Xylene Isomers Research Articles

Influence of the Mesoporosity of Hierarchical ZSM-5 in Toluene Alkylation by Methanol.

Among the different strategies to design highly shape-selective ZSM-5 to obtain para-xylene through toluene alkylation with methanol, the introduction of mesopores to increase reactant and product diffusion has been proposed but barely studied. In this study, we prepared mesoporous ZSM-5 catalysts, named ZSM5-MT(x), from commercial ZSM-5 (Si/Al = 15), using a two-step micelle-templating procedure with octadecyltrimethylammonium bromide as a surfactant in basic medium (x = NaOH/Si). These materials were used as catalysts for the alkylation of toluene by methanol at a low contact time to avoid thermodynamic equilibrium of the xylene isomers. Compared to the parent ZSM-5, the mesoporous ZSM5-MT(x) catalysts did not improve the para-xylene selectivity, revealing that the strategy of increasing diffusion in the catalyst is not a good strategy to follow. However, ZSM5-MT(0.5) showed less deactivation on stream than the parent ZSM-5. Therefore, introducing mesopores to ZSM-5 could be interesting to explore, combined with another strategy of shape selectivity, such as the passivation of the external surface acidity.

Crystals of Ni6L12 Ellipsoidal Tubes as Single-Crystal-to-Single-Crystal Adsorption Matrix: Penetrative Study of Self-Assembled Crystals vs Guest-Exchanged Crystals.

Informative similarities/differences between self-assembled and single-crystal-to-single-crystal (SCSC) guest-exchanged crystals based on both the molecular structure and adsorption nature are observed. The self-assembly of Ni(ClO4)2 with a dicyclopentyldi(pyridine-3-yl)silane bidentate ligand (L) in a mixture of toluene and acetonitrile gives rise to purple crystals consisting of double-stranded ellipsoidal tubes, [Ni6(ClO4)4(CH3CN)8L12]·8ClO4·4CH3CN·5C7H8. The coordinated acetonitriles as well as the solvates are removed at 170 °C to transform the purple crystals into blue crystals of [Ni(ClO4)2L2]n that return to the original crystals in the mixture of toluene and acetonitrile. Further, the toluene and acetonitrile solvates of the original crystals are replaced by o-, m-, and p-xylene isomers within 5 min in a SCSC manner. In the present study, SCSC xylene-exchanged crystals were compared with crystals obtained from direct self-assembly in a mixture of each xylene isomer and acetonitrile.

Solid-State [4+4] Cycloaddition and Cycloreversion with Use of Unpaired Hydrogen-Bond Donors to Achieve Solvatomorphism and Stabilization.

The crystal structure of a commercially available anthracene derivative, anthracene-9-thiocarboxamide, is reported here for the first time. The compound undergoes a [4+4] cycloaddition in the solid state to afford facile synthesis of the cycloadduct (CA). The cycloaddition is also reversible in the solid state using heat or mechanical force. Due to the presence of unpaired, strong hydrogen-bond donor atoms on the CA, significant solvatomorphism is achieved, and components of the solvatomorphs self-assemble into four different classes of supramolecular structures. The CA readily crystallizes with a variety of structurally-diverse solvents including those containing oxygen-, nitrogen-, or pi-acceptors. Some of the solvents the CA crystallized with include thiophene, benzene, and the three xylene isomers; thus, the CA was employed in industrially-relevant solvent separation. However, in competition studies, the CA did not exhibit selectivity. Lastly, it is demonstrated that the CA crystallizes with vinyl-containing monomers and is currently the only compound that crystallizes with both widely used monomers 4-vinylpyridine and styrene. Solid-state complexation of the CA with the monomers affords over a 50 °C increase in the monomer's thermal stabilities. The strategy of designing molecules with unused donors can be applied to achieve separations or volatile liquid stabilization.

