Zhuomin Zhang

Review of online coupling of sample preparation techniques with liquid chromatography

Sample preparation is still considered as the bottleneck of the whole analytical procedure, and efforts has been conducted towards the automation, improvement of sensitivity and accuracy, and low comsuption of organic solvents. Development of online sample preparation techniques (SP) coupled with liquid chromatography (LC) is a promising way to achieve these goals, which has attracted great attention. This article reviews the recent advances on the online SP-LC techniques. Various online SP techniques have been described and summarized, including solid-phase-based extraction, liquid-phase-based extraction assisted with membrane, microwave assisted extraction, ultrasonic assisted extraction, accelerated solvent extraction and supercritical fluids extraction. Specially, the coupling approaches of online SP-LC systems and the corresponding interfaces have been discussed and reviewed in detail, such as online injector, autosampler combined with transport unit, desorption chamber and column switching. Typical applications of the online SP-LC techniques have been summarized. Then the problems and expected trends in this field are attempted to be discussed and proposed in order to encourage the further development of online SP-LC techniques.

Study on seafood volatile profile characteristics during storage and its potential use for freshness evaluation by headspace solid phase microextraction coupled with gas chromatography-mass spectrometry

Seafood volatile profile characteristics at different storage phases are various and can be used for freshness evaluation during storage. It is imperative to obtain the full volatile information prior to the further study of seafood volatile profile characteristics during storage. Also, the efficient data-processing method is another important factor for the interpretation of seafood volatile profile characteristics during storage and related potential volatile markers. In this work, a new analytical strategy, including the efficient sampling technique, sensitive detection and suitable data-processing method, for seafood freshness evaluation was developed based on the volatile profile characteristics during storage. First, the study of volatiles of seafood samples including razor clam, redspot swimming crab and prawn at different storage phases were conducted by headspace solid phase microextraction (HSSPME) followed by gas chromatography-mass spectrometry (GC-MS) detection. Then, seafood volatile profile characteristics at different storage phases were statistically interpreted by a combination data-processing method including normalization, principle component analysis (PCA) and common model strategy. The different seafood volatile profile characteristics and potential volatile markers were attempted to be distilled. The results tentatively suggested that the different seafood volatile profile characteristics during storage could reflect the transitional changing seafood freshness and provide more precise warning information for seafood spoilage during storage than any single chemical markers. This work developed an analytical method for study of seafood volatile profile characteristics and tentatively proposed a new idea of using seafood volatile profile characteristics during storage for the freshness evaluation from the point of view of analytical chemistry.

A hydrazone covalent organic polymer based micro-solid phase extraction for online analysis of trace Sudan dyes in food samples.

Covalent organic polymers (COPs) connected by covalent bonds are a new class of porous network materials with large surface area and potential superiority in sample pretreatment. In this study, a new hydrazone linked covalent organic polymer (HL-COP) adsorbent was well-designed and synthesized based on a simple Schiff-base reaction. The condensation of 1,4-phthalaldehyde and 1,3,5-benzenetricarbohydrazide as organic building blocks led to the synthesis of HL-COP with uniform particle size and good adsorption performance. This HL-COP adsorbent with high hydrophobic property and rich stacking π electrons contained abundant phenyl rings and imine (CN) groups throughout the entire molecular framework. The adsorption mechanism was explored and discussed based on π-π affinity, hydrophobic effect, hydrogen bonding and electron-donor-acceptor (EDA) interaction, which contributed to its strong recognition affinity to target compounds. Enrichment factors were 305-757 for six Sudan dyes by HL-COP micro-solid phase extraction (μ-SPE), indicating its remarkable preconcentration ability. Furthermore, the adsorption amounts by HL-COP μ-SPE were 1.0-11.0 folds as those by three commonly used commercial adsorbents. Then, HL-COP was applied as adsorbent of online μ-SPE coupled with high performance liquid chromatography (HPLC) for enrichment and analysis of trace Sudan dyes in food samples with detection limit of 0.03-0.15μg/L. The method was successfully applied for online analysis of chilli powder and sausage samples. Sudan II and Sudan III in one positive chilli powder sample were actually found and determined with concentrations of 8.3 and 6.8μg/kg, respectively. The recoveries of chilli powder and sausage samples were in range of 75.8-108.2% and 73.8-112.6% with relative standard deviations of 1.2-8.5% and 1.9-9.4% (n=5), respectively. The proposed method was accurate, reliable and convenient for the online simultaneous analysis of trace Sudan dyes in food samples.

