Metal-organic frameworks for the sorption of acetone and isopropanol in exhaled breath of diabetics prior to quantitation by gas chromatography.

A method is described for non-invasive glucose monitoring of diabetics by means of breath analysis. The metal-organic frameworks (MOFs) ZIF-7, UiO-66 and MOF-5 were chosen as sorbents in packed tubes for sampling and preconcentration of acetone and isopropanol which are established diabetes biomarkers. The MOF UiO-66 was found to be the most appropriate sorbent. Following thermal desorption, acetone and isopropanol where quantified by GC. The method has low limits of detection (0.79-0.84 µg·L-1) and wide linear ranges (5-2000 µg·L-1). It is assumed that the good performance of UiO-66 as a sorbent results from its large surface area and unique porous structure, and from van der Waals interactions. The relative standard deviation for six replicate cycles of sampling and preconcentration using one 50 mg UiO-66 packed tube ranged between 2.3 and 6.7% for intra-day assays, and from 2.7 to 4.3% for inter-day assays. A tube packed with 50 mg of UiO-66 packed tube can be used in over 120 cycles of adsorption/desorption without significant loss of collection efficiency. The GC method has been applied for the analysis of diabetic breath samples, and the recoveries from spiked samples ranged from 89.1 to 107.6%. Graphical abstract Schematic presentation of metal-organic frameworks as sorbents combined with thermal desorption-gas chromatography for the determination of acetone and isopropanol in exhaled breath of diabetics.

Removal of acetone from air emissions by biotrickling filters: providing solutions from laboratory to full-scale.

A full-scale biotrickling filter (BTF) treating acetone air emissions of wood-coating activities showed difficulties to achieve outlet concentrations lower than 125 mg C m-3, especially for high inlet concentrations and oscillating emissions. To solve this problem, a laboratory investigation on acetone removal was carried out simulating typical industrial conditions: discontinuous and variable inlet concentrations and intermittent spraying. The results were evaluated in terms of removal efficiency and outlet gas emission pattern. Industrial emissions and operational protocols were simulated: inlet load up to 70 g C m-3 h-1 during 2 cycles of 4 h per day and intermittent trickling of 15 min per hour. The outlet gas stream of the pollutant was affected by intermittent spraying, causing a fugitive emission of pollutant. Complete removal efficiency was obtained during non-spraying. Average removal efficiencies higher than 85% were obtained, showing the feasibility of BTF to treat acetone. The outlet gas stream showed a clear dependence on the pH of the trickling liquid, decreasing the removal at pH < 5.5. Thus, a proper control of alkalinity, with regular NaHCO3 addition, was required for successful operation. The laboratory findings were fruitfully transferred to the industry, and the removal of acetone by full-scale BTF was improved.

Energy efficiency of acetone, butanol, and ethanol (ABE) recovery by heat-integrated distillation.

Acetone, butanol, and ethanol (ABE) is an alternative biofuel. However, the energy requirement of ABE recovery by distillation is considered elevated (> 15.2 MJ fuel/Kg-ABE), due to the low concentration of ABE from fermentation broths (between 15 and 30 g/l). In this work, to reduce the energy requirements of ABE recovery, four processes of heat-integrated distillation were proposed. The energy requirements and economic evaluations were performed using the fermentation broths of several biocatalysts. Energy requirements of the processes with four distillation columns and three distillation columns were similar (between 7.7 and 11.7 MJ fuel/kg-ABE). Double-effect system (DED) with four columns was the most economical process (0.12-0.16 $/kg-ABE). ABE recovery from dilute solutions by DED achieved energy requirements between 6.1 and 8.7 MJ fuel/kg-ABE. Vapor compression distillation (VCD) reached the lowest energy consumptions (between 4.7 and 7.3 MJ fuel/kg-ABE). Energy requirements for ABE recovery DED and VCD were lower than that for integrated reactors. The energy requirements of ABE production were between 1.3- and 2.0-fold higher than that for alternative biofuels (ethanol or isobutanol). However, the energy efficiency of ABE production was equivalent than that for ethanol and isobutanol (between 0.71 and 0.76) because of hydrogen production in ABE fermentation.

