAP-TG and HAP-BR, respectively). The maximum sorption capacity of Pb on the DW-derived HAPs predicted from Langmuir sorption isotherm model was 726-734 mg/g higher than the commercial HAPs and even other well-designed sorbents. TCLP leaching experiments and BCR sequential extraction experiments were conducted to determine the effectiveness of HAP additions on Pb immobilization in soil. A lower addition ratio is required for the DW-derived HAPs than commercial HAPs to reduce Pb leachability to below the harmless level. Meanwhile, the DW-derived HAPs were found to be superior to commercial HAPs in transformation of readily bioavailable forms of Pb to stable speciation in soil, with residual fraction of Pb increased from 6.7% in non-amended soil to 60.7-61.4% in DW-derived HAPs amended soils, 58.3% in HAP-TG amended soil and 42.6% in HAP-BR amended soil, respectively. This study strongly demonstrated the feasibility and low-cost of HAPs derived from the distiller waste for reducing the environmental risks and bioavailability of Pb in soil.

Tuning selectivity via electronic interaction: Preparation and systematic evaluation of serial polar-embedded aryl stationary phases bearing large polycyclic aromatic hydrocarbons.

Aromatic stationary phases showing complementary selectivity to their alkyl counterparts are extremely useful for certain challenging separation tasks. Herein, a series of polar-embedded aryl stationary phases were synthesized from reactive derivatives of large polycyclic aromatic hydrocarbons (PAHs), including anthracene (three-ring, catacondensed), pyrene (four-ring, pericondensed) and triphenylene (four-ring, fully-benzenoid). These PAHs were functionalized with hydroxymethyl group (PAH-CH2OH), then catalytically converted to carbamates (PAH-CH2OC(=O)NH-R) using isocyanate, and finally covalently grafted onto silica to produce corresponding carbamate-embedded PAH stationary phases. To gain insight into the connection and difference among the attached species, the chromatographic behaviors of these new adsorbents were systematically evaluated in terms of surface coverage, hydrophobic and aromatic features, shape selectivity and charge-transfer property, using different classes of analytes, such as alkylbenzenes, PAH congeners and isomeric multi-substituted benzenes, and the results were further compared with conventional octadecyl ones (C18). The relationships between the shape selectivity and the surface chemistry revealed unique behavioral patterns of theses immobilized conjugated ligands, as well as marked differences amongst them, which formed sharp contrast to the case of C18. The effects of temperature and mobile phase compositions on the shape selectivity were further studied. The charge-transfer characteristics demonstrated the great potential of such polar-embedded PAH materials for highly selective separation of electron-deficient compounds through electron donor-acceptor complexation.

Simple Synthesis of High Specific Surface Carbon Nitride for Adsorption-Enhanced Photocatalytic Performance.

TMC-incorporated carbon nitride (CN) with hexagonal and quadrangle honeycomb-like structure and having periodic lattice defects linked by -CONH- bond was synthesized through combining the high calcination with the chemical condensation of melamine and 1,3,5-benzenetricarbonyl trichloride. The obtained CN has a tri-s-triazine ring and benzene ring skeleton, which makes it have excellent mechanical and thermal stability. The BET specific surface area was enhanced to about 125.6 m2/g, and the mean pore size is about 3.43 nm. This CN exhibited an excellent adsorption-enhanced photocatalytic performance.

A versatile polar-embedded polyphenyl phase for multimodal separation in liquid chromatography.

A new polar-embedded aromatic stationary phase has been prepared by covalently attaching p-biphenylacetamide silane to silica spheres. The retention behavior of this phase was compared with an alkylamide counterpart and octadecyl phases using different classes of analytes, including geometric isomers and congeners from Standard Reference Materials 869b, 870 and 1647e, positional isomers of electron-deficient benzenes, as well as alkylbenzenes and alkylbiphenyls. The relationship between shape selectivity and surface chemistry of stationary phase was comparatively studied. Influences of the embedded group and ligand length and/or size on the chromatographic selectivity towards various congeners were established. The new polar-embedded aromatic phase possessed unique benzenoid affinity, enhanced aromatic selectivity, distinct charge-transfer properties, as well as good water-wettablity, as a result it can be employed in normal phase, reversed-phase and per-aqueous modes.

