Molecularly Imprinted Polymer Nanospheres with Hydrophilic Shells for Efficient Molecular Recognition of Heterocyclic Aromatic Amines in Aqueous Solution.

Heterocyclic aromatic amine molecularly imprinted polymer nanospheres with surface-bound dithioester groups (haa-MIP) were firstly synthesized via reversible addition-fragmentation chain transfer (RAFT) precipitation polymerization. Then, a series of core-shell structural heterocyclic aromatic amine molecularly imprinted polymer nanospheres with hydrophilic shells (MIP-HSs) were subsequently prepared by grafting the hydrophilic shells on the surface of haa-MIP via on-particle RAFT polymerization of 2-hydroxyethyl methacrylate (HEMA), itaconic acid (IA), and diethylaminoethyl methacrylate (DEAEMA). The haa-MIP nanospheres showed high affinity and specific recognition toward harmine and its structural analogs in organic solution of acetonitrile, but lost the specific binding ability in aqueous solution. However, after the grafting of the hydrophilic shells on the haa-MIP particles, the surface hydrophilicity and water dispersion stability of the polymer particles of MIP-HSs greatly improved. The binding of harmine by MIP-HSs with hydrophilic shells in aqueous solutions is about two times higher than that of NIP-HSs, showing an efficient molecular recognition of heterocyclic aromatic amines in aqueous solution. The effect of hydrophilic shell structure on the molecular recognition property of MIP-HSs was further compared. MIP-PIA with carboxyl groups containing hydrophilic shells showed the highest selective molecular recognition ability to heterocyclic aromatic amines in aqueous solution.

Smokeless tobacco analysis: Simultaneous extraction and purification of alkaloids, volatile N-nitrosamines, and polycyclic hydrocarbons for GC-MS/MS.

Several smokeless tobacco products are available in the market and comprise complex chemical matrices. Sample preparation for analysis of the multiple classes of harmful compounds in smokeless tobacco products is highly cumbersome. In this study, a simultaneous extraction scheme was developed for three toxic analyte classes in smokeless tobacco products using a two-phase solution consisting of 5% aqueous NaOH and dichloromethane in a 1:4 ratio. The dichloromethane extract was used to analyze four alkaloids directly at levels greater than parts per million; however, passing the layer through a silica cartridge for further purification and concentration was necessary for determining 18 polycyclic aromatic hydrocarbons and four volatile N-nitrosoamines at the ppt level. The multitargets were determined by using gas chromatography with tandem mass spectrometry. The limits of detection for the 18 polycyclic aromatic hydrocarbons, four volatile N-nitrosoamines, three minor alkaloids, and nicotine were 0.2-1.2, 0.2-0.4, 0.6-1.0, and 10.2 µg/g, respectively. Four different smokeless tobacco substrates were fortified with three levels of mixed standards, and the recoveries ranged between 83 and 110%. The method was highly efficient, reduced the sample amounts, solvents, and the time required by approximately 60%. The method was used to assay 18 smokeless tobacco products, and showed potentials in assaying drugs and other plant-based substrates.

Analysis of methyl DNA adducts and metabolites in BEAS-2B cells induced by 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone.

The tobacco-specific nitrosamine 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK) is classified as a Group 1 human carcinogen. It is metabolically activated by P450 enzymes to intermediate methylate and pyridyloxobutylate DNA, resulting in the formation of DNA adduct that is critical for the carcinogenicity of NNK. To directly and objectively examine the DNA adduct formation profiles without the complexity of factors in vivo, in the present study, five kinds of methyl DNA adducts were first identified in the incubation model of NNK established with human lung epithelial cells (BEAS-2B). The level of methyl DNA adducts and metabolites of NNK were quantitatively analyzed, respectively. With the increase of exposure time and dose, the level of methyl DNA adducts and metabolites increased. Furthermore, with the changes of the activity of P450 enzymes, which is the main enzyme regulating the α-hydroxylation of NNK, we found the levels of both methyl adducts and metabolites formed via α-hydroxylation in experimental groups showed the same trend compared with those in control group, while the metabolites formed via other pathways changed in the opposite trend. The result proves that the methyl adducts induced by NNK generate via α-hydroxylation pathway in BEAS-2B cells.