Effects of BTEX on the Removal of Acetone in a Coaxial Non-Thermal Plasma Reactor: Role Analysis of the Methyl Group.

The removal of acetone and benzene series (BTEX) under individual and concurrent conditions is carried out in a coaxial nonthermal plasma (NTP) reactor. The results show that the benzene series has a significant negative impact on acetone conversion and CO2 selectivity under NTP treatment. Furthermore, it is found that p-xylene significantly promotes COx selectivity under co-treatment with acetone because of greater CO generation. Based on the results of transient FTIR, MS, and GC-MS, it is seen that quantities of formic acid, formaldehyde, and ring-opening byproducts from benzene series decomposition are reduced, while quantities of aromatic byproducts with carboxyl, phenolic, and aldehyde groups on the benzene ring increase under coexistence conditions. With the help of theoretical calculation and kinetic analysis, hydrogen abstraction from the methyl group and active hydroxyl radical consumption are proposed as critical factors in the BTEX inhibition effect on acetone degradation.

A dynamic metabolic flux analysis of ABE (acetone-butanol-ethanol) fermentation by Clostridium acetobutylicum ATCC 824, with riboflavin as a by-product.

The present study reveals that supplementing sodium acetate (NaAc) strongly stimulates riboflavin production in acetone-butanol-ethanol (ABE) fermentation by Clostridium acetobutylicum ATCC 824 with xylose as carbon source. Riboflavin production increased from undetectable concentrations to ∼0.2 g L-1 (0.53 mM) when supplementing 60 mM NaAc. Of interest, solvents production and biomass yield were also promoted with fivefold acetone, 2.6-fold butanol, and 2.4-fold biomass adding NaAc. A kinetic metabolic model, developed to simulate ABE biosystem, with riboflavin production, revealed from a dynamic metabolic flux analysis (dMFA) simultaneous increase of riboflavin (ribA) and GTP (precursor of riboflavin) (PurM) synthesis flux rates under NaAc supplementation. The model includes 23 fluxes, 24 metabolites, and 72 kinetic parameters. It also suggested that NaAc condition has first stimulated the accumulation of intracellular metabolite intermediates during the acidogenic phase, which have then fed the solventogenic phase leading to increased ABE production. In addition, NaAc resulted in higher intracellular levels of NADH during the whole culture. Moreover, lower GTP-to-adenosine phosphates (ATP, ADP, AMP) ratio under NaAc supplemented condition suggests that GTP may have a minor role in the cell energetic metabolism compared to its contribution to riboflavin synthesis.

Acetone production with metabolically engineered strains of Acetobacterium woodii.

Expected depletion of oil and fossil resources urges the development of new alternative routes for the production of bulk chemicals and fuels beyond petroleum resources. In this study, the clostridial acetone pathway was used for the formation of acetone in the acetogenic bacterium Acetobacterium woodii. The acetone production operon (APO) containing the genes thlA (encoding thiolase A), ctfA/ctfB (encoding CoA transferase), and adc (encoding acetoacetate decarboxylase) from Clostridium acetobutylicum were cloned under the control of the thlA promoter into four vectors having different replicons for Gram-positives (pIP404, pBP1, pCB102, and pCD6). Stable replication was observed for all constructs. A. woodii [pJIR_actthlA] achieved the maximal acetone concentration under autotrophic conditions (15.2±3.4mM). Promoter sequences of the genes ackA from A. woodii and pta-ack from C. ljungdahlii were determined by primer extension (PEX) and cloned upstream of the APO. The highest acetone production in recombinant A. woodii cells was achieved using the promoters PthlA and Ppta-ack. Batch fermentations using A. woodii [pMTL84151_actthlA] in a bioreactor revealed that acetate concentration had an effect on the acetone production, due to the high Km value of the CoA transferase. In order to establish consistent acetate concentration within the bioreactor and to increase biomass, a continuous fermentation process for A. woodii was developed. Thus, acetone productivity of the strain A. woodii [pMTL84151_actthlA] was increased from 1.2mgL(-1)h(-1) in bottle fermentation to 26.4mgL(-1)h(-1) in continuous gas fermentation.

