Higher sensitivity of gross primary productivity than ecosystem respiration to experimental drought and warming across six European shrubland ecosystems.

Shrubland ecosystems across Europe face a range of threats including the potential impacts of climate change. Within the INCREASE project, six shrubland ecosystems along a European climatic gradient were exposed to ecosystem-level year-round experimental nighttime warming and long-term, repeated growing season droughts. We quantified the ecosystem level CO2 fluxes, i.e. gross primary productivity (GPP), ecosystem respiration (Reco) and net ecosystem exchange (NEE), in control and treatment plots and compared the treatment effects along the Gaussen aridity index. In general, GPP exhibited higher sensitivity to drought and warming than Reco and was found to be the dominant contributor to changes in overall NEE. Across the climate gradient, northern sites were more likely to have neutral to positive responses of NEE, i.e. increased CO2 uptake, to drought and warming partly due to seasonal rewetting. While an earlier investigation across the same sites showed a good cross-site relationship between soil respiration responses to climate over the Gaussen aridity index, the responses of GPP, Reco and NEE showed a more complex response pattern suggesting that site-specific ecosystem traits, such as different growing season periods and plant species composition, affected the overall response pattern of the ecosystem-level CO2 fluxes. We found that the observed response patterns of GPP and Reco rates at the six sites could be explained well by the hypothesized position of each site on site-specific soil moisture response curves of GPP/Reco fluxes. Such relatively simple, site-specific analyses could help improve our ability to explain observed CO2 flux patterns in larger meta-analyses as well as in larger-scale model upscaling exercises and thereby help improve our ability to project changes in ecosystem CO2 fluxes in response to future climate change.

In-situ immobilization of covalent organic frameworks as stationary phase for capillary electrochromatography.

A new kind of covalent organic framework (COF) was first utilized as an stationary phase for open-tubular electrochromatography (OT-CEC) by in situ synthesis immobilized method at room temperature. On the basis of our previous work, 4,4',4″-(1,3,5-Triazine-2,4,6-triyl)trianiline (TZ) and 2,5-bis(2-propyn-1-yloxy)-1,4-benzenedicarboxaldehyde (BPTA) were employed as building blocks for the synthesis of COF TZ-BPTA. The coated capillary and COF TZ-BPTA were characterized by scanning electron microscopy (SEM). Then, Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD) were also applied to characterize COF TZ-BPTA and the modified column. In SEM, it can be seen that COF TZ-BPTA was the spherical shape and the modified capillary was covered with globular particles equably. The COF TZ-BPTA coated column exhibited good separation resolution and efficiency towards two antiepileptic drugs and other kinds of small organic molecules involving alkylbenzene, sulfonamides, polycyclic aromatic hydrocarbon (PAH), parabens, amino acids and herbicides. The maximum column efficiency was over 2.8 × 105 plates·m-1. In addition, the precisions (RSDs) of the retention times for the alkylbenzenes of intra-day runs (n = 3), inter-day runs (n = 3) and column-to-column runs (n = 3) were all less than 1.70% and separation performance was without obvious change within 100 times run. In addition, the real sample was tested on COF TZ-BPTA coated column. Hence, COF TZ-BPTA showed great potential in the separation domain.

Fluorinated covalent-organic polymers as stationary phase for analysis of organic fluorides by open-tubular capillary electrochromatography.

Fluorinated porous materials, which can provide specific fluorine-fluorine interaction, hold great promise for fluoride analysis. Here, a novel fluorinated covalent-organic polymer was prepared by using 2,4,6-tris(4-aminophenyl)-1,3,5-triazine and 2,3,5,6-tetrafluorotelephtal aldehyde as the precursors and introduced as stationary phase for open-tubular capillary electrochromatography. The as-synthesized fluorinated covalent-organic polymer and the modified capillary column were characterized by infrared spectroscopy, scanning electron microscopy, and energy dispersive X-ray spectrometry. Based on strong hydrophobic interaction and fluorine-fluorine interaction provided by fluorinated covalent-organic polymer coating layer, the modified column showed powerful separation selectivity toward hydrophobic compounds, organic fluorides, and fluorinated pesticides. Additionally, the fluorinated covalent-organic polymer with good porosity and regular shape was uniformly and tightly coated on the capillary inner wall. The obtained highest column efficiency could reach up to 1.2 × 105 plates⋅m-1 for fluorophenol. The loading capacity of the modified column can reach 141 pmol for trifluorotoluene. Besides, the relative standard deviations of retention times for intraday run (n = 5), interday run (n = 3), and between columns (n = 3) were all less than 2.55%. Significantly, this novel fluorinated material-based stationary phase shows great application potential in fluorides analysis.