Humic acid removal and easy-cleanability using temperature-responsive ZrO2 tubular membranes grafted with poly(N-isopropylacrylamide) brush chains.

New poly(N-isopropylacrylamide) brushes grafted with ZrO2 (PNIPAAm-g-ZrO2) composite membranes, which had been prepared in our laboratory, were used for humic acid (HA) removal. We found that the fluxes associated with such membranes, when compared to those obtained from unmodified ZrO2 membranes, declined slightly at both 25 °C and 35 °C. The PNIPAAm-g-ZrO2 membrane achieved a high rejection, of 98.0%, at a suitable steady flux of 111.9 L m(-2) h(-1) at 25 °C. This membrane exhibited good anti-fouling properties as well as improved membrane performance during filtration of HA. The important role of pH and Ca(2+) concentration in HA removal was also investigated. Lower adsorption fouling and a higher rejection were obtained at higher pH levels. The Ca(2+) ions reduced the electrostatic exclusion and played a cross-linking role between HA and the PNIPAAm-g-ZrO2 membrane surface. Fouling was severe in the presence of Ca(2+). These tests led to the development of an environment-friendly membrane cleaning method, by means of temperature-change water elution around LCST of PNIPAAm-brushes. After the alternate temperature-change (25 °C/35 °C) cleaning, a flux recovery of 98.2% was obtained for the PNIPAAm-g-ZrO2 membrane. Moreover, after four repeated experiments, the anti-fouling and easy-cleaning properties were still maintained. It is implied that PNIPAAm-brushes were firmly "stuck" to the membrane surface, and could not easily be removed by water cleaning or HA filtration. The PNIPAAm-g-ZrO2 membranes exhibited good stability and great potential for HA removal.

Effective NH2-grafting on attapulgite surfaces for adsorption of reactive dyes.

The amine moiety has an important function in many applications, including, adsorption, catalysis, electrochemistry, chromatography, and nanocomposite materials. We developed an effective adsorbent for aqueous reactive dye removal by modifying attapulgite with an amino-terminated organosilicon (3-aminopropyltriethoxysilane, APTES). Surface properties of the APTES-modified attapulgite were characterized by the Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption-desorption. We evaluated the impact of solvent, APTES concentration, water volume, reaction time, and temperature on the surface modification. NH(2)-attapulgite was used to remove reactive dyes in aqueous solution and showed very high adsorption rates of 99.32%, 99.67%, and 96.42% for Reactive Red 3BS, Reactive Blue KE-R and Reactive Black GR, respectively. These powerful dye removal effects were attributed to strong electrostatic interactions between reactive dyes and the grafted NH(2) groups.

Adsorption of Hg2+ from aqueous solution onto polyacrylamide/attapulgite.

Polyacrylamide/attapulgite (PAM/ATP) was prepared by the solution polymerization of acrylamide (AM) onto gamma-methacryloxypropyl trimethoxy silane (KH-570)-modified attapulgite (ATP). PAM/ATP was characterized using Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS). The effects of contact time, adsorbent dosage, and pH of the initial solution on the adsorption capacities for Hg(2+) were investigated. The adsorption process was rapid; 88% of adsorption occurred within 5 min and equilibrium was achieved at around 40 min. The equilibrium data fitted the Langmuir sorption isotherms well, and the maximum adsorption capacity of Hg(2+) onto PAM/ATP was found to be 192.5 mg g(-1). The adsorption kinetics of PAM/ATP fitted a pseudo-second-order kinetic model. Our results suggest that chemisorption processes could be the rate-limiting steps in the process of Hg(2+) adsorption. Hg(2+) adsorbed onto PAM/ATP could be effectively desorbed in hot acetic acid solution, and the adsorption capacity of the regenerated adsorbents could still be maintained at 95% by the sixth cycle.