A comparative study of the oxidation of toluene and the three isomers of xylene

This paper presents an experimental and modeling study of the oxidation of toluene, ortho-xylene, meta-xylene, and para-xylene in a jet-stirred reactor. In order to facilitate comparisons, the same experimental conditions were used for the four reactants, i.e. temperatures from 600 to 1100 K, a pressure of 1.07 bar, a residence time of 2 s, an initial fuel mole fraction of 0.005, and equivalence ratios of 0.5, 1 and 2. Compared to literature studies using the same type of reactor, due to higher residence time and initial fuel mole fraction, a higher number of oxygenated aromatic products was quantified and some reactivity was observed at lower temperatures, especially for ortho-xylene, which started to react from 700 K. For this fuel, the formation of phthalan, an aromatic compound including an oxetane ring and indicating low-temperature oxidation chemistry, was confirmed. A new detailed kinetic model combining literature mechanisms was proposed and allowed well predicting the reactivity of the four methylated benzenes of interest with an acceptable simulation of most of the quantified products. Flowrate and sensitivity analyses were made to highlight the similarities and to explain the difference of reactivity between the four investigated reactants.

Unconventional seed-assisted strategy for Al-rich hierarchical ZSM-48 zeolite

Inferior diffusion capacity and insufficient acid density hinder the practical application of ZSM-48 zeolite. Finding a simple and practical strategy to simultaneously address these two defects remains a challenge. In response to this dilemma, we developed an unconventional seed-assisted synthesis strategy for Al-rich hierarchical ZSM-48 zeolite. This approach allows for achieving a broader range of silica to alumina ratio and accelerates the entire crystallization process through the selection of unconventional seeds. The synergy between the seed and organic template was demonstrated to play a pivotal role in facilitating nucleation. Direct evidence from 1H-29Si CP MAS NMR, TG, and IR results demonstrates that hexamethonium ions (HM2+) electrostatically adsorb at the defect sites on the seed, thereby promoting nucleation sites formation. Smaller seed crystals undergo more etching during the induction period, resulting in additional defects and enhanced nucleation ability. The obtained catalyst exhibits a diffusion time constant (Deff/L2) nine times that of conventional ZSM-48 zeolite when using p-xylene as a probe molecule. In m-xylene isomerization reaction, Al-rich hierarchical ZSM-48 demonstrates excellent stability along with higher selectivity and yield for p-xylene compared to typical ZSM-5 catalysts. Remarkably, long-term testing of 1000 h yields over 22.5 % of p-xylene, indicating the potential of this catalyst as an alternative for xylene isomerization reaction. This work not only advances the practical application process of ZSM-48 catalyst but also provides valuable insights for optimizing other zeolites.

Liquid‐phase selective adsorption of xylene isomers in ultramicroporous carbon spheres

AbstractThe objective of this work is to investigate adsorption separation of liquid‐phase xylene isomers using ultramicroporous carbon spheres. The synthesized glucose‐based adsorbent (UMC‐xyl) enabled the challenging separation of liquid‐phase p‐xylene/m‐xylene with an adsorption selectivity of 53 as well as p‐xylene uptake of 91mg/g, outperforming a series of commercial adsorbents including the industrial benchmark KBaX. The micropore diffusion model was used to give the best fit to the adsorption kinetics of UMC‐xyl with a rate achieved higher than KBaX. The xylene isomer separation was facilitated by the narrow ultramicropore size distributed at 5.8–6.8 Å in UMC‐xyl via a synergistic kinetic and size‐sieving separation mechanism. Breakthrough experiments confirmed the effectiveness of UMC‐xyl in the dynamic selective separation of p‐xylene from xylene isomers, together with superior multiple‐cycle eluent regenerability under the synergistic effects of the “like‐dissolve‐like” principle and π–π interaction. The work opens a new direction of using porous carbon adsorbents for continuous liquid‐phase separation of challenging hydrocarbon isomers.