ZnO nanorod array solid phase micro-extraction fiber coating: fabrication and extraction capability

In this paper, a ZnO nanorod array has been introduced as a coating to the headspace solid phase micro-extraction (HSSPME) field. The coating shows good extraction capability for volatile organic compounds (VOCs) by use of BTEX as a standard and can be considered suitable for sampling trace and small molecular VOC targets. In comparison with the randomly oriented ZnO nanorod HSSPME coating, ZnO nanorod array HSSPME fiber coating shows better extraction capability, which is attributed to the nanorod array structure of the coating. Also, this novel nanorod array coating shows good extraction selectivity to 1-propanethiol.

Preparation of novel alumina nanowire solid-phase microextraction fiber coating for ultra-selective determination of volatile esters and alcohols from complicated food samples

A novel alumina nanowire (ANW) solid-phase microextraction (SPME) fiber coating was prepared by a simple and rapid anodization-chemical etching method for ultra-selective determination of volatile esters and alcohols from complicated food samples. Preparation conditions for ANW SPME fiber coating including corrosion solution concentration and corrosion time were optimized in detail for better surface morphology and higher surface area based on scanning electron microscope (SEM). Under the optimum conditions, homogeneous alumina nanowire structure of ANW SPME fiber coating was achieved with the average thickness of 20 μm around. Compared with most of commercial SPME fiber coatings, ANW SPME fiber coatings achieved the higher extraction capacity and special selectivity for volatile esters and alcohols. Finally, an efficient gas sampling technique based on ANW SPME fiber coating as the core was established and successfully applied for the ultra-selective determination of trace volatile esters and alcohols from complicated banana and fermented glutinous rice samples coupled with gas chromatography/mass spectrometry (GC/MS) detection. It was interesting that 25 esters and 2 alcohols among 30 banana volatile organic compounds (VOCs) identified and 4 esters and 7 alcohols among 13 identified VOCs of fermented glutinous rice were selectively sampled by ANW SPME fiber coatings. Furthermore, new analytical methods for the determination of some typical volatile esters and alcohols from banana and fermented glutinous rice samples at specific storage or brewing phases were developed and validated. Good recoveries for banana and fermented glutinous rice samples were achieved in range of 108-115% with relative standard deviations (RSDs) of 2.6-6.7% and 80.0-91.8% with RSDs of 0.3-1.3% (n=3), respectively. This work proposed a novel and efficient gas sampling technique of ANW SPME which was quite suitable for ultra-selectively sampling trace volatile esters and alcohols from complicated food samples.

Fabrication of novel nanoporous array anodic alumina solid-phase microextraction fiber coating and its potential application for headspace sampling of biological volatile organic compounds

In the study, nanoporous array anodic alumina (NAAA) prepared by a simple, rapid and stable two-step anodic oxidization method was introduced as a novel solid-phase microextraction (SPME) fiber coating. The regular nanoporous array structure and chemical composition of NAAA SPME fiber coating was characterized and validated by scanning electron microscopy and energy dispersive spectroscopy, respectively. Compared with the commercial polydimethylsiloxane (PDMS) SPME fiber coating, NAAA SPME fiber coating achieved the higher enrichment capability (1.7-4.7 folds) for the mixed standards of volatile organic compounds (VOCs). The selectivity for volatile alcohols by NAAA SPME fiber coating demonstrated an increasing trend with the increasing polarity of alcohols caused by the gradually shortening carbon chains from 1-undecanol to 1-heptanol or the isomerization of carbon chains of some typical volatile alcohols including 2-ethyl hexanol, 1-octanol, 2-phenylethanol, 1-phenylethanol, 5-undecanol, 2-undecanol and 1-undecanol. Finally, NAAA SPME fiber coating was originally applied for the analysis of biological VOCs of Bailan flower, stinkbug and orange peel samples coupled with gas chromatography-mass spectrometry (GC-MS) detection. Thirty, twenty-seven and forty-four VOCs of Bailan flower, stinkbug and orange peel samples were sampled and identified, respectively. Moreover, the contents of trace 1-octanol and nonanal of real orange peel samples were quantified for the further method validation with satisfactory recoveries of 106.5 and 120.5%, respectively. This work proposed a sensitive, rapid, reliable and convenient analytical method for the potential study of trace and small molecular biological VOCs by the novel NAAA SPME fiber coating.