Long-term temporal patterns in ecosystem carbon flux components and overall balance in a heathland ecosystem.

Terrestrial ecosystems have strong feedback to atmospheric CO2 concentration and climate change. However, the long-term whole life cycle dynamics of ecosystem carbon (C) fluxes and overall balance in some ecosystem types, such as heathland ecosystems, have not been thoroughly explored. We studied the changes in ecosystem CO2 flux components and overall C balance over a full ecosystem lifecycle in stands of Calluna vulgaris (L.) Hull by using a chronosequence of 0, 12, 19 and 28 years after vegetation cutting. Overall, the ecosystem C balance was highly nonlinear over time and exhibited a sinusoidal-like curvature of C sink/source change over the three-decade timescale. After cutting, plant-related C flux components of gross photosynthesis (PG), aboveground autotrophic respiration (Raa) and belowground autotrophic respiration (Rba) were higher at the young age (12 years) than at middle (19 years) and old (28 years) ages. The young ecosystem was a C sink (12 years: -0.374 kg C m-2 year-1) while it became a C source with aging (19 years: 0.218 kg C m-2 year-1) and when dying (28 years: 0.089 kg C m-2 year-1). The post-cutting C compensation point was observed after four years, while the cumulative C loss in the period after cutting had been compensated by an equal amount of C uptake after seven years. Annual ecosystem C payback from the ecosystem to the atmosphere started after 16 years. This information may be used directly for optimizing vegetation management practices for maximal ecosystem C uptake capacity. Our study highlights that whole life cycle observational data of changes in C fluxes and balance in ecosystems are important and the ecosystem model needs to take the successional stage and vegetation age into account when projecting component C fluxes, ecosystem C balance, and overall feedback to climate change.

Determination of water in organic solvents and raw food products by fluorescence quenching of a crystalline vinyl-functionalized COF.

Covalent organic frameworks (COFs) with good chemical stability, flexible chemical functionalization, tunable pore sizes, and high specific surface areas have been increasingly employed in the field of fluorescence sensing. In this work, a crystalline vinyl-functionalized COF TzDa-V was facilely prepared through a room-temperature synthetic method via condensation reaction between 4,4',4″-(1,3,5-triazine-2,4,6-triyl)trianiline (Tz) and 2,5-diallyloxyterephthalaldehyde (Da-V). The intermolecular charge transfer (ICT) effect endowed the TzDa-V with fluorescence characteristic, and it was sensitive to trace water and can be quenched due to the disruption of ICT process by water. On this base, the prepared COF TzDa-V with excellent chemical/thermal stability was applied to sensing of trace water in common organic solvents such as DMF, acetone, THF, and ethyl acetate with rapid response (less than 10 s), satisfactory sensing range (0.5-18% water in DMF, 0.5-15% water in acetone, 0.5-16% water in THF, 0.5-5% in ethyl acetate, v/v), and high sensitivity. The limits of detection for water in DMF, acetone, THF, and ethyl acetate were 0.0497%, 0.0590%, 0.0502%, and 0.0766% (v/v), respectively. The proposed probe was successfully used for the detection of trace water in food products such as salt and sugar. The COF TzDa-V would be a good candidate for application in water sensing.

Synthesis of carbon dots-based covalent organic nanomaterial as stationary phase for open tubular capillary electrochromatography.