A new organic soluble cucurbit[7]uril-truxene derivative as stationary phase for gas chromatographic separation of some challenging isomers

The insolubility of parent cucurbit[n]uril or substituted-cucurbit[n]uril derivatives in organic solvents has always been a key factor restricting the column efficiency and selectivity of capillary gas chromatography column based on cucurbit[n]uril. In this work, a novel organic soluble cucurbit [7]uril-truxene derivative (Q [7]-Tr) was synthesized by Heck coupling reaction between the mono-iodinated hexahexyl-truxene and 4-vinylbenzyloxy-Q [7]. A capillary gas chromatographic column was prepared by static method with this derivative as stationary phase. The column exhibited moderate polarity and an efficiency of 5857 plates/m using n-dodecane as analyte at 120 °C, indicating the highest column efficiency of all the based-cucurbit[n]uril columns published. The Q [7]-Tr column showed high resolutions for a wide range of analytes with different polarities and better separated selectivity towards tough isomers such as aromatic amines isomers and xylene isomers compared to commercial HP-5, DB-35, Stabilwax and Q [7]-based columns. Moreover, the new column exhibited high thermal stability up to 320 °C and excellent repeatability, demonstrating a great potential as a new stationary phase in capillary gas chromatography.

Synthesis of hierarchically porous zirconium-based metal-organic framework@silica core-shell stationary phase through etching strategy for liquid chromatography

Metal organic frameworks (MOFs) show promise to be employed as stationary phase for high performance liquid chromatography (HPLC), however, the microporous structures of MOFs seriously restrict the diffusion and mass transfer of solute molecules, leading to a low column efficiency. In this paper, the fabrication of hierarchically porous UiO-66@SiO2 (HP- UiO-66@SiO2) core-shell microspheres via H2O2 etching has been proposed as a viable approach to enhance the separation performance of MOFs-based columns for HPLC. Through the direct treatment of the preliminary prepared UiO-66@SiO2 microspheres with H2O2 etching, HP-UiO-66@SiO2 core-shell microspheres were successfully synthesized with an enlarged pore size of up to 9 nm, facilitating efficient mass transfer in chromatographic separation. The prepared HP-UiO-66@SiO2 core-shell microspheres were then explored as stationary phase in HPLC to separate the nonpolar alkyl benzene homologues, the polar aromatic alcohol homologues and the xylene isomers. The results indicated that the baseline separations of these solutes were achieved successfully with narrow peak width and higher resolution than the UiO-66@SiO2 column. The HP-UiO-66@SiO2 column exhibited superior separation performance, reaching a maximum plate number of 134,459/m for fluorene, and showing good reproducibility. As a result, this template-free approach suggests that the fabrication of hierarchically porous MOFs@silica core-shell microspheres is a successful approach to enhance the column efficiency of MOFs-based columns in HPLC.

MOF-composite sensors to eliminate the QCM positive frequency shift

In a quartz crystal microbalance (QCM) Sauerbrey equation can usually be applied in the ideal scenario and when the QCM frequency shift goes to the negative direction. In some cases, however, the requirements to achieve the ideal condition are not fulfilled and thus leading to QCM positive frequency shift phenomenon. Herein we have also observed that a porphyrin-based metal organic frameworks (MOF), namely MOF-525(Zn), QCM sensor also exhibits the positive frequency shift phenomenon when exposed to xylene isomers, which could be caused by the loose attachment of the MOF nanoparticles on the QCM surface. Therefore, in the presence of the analytes, the bonding between the MOF and the QCM surface is disturbed and higher analyte concentration also leads to the increase of the sensitive layer stiffness, resulting in higher positive frequency shift. However, such a phenomenon can be completely eliminated by simply adding polymer to MOF nanoparticle sensors to strengthen the bonding of MOF nanoparticles to the QCM surface. Through this study we have shown that adjusting the amount of polymer is very crucial to completely reverse the positive frequency response. Otherwise, it appears a critical analyte concentration of gas analytes where the QCM frequency shift changes its direction from negative to positive response. Lastly, the same strategy has also been used to other MOF-based QCM sensor systems where their sensitive layer is built from other MOFs, namely MOF-525 and NU-902, and ethanol is used as the analyte to prove the generalizability of this simple approach.