A Portable Real-Time Ringdown Breath Acetone Analyzer: Toward Potential Diabetic Screening and Management.

Breath analysis has been considered a suitable tool to evaluate diseases of the respiratory system and those that involve metabolic changes, such as diabetes. Breath acetone has long been known as a biomarker for diabetes. However, the results from published data by far have been inconclusive regarding whether breath acetone is a reliable index of diabetic screening. Large variations exist among the results of different studies because there has been no "best-practice method" for breath-acetone measurements as a result of technical problems of sampling and analysis. In this mini-review, we update the current status of our development of a laser-based breath acetone analyzer toward real-time, one-line diabetic screening and a point-of-care instrument for diabetic management. An integrated standalone breath acetone analyzer based on the cavity ringdown spectroscopy technique has been developed. The instrument was validated by using the certificated gas chromatography-mass spectrometry. The linear fittings suggest that the obtained acetone concentrations via both methods are consistent. Breath samples from each individual subject under various conditions in total, 1257 breath samples were taken from 22 Type 1 diabetic (T1D) patients, 312 Type 2 diabetic (T2D) patients, which is one of the largest numbers of T2D subjects ever used in a single study, and 52 non-diabetic healthy subjects. Simultaneous blood glucose (BG) levels were also tested using a standard diabetic management BG meter. The mean breath acetone concentrations were determined to be 4.9 ± 16 ppm (22 T1D), and 1.5 ± 1.3 ppm (312 T2D), which are about 4.5 and 1.4 times of the one in the 42 non-diabetic healthy subjects, 1.1 ± 0.5 ppm, respectively. A preliminary quantitative correlation (R = 0.56, p < 0.05) between the mean individual breath acetone concentration and the mean individual BG levels does exist in 20 T1D subjects with no ketoacidosis. No direct correlation is observed in T1D subjects, T2D subjects, and healthy subjects. The results from a relatively large number of subjects tested indicate that an elevated mean breath acetone concentration exists in diabetic patients in general. Although many physiological parameters affect breath acetone, under a specifically controlled condition fast (<1 min) and portable breath acetone measurement can be used for screening abnormal metabolic status including diabetes, for point-of-care monitoring status of ketone bodies which have the signature smell of breath acetone, and for breath acetone related clinical studies requiring a large number of tests.

The secondary drying and the fate of organic solvents for spray dried dispersion drug product.

PURPOSE: To understand the mechanisms of secondary drying of spray-dried dispersion (SDD) drug product and establish a model to describe the fate of organic solvents in such a product. METHODS: The experimental approach includes characterization of the SDD particles, drying studies of SDD using an integrated weighing balance and mass spectrometer, and the subsequent generation of the drying curve. The theoretical approach includes the establishment of a Fickian diffusion model. RESULTS: The kinetics of solvent removal during secondary drying from the lab scale to a bench scale follows Fickian diffusion model. Excellent agreement is obtained between the experimental data and the prediction from the modeling. CONCLUSIONS: The diffusion process is dependent upon temperature. The key to a successful scale up of the secondary drying is to control the drying temperature. The fate of primary solvents including methanol and acetone, and their potential impurity such as benzene can be described by the Fickian diffusion model. A mathematical relationship based upon the ratio of diffusion coefficient was established to predict the benzene concentration from the fate of the primary solvent during the secondary drying process.

Assessment of morphological changes of Clostridium acetobutylicum by flow cytometry during acetone/butanol/ethanol extractive fermentation.