Rapid analysis of trace volatile formaldehyde in aquatic products by derivatization reaction-based surface enhanced Raman spectroscopy

Toxic formaldehyde is sometimes used illegally as a food preservative, however, on-site rapid analysis of trace formaldehyde in aquatic products remains a challenge. In this work, a simple on-site rapid quantification method for trace volatile formaldehyde in aquatic products was developed by a derivative reaction-based surface enhanced Raman spectroscopy (SERS) technique coupled with a homemade portable purge-sampling device. Trace formaldehyde separated from complicated aquatic matrices via a purge-sampling procedure was reacted with a derivative reagent to produce a Raman-active analyte for consequent SERS analysis. Au/SiO2 nanoparticles (NPs) were employed as the enhancement substrate to achieve significant enhancement of Raman signal intensity. Conditions of derivative reaction and SERS detection were optimized in detail, and the selectivity of this analytical method was also evaluated based on related analogs. Under optimal conditions, an extremely low detection limit of 0.17 μg L(-1) was achieved. Trace volatile formaldehyde can be found in fresh squid and shrimp samples without obvious matrix interference, and this was quantified to be 0.13-0.21 mg kg(-1) using the described method. The recoveries of spiked aquatic product samples were found to be 70.0-89.1% with RSDs of 2.3-7.2% (n = 3). The results suggest that the proposed method is reliable and suitable for on-site rapid analysis of trace formaldehyde in aquatic products.

Preparation of sulfonated graphene/polypyrrole solid-phase microextraction coating by in situ electrochemical polymerization for analysis of trace terpenes ☆

In this study, a novel sulfonated graphene/polypyrrole (SG/PPy) solid-phase microextraction (SPME) coating was prepared and fabricated on a stainless-steel wire by a one-step in situ electrochemical polymerization method. Crucial preparation conditions were optimized as polymerization time of 15min and SG doping amount of 1.5mg/mL. SG/PPy coating showed excellent thermal stability and mechanical durability with a long lifespan of more than 200 stable replicate extractions. SG/PPy coating demonstrated higher extraction selectivity and capacity to volatile terpenes than commonly-used commercial coatings. Finally, SG/PPy coating was practically applied for the analysis of volatile components from star anise and fennel samples. The majority of volatile components identified were terpenes, which suggested the ultra-high extraction selectivity of SG/PPy coating to terpenes during real analytical projects. Four typical volatile terpenes were further quantified to be 0.2-27.4μg/g from star anise samples with good recoveries of 76.4-97.8% and 0.1-1.6μg/g from fennel samples with good recoveries of 80.0-93.1%, respectively.

Progress on the analytical methodology for biological volatile organic compounds

Biological terminal metabolites are volatile organic compounds (VOCs) with strong volatility, containing important bio-information related with biological metabolism. As a crucial research precondition, analytical methodology for biological VOCs has attracted much attention to achieve the adequate composition information of biological VOCs at different physiological status and metabolism phases. In this article, the analytical methodology for biological VOCs is summarized, focusing on the latest advances on sampling and analytical techniques followed by the preliminary application of distilling potential, but crucial, bio-information. Systematic study of the relationship among biological VOCs, biological VOC characteristics and corresponding biomarkers would result in a potential but promising research field, bioodoromics. The concept of bioodoromics is described, and the developing trend of bioodoromics in the future is proposed in this paper. It is believed that bioodoromics possesses the power to describe potential but crucial bio-information related with metabolism pathway. The study of biological VOCs and potential bioodoromics would facilitate relevant fields such as insect prevention, disease diagnosis, criminal track-down, agricultural product quality control and food safety, etc..

Separation and analysis of trace volatile formaldehyde in aquatic products by a MoO3/polypyrrole intercalative sampling adsorbent with thermal desorption gas chromatography and mass spectrometry

An in situ embedded synthesis strategy was developed for the preparation of a MoO3 /polypyrrole intercalative sampling adsorbent for the separation and analysis of trace volatile formaldehyde in aquatic products. Structural and morphological characteristics of the MoO3 /polypyrrole intercalative adsorbent were investigated by a series of characterization methods. The MoO3 /polypyrrole sampling adsorbent possessed a higher sampling capacity and selectivity for polar formaldehyde than commonly used commercial adsorbent Tenax TA. Finally, the MoO3 /polypyrrole adsorbent was packed in the thermal desorption tube that was directly coupled to gas chromatography with mass spectrometry for the analysis of trace volatile formaldehyde in aquatic products. Trace volatile formaldehyde from real aquatic products could be selectively sampled and quantified to be 0.43-6.6 mg/kg. The detection limit was achieved as 0.004 μg/L by this method. Good recoveries for spiked aquatic products were achieved in range of 75.0-108% with relative standard deviations of 1.2-9.0%.