Characterization of inhalation exposures at a wildfire incident during the Wildland Firefighter Exposure and Health Effects (WFFEHE) Study.

Wildland firefighters (WFFs) are exposed to many inhalation hazards working in the wildland fire environment. To assess occupational exposures and acute and subacute health effects among WFFs, the wildland firefighter exposure and health effects study collected data for a 2-year repeated measures study. This manuscript describes the exposure assessment from one Interagency Hotshot Crew (N = 19) conducted at a wildfire incident. Exposures to benzene, toluene, ethylbenzene, xylene isomers, formaldehyde, acetaldehyde, and naphthalene were measured through personal air sampling each work shift. Biological monitoring was done for creatinine-adjusted levoglucosan in urine pre- and post-shift. For 3 days sampling at the wildfire incident, benzene, toluene, ethylbenzene, xylene isomers (m and p, and o) exposure was highest on day 1 (geometric mean [GM] = 0.015, 0.042, 0.10, 0.42, and 0.15 ppm, respectively) when WFFs were not exposed to smoke but used chainsaws to remove vegetation and prepare fire suppression breaks. Exposure to formaldehyde and acetaldehyde was highest on day 2 (GM = 0.03 and 0.036 ppm, respectively) when the WFFs conducted a firing operation and were directly exposed to wildfire smoke. The greatest difference of pre- and post-shift levoglucosan concentrations were observed on day 3 (pre-shift: 9.7 and post-shift: 47 μg/mg creatinine) after WFFs conducted mop up (returned to partially burned area to extinguish any smoldering vegetation). Overall, 65% of paired samples (across all sample days) showed a post-shift increase in urinary levoglucosan and 5 firefighters were exposed to benzene at concentrations at or above the National Institute for Occupational Safety and Health (NIOSH) recommended exposure limit. Our findings further demonstrate that exposure to inhalation hazards is one of many risks that wildland firefighters experience while suppressing wildfires.

Separating Xylene Isomers with a Calcium Metal-Organic Framework.

The purification of p-xylene (pX) from its xylene isomers represents a challenging but important industrial process. Herein, we report the efficient separation of pX from its ortho- and meta- isomers by a microporous calcium-based metal-organic framework material (HIAM-203) with a flexible skeleton. At 30 °C, all three isomers are accommodated but the adsorption kinetics of o-xylene (oX) and m-xylene (mX) are substantially slower than that of pX, and at an elevated temperature of 120 °C, oX and mX are fully excluded while pX can be adsorbed. Multicomponent column breakthrough measurements and vapor-phase/liquid-phase adsorption experiments have demonstrated the capability of HIAM-203 for efficient separation of xylene isomers. Ab initio calculations have provided useful information for understanding the adsorption mechanism.

Separating Xylene Isomers with a Calcium Metal‐Organic Framework

AbstractThe purification of p‐xylene (pX) from its xylene isomers represents a challenging but important industrial process. Herein, we report the efficient separation of pX from its ortho‐ and meta‐ isomers by a microporous calcium‐based metal–organic framework material (HIAM‐203) with a flexible skeleton. At 30 °C, all three isomers are accommodated but the adsorption kinetics of o‐xylene (oX) and m‐xylene (mX) are substantially slower than that of pX, and at an elevated temperature of 120 °C, oX and mX are fully excluded while pX can be adsorbed. Multicomponent column breakthrough measurements and vapor‐phase/liquid‐phase adsorption experiments have demonstrated the capability of HIAM‐203 for efficient separation of xylene isomers. Ab initio calculations have provided useful information for understanding the adsorption mechanism.

PH-Regulated Refinement of Pore Size in Carbon Spheres for Size-Sieving of Gaseous C8 , C6 and C3 Hydrocarbon Pairs.