Acetone/butanol/ethanol (ABE) fermentation by Clostridium acetobutylicum was investigated in extractive fed-batch experiments. In conventional fermentations, metabolic activity ceases when a critical threshold products concentration is reached (~21.6 g solvents l(-1)). Solvents production was increased up to 36.6 and 37.2 g l(-1), respectively, using 2-butyl-1-octanol (aqueous to organic ratio: 1:0.25 v/v) and pomace olive oil (1:1 v/v) as extraction solvents. The morphological changes of different cell types were monitored and quantified using flow cytometry. Butanol production in extractive fermentations with pomace olive oil was achieved mainly by vegetative cells, whereas the percentage of sporulating cells was lower than 10%.

Improvement of acetone, butanol, and ethanol production from woody biomass using organosolv pretreatment.

A suitable pretreatment is a prerequisite of efficient acetone-butanol-ethanol (ABE) production from wood by Clostridia. In this study, organosolv fractionation, an effective pretreatment with ability to separate lignin as a co-product, was evaluated for ABE production from softwood pine and hardwood elm. ABE production from untreated woods was limited to the yield of 81 g ABE/kg wood and concentration of 5.5 g ABE/L. Thus, the woods were pretreated with aqueous ethanol at elevated temperatures before hydrolysis and fermentation to ABE by Clostridium acetobutylicum. Hydrolysis of pine and elm pretreated at 180 °C for 60 min resulted in the highest sugar concentrations of 16.8 and 23.2 g/L, respectively. The hydrolysate obtained from elm was fermented to ABE with the highest yield of 121.1 g/kg and concentration of 11.6 g/L. The maximum yield of 87.9 g/kg was obtained from pine pretreated for 30 min at 150 °C. Moreover, structural modifications in the woods were investigated and related to the improvements. The woody biomasses are suitable feedstocks for ABE production after the organosolv pretreatment. Effects of the pretreatment conditions on ABE production might be related to the reduced cellulose crystallinity, reduced lignin and hemicellulose content, and lower total phenolic compounds in the hydrolysates.

Solvent screening methodology for in situ ABE extractive fermentation.

Solvent screening for in situ liquid extraction of products from acetone-butanol-ethanol (ABE) fermentation was carried out, taking into account biological parameters (biocompatibility, bioavailability, and product yield) and extraction performance (partition coefficient and selectivity) determined in real fermentation broth. On the basis of different solvent characteristics obtained from literature, 16 compounds from different chemical families were selected and experimentally evaluated for their extraction capabilities in a real ABE fermentation broth system. From these compounds, nine potential solvents were also tested for their biocompatibility towards Clostridium acetobutylicum. Moreover, bioavailability and differences in substrate consumption and total n-butanol production with respect to solvent-free fermentations were quantified for each biocompatible solvent. Product yield was enhanced in the presence of organic solvents having higher affinity for butanol and butyric acid. Applying this methodology, it was found that the Guerbet alcohol 2-butyl-1-octanol presented the best extracting characteristics (the highest partition coefficient (6.76) and the third highest selectivity (644)), the highest butanol yield (27.4 %), and maintained biocompatibility with C. acetobutylicum.

A modified pathway for the production of acetone in Escherichia coli.

A modified synthetic acetone operon was constructed. It consists of two genes from Clostridium acetobutylicum (thlA coding for thiolase and adc coding for acetoacetate decarboxylase) and one from Bacillus subtilis or Haemophilus influenzae (teII(srf) or ybgC, respectively, for thioesterase). Expression of this operon in Escherichia coli resulted in the production of acetone starting from the common metabolite acetyl-CoA via acetoacetyl-CoA and acetoacetate. The thioesterases do not need a CoA acceptor for acetoacetyl-CoA hydrolysis. Thus, in contrast to the classic acetone pathway of Clostridium acetobutylicum and related microorganisms which employ a CoA transferase, the new pathway is acetate independent. The genetic background of the host strains was crucial. Only E. coli strains HB101 and WL3 were able to produce acetone via the modified plasmid based pathway, up to 64mM and 42mM in 5-ml cultures, respectively. Using glucose fed-batch cultures the concentration could be increased up to 122mM acetone with HB101 carrying the recombinant plasmid pUC19ayt (thioesterase from H. influenzae). The formation of acetone led to a decreased acetate production by E. coli.