The transformation of zero-dimensional carbon dots (CDs) to cross-linked nanomaterials is rare. In this work, a novel carbon dots-based covalent organic nanomaterial (CON CDs-TAPB) consisted of 1,3,5-tris(4-aminophenyl)-benzene (TAPB) and carbon dots (CDs) through facile Schiff-base reaction was synthesized and then employed as a stationary phase for open-tubular capillary electrochromatography (OT-CEC). The CON CDs-TAPB and the CDs-TAPB coated column were characterized through Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), UV-spectra experiments and X-ray photoelectron spectroscopy (XPS). Thanks to CON CDs-TAPB unique structure and abundant accessibility and interaction sites, the prepared column exhibited a satisfactory separation ability towards analytes including parabens, phenolic compounds. Among all analytes, the highest column efficiency was over 1.6 × 105 plates·m-1. In addition, affording methylbenzene loading capacity of 156.9 pmole, surpassing most of those materials-based OT-CEC reported thus far. Thus, the prepared carbon dots-based covalent organic nanomaterial (CON CDs-TAPB) gave a potential as a stationary phase in the separation science.

Synthesis of multifunctional crown ether covalent organic nanospheres as stationary phase for capillary electrochromatography.

Crown ethers are macrocyclic polyether compounds containing multiple -oxo-methylene-structural units, which are often used for recognition of metal ions and ammonium ions. Inspired by the molecular design of rotaxanes, a novel covalent organic nanospheres material (CON ADBC-Tp) constructed by 4,4'-diaminodibenzo-18-crown-6 (ADBC) and 2,4,6-triformylphloroglucinol (Tp) was rationally designed as stationary phase for the separation of compounds containing imidazole structure. Scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FT-IR) were carried out to confirm the morphology and composition of ADBC-Tp and ADBC-Tp modified capillary column. Thanks to the introduction of crown ether building ligands, the prepared capillary column exhibited excellent separation selectivity towards protonated imidazole structure, with benzimidazole and its 2-substituted derivatives as modal analytes. Moreover, separation of fungicides, nucleobases, short peptides and sulfanilamides were achieved on ADBC-Tp@capillary. The multifunctional ADBC-Tp@capillary with satisfactory reproducibility and stability gives great promise for separation science.

Synthesis of crystalline covalent organic framework as stationary phase for capillary electrochromatography.

The development of novel stationary phases to achieve high-efficiency separation is still an important topic in separation sciences. Covalent organic frameworks (COFs) with the advantages of large specific surface areas, high porosity and stability have attracted great attention in chromatographic field. Here, a novel crystalline covalent organic framework (TzDa-V) was designed and synthesized by condensation reaction between 4,4',4″-(1,3,5-Triazine-2,4,6-triyl)trianiline (Tz) and 2,5-diallyloxyterephthalaldehyde (Da-V) for open-tubular capillary electrochromatography (OT-CEC). Thanks to the regular shape, strong hydrophobicity and microporous structure of COF TzDa-V, the TzDa-V modified capillary column exhibited excellent efficiency for the separation of several groups of small molecules, including alkylbenzenes, chlorobenzenes, sulfonamides and so on. The maximum column efficiency can reach about 2.0 × 105 plates•m-1 (for chlorobenzene). Besides, the prepared COF TzDa-V modified OT-column can afford methylbenzene loading capacity of 127.72 pmol. Also, the OT-columns were considerably stable and reproducible. The RSDs of intra-day (n = 3), inter-day (n = 3) and three batches runs for the retention times of four benzenes were all below 1.89%. Our successful work indicates the great potential of COF TzDa-V in CEC for high-efficiency separation.

Insight into the enhancing activity and stability of Ce modified V2O5/AC during cyclic desulfurization-regeneration-denitrification.

Cyclic desulfurization-regeneration-denitrification over carbon-based catalysts is a promising technology for SO2 and NOx simultaneous elimination in steel industry. Regeneration is imperative to the long-term operation of the process, while the research is limited. In this work, Ce modified V2O5/AC catalyst (CeVOx/AC) with higher desulfurization and denitrification activity was prepared and the effect of cyclic regeneration was investigated. Results illustrated that the desulfurization and denitrification activity of CeVOx/AC gradually improved with increasing the regeneration cycles at the optimum regeneration temperature of 470 °C in N2. The increasing Ce3+, V5+ and oxygen vacancies, enhanced surface acidity and improved redox ability contributed to the catalytic activity of regenerated catalysts. For desulfurization, more SO2 transformed into H2SO4 rather than to metal sulfates after cyclic regeneration. For denitrification, the improved redox ability accelerated the oxidation of NO to active NO2, bridged nitrites and nitrates, and the enhanced acidity facilitated the NH3 adsorption, further generating more -NH2 and promoting the SCR activity of regenerated samples. The CeVOx/AC with good activity and regenerative stability shows great application potential in steel industry for the simultaneous SO2 and NOx removal.