Selective separation of industrial important C8 , C6 and C3 hydrocarbon pairs by physisorbents can greatly reduce the energy intensity related to the currently used cryogenic distillation techniques. The achievement of size-sieving based on carbonaceous materials is desirable, but commonly hindered by the random structure of carbons often with a broad pore size distribution. Herein, a pH-regulated pre-condensation strategy was introduced to control the carbon pore architecture by the sp2 /sp3 hybridization of precursor. The lower pH value during pre-condensation of glucose facilitates the growth of aromatic nanodomains, rearrangement of stacked layers and a concomitant transition from sp3 -C to sp2 -C. The subsequent pyrolysis endows the pore size manipulated from 6.8 to 4.8 Å and narrowly distributed over a range of 0.2 Å. The refined pores enable effective size-sieving of C8 , C6 and C3 hydrocarbon pairs with high separation factor of 1.9 and 4.9 for C8 xylene (X) isomers para-X/meta-X and para-X/ortho-X, respectively, 5.1 for C6 alkane isomers n-hexane/3-methylpentane, and 22.0 for C3 H6 /C3 H8 . The excellent separation performance based-on size exclusion effect is validated by static adsorption isotherms and dynamic breakthrough experiments. This synthesis strategy provides a means of exploring advanced carbonaceous materials with controlled hybridized structure and pore sizes for challenging separation needs.

Core-shell metal-organic framework/silica hybrid with tunable shell structure as stationary phase for high performance liquid chromatography

Metal-organic framework/silica composite (SSU) were prepared by growing UiO-66 on the amino-functionalized SiO2 core-shell spheres (SiO2@dSiO2) via a simple one-pot synthesis approach. By controlling the concentration of Zr4+, the obtained SSU have two different morphologies: spheres-on-sphere and layer-on-sphere. The spheres-on-sphere structure is formed by the aggregation of UiO-66 nanocrystals on the surface of SiO2@dSiO2 spheres. SSU-5 and SSU-20, which contain spheres-on-sphere composites have mesopores with a pore size of about 45 nm in addition to the characteristic micropores of UiO-66 with a pore size of 1 nm. In addition, UiO-66 nanocrystals were grown both inside and outside the pores of SiO2@dSiO2, resulting in a 27% loading of UiO-66 in the SSU. The layer-on-sphere is the surface of SiO2@dSiO2 covered with a layer of UiO-66 nanocrystals. SSU with this structure has only a characteristic pore size of about 1 nm belonging to UiO-66 and is therefore not suitable as a packed stationary phase for high performance liquid chromatography. The SSU spheres were packed into columns and tested for the separation of xylene isomers, aromatics, biomolecules, acidic and basic analytes. With both micropores and mesopores, SSU with spheres-on-sphere structure achieved baseline separation of both small and large molecules. Efficiencies up to 48,150, 50,452 and 41,318 plates m − 1 were achieved for m-xylene, p-xylene and o-xylene, respectively. The relative standard deviations of the retention times of anilines for run-to-run, day-to-day and column-to-column were all less than 6.1%. The results show that the SSU with spheres-on-sphere structure has great potential for high performance chromatographic separation.

Structural functionalization in robust metal–organic frameworks for p-xylene separation with superior adsorption capacity