Acetone extract from Streptoverticillium sp., a bacterium isolated from Brazilian Cerrado soil, induces anti-inflammatory activity in mice.

The Streptoverticillium sp. Z1 is an actinomycete isolated from the soil under Cerrado vegetation, the extract of this strain was investigated in nociceptive and inflammatory models. The Streptoverticillium extract (ExS) 50 and 100 mg/kg (s.c.) produced a significant inhibition of acetic acid-induced abdominal writhings thereby demonstrating an anti-nociceptive effect. In the tail flick test the ExS (s.c.) was inactive. This result implited that ExS does not contain opioid-like compounds with central analgesic properties. In the inflammatory models, ExS 100 and 200 mg/kg (s.c.) were able to inhibit the croton oil-induced ear edema and, ExS 200 and 500 mg/kg (s.c.) inhibited the leukocyte migration on the carrageenan-induced peritonitis. The phospholipase A2 enzymatic assay showed that the anti-inflammatory activity of ExS was not due to direct effect on phospholipase A2 activity. These data suggest that Streptoverticillium sp. produces metabolites with anti-inflammatory effect and that these metabolites are unable to directly inhibit phospholipase A2 enzyme.

Microbial production of a biofuel (acetone-butanol-ethanol) in a continuous bioreactor: impact of bleed and simultaneous product removal.

Acetone butanol ethanol (ABE) was produced in an integrated continuous one-stage fermentation and gas stripping product recovery system using Clostridium beijerinckii BA101 and fermentation gases (CO(2) and H(2)). In this system, the bioreactor was fed with a concentrated sugar solution (250-500 g L(-1) glucose). The bioreactor was bled semi-continuously to avoid accumulation of inhibitory chemicals and products. The continuous system was operated for 504 h (21 days) after which the fermentation was intentionally terminated. The bioreactor produced 461.3 g ABE from 1,125.0 g total sugar in 1 L culture volume as compared to a control batch process in which 18.4 g ABE was produced from 47.3 g sugar. These results demonstrate that ABE fermentation can be operated in an integrated continuous one-stage fermentation and product recovery system for a long period of time, if butanol and other microbial metabolites in the bioreactor are kept below threshold of toxicity.

Comparison of imidazolium ionic liquids and traditional organic solvents: effect on activated sludge processes.

Data concerning the biodegradability and ecotoxicity of ionic liquids (ILs) obtained so far are insufficient in the context of IL removal from wastewater in activated sludge systems. Thus, in this work the selected imidazolium ionic liquids and two organic solvents (methanol and acetone) were tested with respect to their influence on activated sludge processes, particularly on the morphology of sludge flocs. The presence of ionic liquids with the chemical structure of 1-alkyl-3-methyl imidazolium bromide in wastewater did not deteriorate biological wastewater treatment processes if their concentration was not higher than 5 mg l(-1). Regarding the structure of the ILs studied, the longer the alkyl substituent was, the stronger the effect on sludge flocs. The highest decrease in activated sludge floc area and biomass concentration was exerted by the ionic liquid with the longest alkyl chain, i.e. 1-decyl-3-methylimidazolium bromide. The action of both methanol and acetone on floc size, activated sludge concentration and efficiency of organic pollutants removal was weaker compared to all tested 1-alkyl-3-methyl imidazolium bromides.

Targeted mutagenesis of the Clostridium acetobutylicum acetone-butanol-ethanol fermentation pathway.