Baicalin suppresses glaucoma pathogenesis by regulating the PI3K/AKT signaling in vitro and in vivo.

Glaucoma, characterized with progressive degeneration of retinal ganglion cells (RGCs), is the second frequently leading cause of sight loss in the word after cataract. Baicalin plays a protective role in age-related macular degeneration, retinopathy of prematurity, branch retinal vein occlusion, and ischemia-induced neurodegeneration in the retina. The present study aimed to investigate the role of baicalin in glaucoma. RGCs were stimulated with N-methyl-D-aspartate (NMDA) to mimic the in vitro model of glaucoma. A mouse model of glaucoma induced by chronic elevated intraocular pressure was also established. The apoptosis, oxidative stress, and autophagy of RGCs were detected by flow cytometry analysis, 2,7-dichlorodihydrofluorescein diacetate staining, and Western blotting, respectively. Retinal pathological changes were exhibited by hemotoxylin and eosin staining. Baicalin restrained the NMDA-induced cell apoptosis, autophagy, and oxidative stress of RGCs by activating the PI3K/AKT signaling in vitro. The elevated intraocular pressure-induced pathological changes in retinas of glaucoma mice were attenuated by baicalin. Moreover, the number of RGCs was significantly decreased in glaucoma mice, and then increased by baicalin treatment. Baicalin also inhibited autophagy and activated PI3K/AKT signaling in vivo. In conclusion, baicalin suppresses glaucoma pathogenesis by regulating the PI3K/AKT signaling in vitro and in vivo.

Identification of a prognostic chemoresistance-related gene signature associated with immune microenvironment in breast cancer.

Breast cancer is the most common form of cancer among women globally, and chemoresistance is a major challenge to disease treatment that is associated with a poor prognosis. This study was formulated to identify a reliable prognostic biosignature capable of predicting the survival of patients with chemoresistant breast cancer (CRBC) and evaluating the associated tumor immune microenvironment. Through a series of protein-protein interaction and weighted correlation network analyses, genes that were significantly associated with breast cancer chemoresistance were identified. Moreover, univariate Cox regression and lasso-penalized Cox regression analyses were employed to generate a prognostic model, and the prognostic utility of this model was then assessed using time-dependent receiver operating characteristic (ROC) and Kaplan-Meier survival curves. Finally, The CIBERSORT and ESTIMATE algorithms were additionally leveraged to assess relationships between the tumor immune microenvironment and patient prognostic signatures. Overall, a multigenic prognostic biosignature capable of predicting CRBC patient risk was successfully developed based on bioinformatics analysis and in vitro experiments. This biosignature was able to stratify CRBC patients into high- and low-risk subgroups. ROC curves also revealed that this biosignature achieved high diagnostic efficiency, and multivariate regression analyses indicated that this risk signature was an independent risk factor linked to CRBC patient outcomes. In addition, this signature was associated with the infiltration of the tumor microenvironment by multiple immune cell types. In conclusion, the chemoresistance-associated prognostic gene signature developed herein was able to effectively evaluate the prognosis of CRBC patients and to reflect the overall composition of the tumor immune microenvironment.

Room-temperature growth of covalent organic frameworks as the stationary phase for open-tubular capillary electrochromatography.