The subtle differences between the xylene isomers make the separation of p-xylene/m-xylene/o-xylene mixtures one of the most challenging tasks in the petrochemical industry. In this study, CAU-1 was used as a platform compound to construct functionalized pore environment with high stability for selective PX adsorption and separation. Single-component adsorption tests and liquid-phase multicomponent adsorption experiments showed that a series of functionalized scaffolds exhibited PX selective adsorption compared to the other two isomers, among them functional groups optimized CAU-1-OH ([Al8(OH)4(OCH3)8(BDC-OH)6])(BDC = 1,4-benzenedicarboxylate) showed ultra-high PX adsorption capacity (460 mg/g), superior to most reported MOFs. And the PX/MX selectivity of functionalized CAU-1-OH was improved by 18% compared to the original CAU-1. Furthermore, vapor breakthrough experiments on CAU-1-OH showed that it can effectively extract PX from ternary PX/MX/OX mixtures. The fundamental PX selective adsorption mechanism was also visually illustrated using grand canonical Monte Carlo simulation. In addition, the stability of the adsorbent was investigated under different conditions (RH = 40% and 80%, pH = 1–11, different solvents, and high temperatures), and the unchanged PXRD and BET curves indicate that the adsorbent has excellent structural stability. As thus, the large PX adsorption capacity, ultra-high structural stability, and excellent isomer separation performance make these materials good candidates for industrial PX purification from xylene isomers mixture.

Mathematical simulation and optimization of xylene isomerization reactor to enhance p‐xylene production

AbstractThis study investigated mathematical modeling and optimization of the xylene isomerization reaction in a commercial adiabatic reactor. The proposed model, consisting of a set of algebraic and ordinary differential equations, is based on a heterogeneous one‐dimensional steady‐state formulation. To verify the proposed model, the simulation results have been compared to available data from an industrial reactor. A good agreement has been found between the simulation and plant data. The genetic algorithm (GA) method is applied to optimize the reactor operating conditions considering the para‐xylene (p‐xylene) mole fraction in reactor outlet as the main objective function. According to the simulation results, there is an optimum initial temperature for maximizing the objective function. In the optimization process, the p‐xylene mole fraction was enhanced by 3.0% at an optimized feed temperature of 678.04K.

Expanding the ethanol blend wall in California: Emissions comparison between E10 and E15

This study assessed the potential of increasing ethanol content in California reformulated gasoline (CaRFG) by investigating the exhaust emissions from a fleet of 20 light-duty vehicles. A baseline CaRFG E10 (10% ethanol by volume) fuel was splash blended with denatured ethanol to create a E15 fuel. Each vehicle/fuel combination were exercised over triplicate Federal Test Procedure (FTP) cycles on a chassis dynamometer. Our results showed no statistically significant fuel effect on nitrogen oxide (NOx) emissions for E15, whereas total hydrocarbons (THC), non-methane hydrocarbons (NMHC), and carbon monoxide (CO) showed either marginally or statistically significant reductions for E15. Particulate matter (PM) and solid particle number emissions were positively impacted by ethanol, exhibiting statistically significant reductions. Acetaldehyde and ethanol emissions responded strongly with ethanol across the fleet of 20 vehicles, while formaldehyde emissions did not show a statistically significant effect. Monoaromatic species and 1,3-butadiene showed mixed results, with ethylbenzene and the xylene isomers showing strong fuel differences. Although no strong differences were found for carbon dioxide (CO2) emissions, E15 showed life cycle greenhouse gas (GHG) emissions savings when compared to E10.

Indoor level of BTEX and health risk assessment at science laboratories in a university

The levels of volatile organic compounds (VOCs) such as Benzene, Toluene, Ethylbenzene, and Xylene isomers (BTEX) are important parameters for an indoor air quality assessment. Exposure to BTEX in science laboratories in a university can potentially cause health risks to workers. Active sampling was carried out using Tenax® GR sorbent tubes and analyzed with thermal desorption gas chromatography-mass spectrometry (TD-GCMS) to measure the BTEX levels at selected indoor areas. The average concentration of individual BTEX at the laboratories complex were as follows: Benzene (1.76 ± 0.44 μg/m3), Toluene (8.15 ± 2.99 μg/m3), Ethylbenzene (3.75 ± 0.69 μg/m3), m, p-Xylene (6.07 ± 1.19 μg/m3) and o-Xylene (4.84 ± 0.43 μg/m3). The distribution of the BTEX components varied depending on the floor level, laboratory activities, laboratory size, and interior furniture. Non-cancer risk estimates based on hazard quotient value for BTEX were < 1, indicating unlikely non-cancer risk. Lifetime cancer risk estimates for Benzene were in the range of 1.16 × 10-6 – 2.54 × 10-6 indicating possible cancer risk at the sampled indoor locations. Therefore, science laboratories can potentially pose a health risk to workers from long-term exposure to BTEX.