The production of the chemical solvents acetone and butanol by the bacterium Clostridium acetobutylicum was one of the first large-scale industrial processes to be developed, and in the first part of the last century ranked second in importance only to ethanol production. After a steep decline in its industrial use, there has been a recent resurgence of interest in the acetone-butanol-ethanol (ABE) fermentation process, with a particular emphasis on butanol production. In order to generate strains suitable for efficient use on an industrial scale, metabolic engineering is required to alter the AB ratio in favour of butanol, and eradicate the production of unwanted products of fermentation. Using ClosTron technology, a large-scale targeted mutagenesis in C. acetobutylicum ATCC 824 was carried out, generating a set of 10 mutants, defective in alcohol/aldehyde dehydrogenases 1 and 2 (adhE1, adhE2), butanol dehydrogenases A and B (bdhA, bdhB), phosphotransbutyrylase (ptb), acetate kinase (ack), acetoacetate decarboxylase (adc), CoA transferase (ctfA/ctfB), and a previously uncharacterised putative alcohol dehydrogenase (CAP0059). However, inactivation of the main hydrogenase (hydA) and thiolase (thl) could not be achieved. Constructing such a series of mutants is paramount for the acquisition of information on the mechanism of solvent production in this organism, and the subsequent development of industrial solvent producing strains. Unexpectedly, bdhA and bdhB mutants did not affect solvent production, whereas inactivation of the previously uncharacterised gene CAP0059 resulted in increased acetone, butanol, and ethanol formation. Other mutants showed predicted phenotypes, including a lack of acetone formation (adc, ctfA, and ctfB mutants), an inability to take up acids (ctfA and ctfB mutants), and a much reduced acetate formation (ack mutant). The adhE1 mutant in particular produced very little solvents, demonstrating that this gene was indeed the main contributor to ethanol and butanol formation under the standard batch culture conditions employed in this study. All phenotypic changes observed could be reversed by genetic complementation, with exception of those seen for the ptb mutant. This mutant produced around 100 mM ethanol, no acetone and very little (7 mM) butanol. The genome of the ptb mutant was therefore re-sequenced, together with its parent strain (ATCC 824 wild type), and shown to possess a frameshift mutation in the thl gene, which perfectly explained the observed phenotype. This finding reinforces the need for mutant complementation and Southern Blot analysis (to confirm single ClosTron insertions), which should be obligatory in all further ClosTron applications.

Bioproduction of butanol in bioreactors: new insights from simultaneous in situ butanol recovery to eliminate product toxicity.

Simultaneous acetone butanol ethanol (ABE) fermentation by Clostridium beijerinckii P260 and in situ product recovery was investigated using a vacuum process operated in two modes: continuous and intermittent. Integrated batch fermentations and ABE recovery were conducted at 37 °C using a 14-L bioreactor (7.0 L fermentation volume) containing initial substrate (glucose) concentration of 60 g/L. The bioreactor was connected in series with a condensation system and vacuum pump. Vacuum was applied continuously or intermittently with 1.5 h vacuum sessions separated by 4, 6, and 8 h intervals. A control ABE fermentation experiment was characterized by incomplete glucose utilization due to butanol toxicity to C. beijerinckii P260, while fermentation coupled with in situ recovery by both continuous and intermittent vacuum modes resulted in complete utilization of glucose, greater productivity, improved cell growth, and concentrated recovered ABE stream. These results demonstrate that vacuum technology can be applied to integrated ABE fermentation and recovery even though the boiling point of butanol is greater than that of water.

Simple and automatic determination of aldehydes and acetone in water by headspace solid-phase microextraction and gas chromatography-mass spectrometry.