Covalent organic frameworks (COFs) are a class of porous materials with high surface area, high porosity, good stability and tunable structure that have been widely used in the separation area. In this work, we have proposed the in situ synthesis of a novel COF composed of 4,4',4''-(1,3,5-triazine-2,4,6-triyl)trianiline (Tz) and 1,4-dihydroxyterephthalaldehyde (Da) onto the capillary inner surface for electrochromatographic separation. Fourier transform infrared (FT-IR) spectroscopy, elemental analysis (EA) and scanning electron microscopy (SEM) have facilitated the characterization of the prepared capillary columns. The COF (TzDa) modified OT-CEC column exhibited satisfactory separation selectivity towards neutral compounds (such as chlorobenzenes and alkylbenzenes), acidic and basic compounds (such as phenols and anilines), food additives (vanillin and its analogues) and small biomolecules (such as amino acids and polypeptides). Furthermore, the TzDa modified capillary was quite stable and reproducible. The relative standard deviations for retention times of the test analytes (alkylbenzenes) were as follows: for intra-day (n = 3) runs (≤1.74%), inter-day (n = 3) runs (≤2.25%) and between columns (n = 3) (≤4.83%). This new type of COF-based stationary phase has tremendous potential in separation science.

A lipase-based chiral stationary phase for direct chiral separation in capillary electrochromatography.

Candida antarctica lipase B (CALB) is a natural biocatalyst with an intrinsically strong chiral environment and a high degree of enantio-selectivity, which is widely used in the separation of racemates. Here, a facile and efficient covalent immobilization approach was utilized to immobilize CALB onto the capillary inner wall as a novel chiral stationary phase to explore and broaden its application in the direct chiral separation by electrochromatography. The obtained CALB immobilized capillary column was characterized by scanning electron microscopy (SEM), fluorescence imaging and Fourier transform infrared spectroscopy (FT-IR). The enantioseparation property of the CALB immobilized capillary column was confirmed by direct chiral separation of several pairs of monoamine neurotransmitter enantiomers in OT-CEC mode. Outstanding enantioseparation performance for three types of monoamine neurotransmitter enantiomers including epinephrine, norepinephrine and phenylephrine was obtained by the CALB immobilized column. Thanks to the effectiveness of covalent bonding method and the intrinsic stability of CALB, the prepared CALB immobilized capillary columns were quite steady and reproducible. The relative standard deviations for retention times of the enantiomers were as follows: for intra-day (n = 5) runs (≤0.25%), inter-day (n = 3) runs (≤0.72%) and between-columns (n = 3) (≤2.42%). After 90 consecutive runs in CEC mode, the CALB immobilized column still exhibited desirable enantionseparation performance.

Managing Defects Density and Interfacial Strain via Underlayer Engineering for Inverted CsPbI2 Br Perovskite Solar Cells with All-Layer Dopant-Free.

Inorganic perovskite CsPbI2 Br has advantages of excellent thermal stability and reasonable bandgap, which make it suitable for top layer of tandem solar cells. Nevertheless, solution-processed all-inorganic perovskites generally suffer from high-density defects as well as significant tensile strain near underlayer/perovskite interface, both leading to compromised device efficiency and stability. In this work, the defect density as well as interfacial tensile strain in inverted CsPbI2 Br perovskite solar cells (PeSCs) is remarkably reduced by using a bilayer underlayer composed of dopant-free 2,2',7,7'-tetrakis(N,N-dip-methoxyphenylamine)-9,9'-spirobifluorene (Spiro-OMeTAD) and copper phthalocyanine 3,4',4″,4'″-tetrasulfonated acid tetrasodium salt (TS-CuPc) nanoparticles. As compared to control devices with pristine Spiro-OMeTAD, devices based on Spiro-OMeTAD/TS-CuPc exhibit remarkably improved photovoltaic performance and enhanced thermal/humidity stability due to the better perovskite crystallization, improved interfacial passivation, and hole-collection as well as efficient interfacial strain release. As a result, a champion efficiency of 14.85% can be achieved, which is approaching to the best reported for dopant-free and inverted all-inorganic PeSCs. The work thus provides an efficient strategy to simultaneously regulate the defects density and strain issue related to inorganic perovskites.

MiR-142-3p ameliorates high glucose-induced renal tubular epithelial cell injury by targeting BOD1.