Hematological Changes in Gas Station Workers.

(1) Background: Benzene, toluene, and xylene isomers (BTX) are present in gasoline. Exposure to benzene may lead to the appearance of a series of signs, symptoms, and complications, which are characterized by benzene poisoning, which is an occupational disease. This study evaluated the presence of signs and symptoms related to occupational exposure and whether occupational exposure to BTX is associated with the development of hematological changes. (2) Material and Methods: This cross-sectional epidemiological study included 542 participants, in which 324 were gas station workers (GSWs) and 218 were office workers (OWs) with no occupational exposure to benzene. To characterize the type of exposure (exposed and not exposed), trans,trans-Muconic acid (tt-MA), Hippuric acid (HA), and Methylhippuric acid (MHA) were used as exposure biomarkers. The tt-MA analysis revealed that the GSWs had 0.29 mg/g of urinary creatinine and the OWs had 0.13 mg/g of urinary creatinine. For HA, the GSWs presented 0.49 g/g of creatinine while the OWs presented 0.07. MHA analysis revealed that the GSWs had 1.57 g/g creatinine and the OWs had 0.01 g/g creatinine. Occupation habits and clinical symptoms were collected by questionnaire and blood samples were analyzed for hematological parameters. The persistence of hematological changes was evaluated with three serial blood collections every 15 days followed by laboratory hematological analysis. A descriptive analysis by the Chi-square test method was performed to evaluate the association between occupational exposure to fuels and the occurrence of changes in hematological parameters. (3) Results: In the GSWs, the most described signs and symptoms were somnolence (45.1%), headache (38.3%), dizziness (27.5%), tingling (25.4%), and involuntary movement (25%). Twenty GSWs that presented hematological alterations performed serial collections fifteen days apart. In addition, these workers presented total leukocyte counts above the upper limit and lymphocyte counts close to the lower limit. Leukocytosis and lymphopenia are hematological alterations present in chronic benzene poisoning. (4) Conclusions: The results found an initial change in different hematological parameters routinely used in clinics to evaluate health conditions. These findings reveal the importance of valuing clinical changes, even in the absence of disease, during the health monitoring of gas station workers and other groups that share the same space.

Particle Size Regulation of Single-Crystalline Covalent Organic Frameworks for High Performance of Gas Chromatography.

Although polycrystalline covalent organic frameworks (PCOFs) have already shown great potential as stationary phases for chromatography, irregular shape and size distribution of PCOFs make regulation of particle size of PCOFs for high separation performance impossible, which is accessible by the application of single-crystalline COFs (SCOFs). Herein, we showed preparation of three-dimensional SCOF (SCOF-303) bonded capillaries (SCOF-303-capillary) with different particle sizes (about 0.4-1.6 μm) and further investigated gas chromatographic separation ability of these SCOF-303-capillaries for isomers of xylene, dichlorobenzene, and pinene. It was found resolution and column efficiency of SCOF-303-capillaries for isomers decreased with the increase in particle size, mainly resulting from the weaker size-exclusion effect and higher mass transfer resistance of the larger particle size of flexible SCOF-303. The obtained SCOF-303-capillary (particle size of ∼0.4 μm) offered baseline separation of xylene isomers with the high resolution of 2.26-3.52, great efficiency of 7879 plates m-1 for p-xylene, better than PCOF-303-capillary, and commercial DB-5 and HP-FFAP capillary columns as well as many reported capillaries. This work not only shows the great potential of SCOFs for gas chromatography but also provides the theoretical direction for the design of the efficient COF based stationary phase by adjusting the particle sizes.