We describe a simple and automatic method to determine nine aldehydes and acetone simultaneously in water. This method is based on derivatization with 2,2,2-trifluoroethylhydrazine (TFEH) and consecutive headspace-solid-phase microextraction and gas chromatography-mass spectrometry. Acetone-d(6) was used as the internal standard. Aldehydes and acetone in water reacted for 30 min at 40°C with TFEH in a headspace vial and the formed TFEH derivatives were simultaneously vaporized and adsorbed on polydimethylsiloxane-divinylbenzene. Under the established condition, the method detection limit was 0.1-0.5 µg/L in 4 mL water and the relative standard deviation was less than 13% at concentrations of 0.25 and 0.05 mg/L. This method was applied to determine aldehydes and acetone in 5 mineral water and 114 surface water samples. All mineral water samples had detectable levels of methanal (24.0-61.8 µg/L), ethanal (57.7-110.9 µg/L), propanal (11.5-11.7 µg/L), butanal, pentanal (3.3-3.4 µg/L) and nonanal (0.3-0.4 µg/L). Methanal and ethanal were also detected in concentration range of 2.7-117.2 and 1.2-11.9 µg/L, respectively, in surface water of 114 monitoring sites in Korea.

Ionic liquid-based in situ product removal design exemplified for an acetone-butanol-ethanol fermentation.

Selecting an appropriate separation technique is essential for the application of in situ product removal (ISPR) technology in biological processes. In this work, a three-stage systematic design method is proposed as a guide to integrate ionic liquid (IL)-based separation techniques into ISPR. This design method combines the selection of a suitable ISPR processing scheme, the optimal design of an IL-based liquid-liquid extraction (LLE) system followed by process simulation and evaluation. As a proof of concept, results for a conventional acetone-butanol-ethanol fermentation are presented (40,000 ton/year butanol production). In this application, ILs tetradecyl(trihexyl)phosphonium tetracyanoborate ([TDPh][TCB]) and tetraoctylammonium 2-methyl-1-naphthoate ([TOA] [MNaph]) are identified as the optimal solvents from computer-aided IL design (CAILD) method and reported experimental data, respectively. The dynamic simulation results for the fermentation process show that, the productivity of IL-based in situ (fed-batch) process and in situ (batch) process is around 2.7 and 1.8fold that of base case. Additionally, the IL-based in situ (fed-batch) process and in situ (batch) process also have significant energy savings (79.6% and 77.6%) when compared to the base case.

Hybrid ZIF-8-90 for Selective Solid-Phase Microextraction of Exhaled Breath from Gastric Cancer Patients.

Metal-organic frameworks (MOFs) are a new kind of microporous materials whose unique properties make them promising as coatings for solid phase microextraction (SPME). However, previous MOF coatings for SPME exclusively focus on single-linker MOFs, and the selective enrichment of polar or nonpolar targets depends on the polarity of linker on the surface of MOFs, which greatly limits the application of MOF coating for SPME in real samples. Here, we report a hybrid MOF-coated stainless steel fiber for SPME of biomarkers in exhaled breath from gastric cancer patients. Zeolitic imidazolate framework-8-90 (ZIF-8-90) possesses the aldehyde groups and methyl groups in the framework as a model MOF, and eight biomarkers (ethanol, acetone, hexanal, hexanol, nonane, isoprene, heptane, and decane) were used as the target analytes. The ZIF-8-90-coated fiber shows high enrichment efficiency for hydrophilic targets and hydrophobic targets, wide linearity (three orders of magnitude), and low detection limits (0.82-2.64 µg L-1). The ZIF-8-90-coated fiber exhibited higher enrichment performance for all the investigated analytes as a result of the synergy of methyl and aldehyde groups, the porous structure, and the suitable pore size of ZIF-8-90 (4-5 Å). The relative standard deviation (RSD) of six repetitions for extractions using the same ZIF-8-90-coated fiber ranged from 2.5 to 7.3%. The reproducibility between the three fibers prepared in parallel varied in the range of 4.8-12% (RSD). The fabricated ZIF-8-90-coated fiber lasted for at least 120 cycles of extraction/desorption/conditioning without an obvious reduction in extraction efficiency and precision. Finally, the developed ZIF-8-90-coated SPME fiber has been successfully used for the analysis of exhaled breath samples from gastric patients with satisfied recoveries (88-106%).