BACKGROUND: Tubular injury plays a crucial role in the pathogenesis of diabetic nephropathy (DN). It is well known that many microRNAs (miRNAs) exert crucial effects on tubular injury. This study intends to explore the effect of miR-142-3p on the apoptosis and oxidative stress of high glucose (HG)-treated renal tubular epithelial cells (HK-2) and its underlying mechanism. MATERIALS AND METHODS: HK-2 cells were exposed to HG to mimic cell injury. MTT assays and flow cytometry analyses were conducted to measure cell viability and cell apoptosis, respectively. RT-qPCR and western blot analyses were carried out to detect RNA and protein levels, respectively. The levels of oxidative stress markers were evaluated by ELISA. The binding between miR-142-3p and biorientation of chromosomes in cell division 1 (BOD1) was validated by a luciferase reporter assay. RESULT: MiR-142-3p is low-expressed in HG-stimulated HK-2 cells. Functionally, miR-142-3p overexpression attenuates the apoptosis and oxidative stress of HG-stimulated HK-2 cells. Mechanistically, BOD1 was confirmed to be targeted by miR-142-3p in HK-2 cells. Moreover, BOD1 overexpression reversed the suppressive effect of miR-142-3p overexpression on the apoptosis and oxidative stress of HK-2 cells treated with HG. CONCLUSION: MiR-142-3p ameliorates HG-induced renal tubular epithelial cell injury by targeting BOD1. The finding might provide novel insight into the role of miR-142-3p/BOD1 axis in DN treatment.

Benzoic acid-modified monolithic column for separation of hydrophilic compounds by capillary electrochromatography with high content of water in mobile phase.

Hydrophilic column combined with mobile phase containing high content of water is a green method for the separation of polar compounds, but there are few related studies, and the separation efficiency and performance of existing columns still needs to be improved. In this work, a novel monolithic column for separation of hydrophilic compounds under both high water content and HILIC condition, was prepared by in-situ polymerization using 4-vinylbenzoic acid (VBA) and 1-(Acryloyloxy)-3-(methacryloyloxy)-2-propanol (AMAP) as functional monomers. The poly(VBA-co-AMAP) monolithic column showed good separation performance towards various polar compounds under different chromatographic conditions based on the π-interaction, hydrophobic and hydrogen bonding interactions provided by 4-vinylbenzoic acid functional monomer. The highest column efficiency for adenine was over 2.15 × 105 plates m-1 (theoretical plate, N). In addition, the monolith showed good stability and reproducibility, the relative standard deviations (RSDs) of retention times within days (n = 5), between days (n = 5), between columns (n = 3) and between batches (n = 3) were 0.47-1.13%, 1.20-2.68%, 0.59-1.78% and 1.54-3.60%, respectively. This novel type of monolith has great application potential in the separation of hydrophilic compounds.

In situ room-temperature preparation of a covalent organic framework as stationary phase for high-efficiency capillary electrochromatographic separation.

Covalent organic frameworks (COFs), considered as a series of newly emerging porous organic materials, have been widely utilized in separation fields. Herein, a novel COF (TFPB-BD) was first employed as stationary phase for high-efficiency capillary electrochromatographic separation. Benzidine (BD) and 1,3,5-Tris-(4-formylphenyl)benzene (TFPB) were selected as organic linkers and then introduced into the aldehyde group modified capillary for the in situ growth of TFPB-BD onto the capillary inner wall at room temperature. The morphology and formation of TFPB coated capillary column were confirmed by a variety of tools including Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) and energy dispersive X-ray spectrometry (EDS). It's interesting that the TFPB globular crystals with nanoscale were uniformly and densely modified on the capillary inner surface. Hence, the prepared column exhibited prominent separation performance for the test analytes including alkylbenzenes, chlorobenzenes and phenolic compounds with high efficiency and high resolution. The maximum column efficiency can reach about 1.8 × 105 plates•m-1. Additionally, the high resolutions of anilines, amino acids and parabens were also achieved on the TFPB modified capillary. The precisions (RSDs) of the retention times of alkylbenzenes of intra-day runs (n = 3), inter-day runs (n = 3) and parallel columns (n = 3) were all less than 2.83%. This innovative COF-based stationary phase gives great promise for the chromatographic separation field.

Facile preparation of ethanediamine-ß-cyclodextrin modified capillary column for electrochromatographic enantioseparation of Dansyl amino acids.

Herein, the fabrication of a fascinating multifunctional cyclodextrin (CD) chiral stationary phase and its chiral separation performance in capillary electrochromatography are proposed. A facile interfacial polymerization was used to anchor ethanediamine-ß-cyclodextrin (EDA-ß-CD) polymerized with trimesoyl chloride (TMC) and to form the chiral stationary phase (CSP) composite onto the surface wall of the capillary. The characters of prepared columns were confirmed by Fourier transform infrared spectroscopy (FT-IR), X-ray Photoelectron Spectrometer (XPS), scanning electron microscopy (SEM) and energy dispersive X-ray spectrometry (EDS). This novel CSP offers multi-typical interactions including hydrogen bonding, π-interaction, hydrophobic and electrostatic interaction as well as steric effects which contribute to prominent chiral recognition for Dansyl-DL-amino acids in CEC modes. The EDA-ß-CD modified column showed eminent enantioseparation performance towards five Dansyl-DL-amino acids (the DL-forms of valine, threonine, leucine, phenylalanine, serine). Besides, the prepared columns were perfectly reproducible and stable. The relative standard deviations of the enantiomer retention times for intra-day (n = 5), inter-day (n = 3) runs and column-to-columns (n = 3) are below 0.54%, 1.35% and 4.89%, individually. This innovative chiral stationary phase shows a broader application view and scope in chiral recognition domain.

Glycine-modified organic polymer monolith featuring zwitterionic functionalities for hydrophilic capillary electrochromatography.

Allylglycine, a conventional amino acid derivative, possesses typical zwitterionic and hydrophilic functionalities deriving from the carboxyl and amino groups in its structure. A novel monolithic column poly(allylglycine-co-1, 3, 5-triacryloylhexahydro-1, 3, 5-triazine) (AGly-co-TAT) with powerful hydrophilic selectivity and obvious zwitterionic feature was synthesized successfully with the monomer allyglycine and the cross-linker 1, 3, 5-triacryloylhexahydro-1, 3, 5-triazine through in-situ copolymerization for capillary electrochromatography. The obtained monolithic column has good permeability. Due to the zwitterionic functional groups of allylglycine, the poly(AGly-co-TAT) monolithic column can generate a cathodic and anodic electroosmotic flow (EOF) by changing the mobile phase pH, which is beneficial to expand its application range. The separations of different series of polar analytes, thioureas, xanthines, phenols, peptides and acidic compounds are achieved on this hydrophilic monolithic column due to the powerful hydrophilic, electrostatic and hydrogen bond interactions. Using this monolithic column, hydrophilic separations are achieved even at a lower level of 50% organic solvent. The separation efficiency up to 1.41 × 105 N m-1 and 1.19 × 105 N m-1 is achieved for the separation of theophylline and phenol, respectively. For a real sample, cytochrome C digestion, the monolithic column shows good separation performance, which offers the potential application of the monolithic column on proteomics study.

Fluoro-functionalized stationary phases for electrochromatographic separation of organic fluorides.

Fluorous affinity means remarkably specific interaction between highly organic fluorides. This work aims to explore the potential of fluoro-functionalized stationary phase for the separation of organic fluorides by means of fluorous-fluorous interaction. Here, by using the Michael addition strategy between 1H,1H,2H,2H-perfluorodecanethiol (PFDT) and polydopamine (PD), a novel fluoro-functionalized stationary phase was synthesized for open-tubular capillary electrochromatography (OT-CEC). The PFDT@PD was characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR) and X-ray Photoelectron Spectrometer (XPS). The PFDT@PD@capillary exhibited outstanding separation performance towards neutral compounds (such as alkylbenzenes and chlorobenzenes) and organic fluorides (such as fluorobenzenes and perfluoroalkyl methacrylates etc.) with high resolution and high separation efficiency by hydrophobic interaction and fluorous-fluorous interaction. In addition, the column shows good stability and reproducibility. The relative standard deviations (RSDs) of the retention time for intra-day (n = 5) and inter-day (n = 3) runs and between columns (n = 3) are less than 0.39%, 1.22% and 3.87%, respectively. This novel type of fluoro-functionalized stationary phase represents a great application potential in organic fluorides separation field.