Simultaneous quantification of ten Amadori compounds in tobacco using liquid chromatography with tandem mass spectrometry.

Amadori compounds are aroma precursors formed in the initial phase of the Maillard reaction. Based on their similar structures, simultaneous quantification of more than six Amadori compounds in tobacco has not been reported yet. In this study, a simple and rapid method was developed to simultaneously quantify ten Amadori compounds including the isomers of Fructose-isoleucine and Fructose-leucine in tobacco. The separation was performed on an Atlantis T3 column (2.1 × 250 mm, 5 µm) by gradient elution using acetonitrile and water as the mobile phases. The quantification method was systematically evaluated and proven to be sensitive and accurate. The linearity was good, with correlation coefficients of 0.9977-0.9999. The limits of detection and quantitation were 1.354-2.532 and 4.516-8.444 ng/mL, respectively. The recoveries were 84.0-119.6%, and the relative standard deviations were 1.33-5.40%. The method was used to analyze the changes in the amounts of ten Amadori compounds in tobacco before and after tobacco primary processing. The analysis shows that the Maillard reaction occurs during the short processing period.

Robust SiO2-modified CoFe2O4 hollow nanofibers with flexible room temperature magnetic performance.

A range of robust SiO2-modified CoFe2O4 hollow nanofibers with high uniformity and productivity were successfully prepared via polyvinylpyrrolidone-sol assisted electrospinning followed by annealing at a high temperature of 1000 °C, and they were characterized using scanning electron microscopy, transmission electron microscopy, vibrating sample magnetometry, X-ray diffraction and X-ray photoelectron spectroscopy in detail. It was demonstrated that amorphous SiO2 has a significant influence on not only the surface morphology, microstructure and crystalline size but also the room temperature magnetic performance of the inverse spinel CoFe2O4 nanofibers. The pure CoFe2O4 sample shows a particle chain rod-shape appearance but the SiO2-modified CoFe2O4 sample shows a robust hollow fibrous structure. With increasing SiO2 content, an increase at first and then a decrease in coercivity (Hc) and monotonously a decrease in saturation magnetization (Ms) have been determined in the obtained modified CoFe2O4 hollow nanofibers. A maximum Ms of about 80 emu g(-1) and a maximum Hc of about 1477 Oe could be, respectively, acquired from the pure CoFe2O4 nanorods and the modified CoFe2O4 hollow nanofibers with about 14.9% SiO2. The changes in Ms, Hc and the structure evolution mechanism of these SiO2-modified CoFe2O4 hollow nanofibers have been elaborated systematically. Furthermore, it is suggested that amorphous SiO2 enables effectively improving the structure endurance of 1D electrospun inorganic oxide hollow nanostructures being subjected to high temperatures.

Determination of multi-pesticide residue in tobacco using multi-walled carbon nanotubes as a reversed-dispersive solid-phase extraction sorbent.

A multi-pesticide residue determination method based on a modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) method using multiwalled carbon nanotubes as reversed-dispersive solid-phase extraction material was validated in 37 representative pesticides in tobacco. Determination was performed using liquid chromatography with tandem mass spectrometry in multiple reaction monitoring mode. Three major types of tobacco leaf samples, namely, flue-cured, burley, and oriental tobacco were studied and compared. Three factors (extraction time, external diameter, and amount of extraction material used) that could affect the performance of multi-walled carbon nanotubes were investigated. Optimization of sample preparation and determination allowed recoveries between 70.8 and 114.8% for all 37 pesticides with < 20.0% relative standard deviations at three spiking levels of 20, 50, and 200 µg/kg. The limits of quantification and limits of detection for the 37 pesticides ranged within 0.46-28.57 and 0.14-8.57 µg/kg at a signal-to-noise ratio of 10 and 3, respectively.

Human brain state dynamics reflect individual neuro-phenotypes.

Neural activity and behavior manifest state and trait dynamics, as well as variation within and between individuals. However, the mapping of state-trait neural variation to behavior is not well understood. To address this gap, we quantify moment-to-moment changes in brain-wide co-activation patterns derived from resting-state functional magnetic resonance imaging. In healthy young adults, we identify reproducible spatio-temporal features of co-activation patterns at the single subject level. We demonstrate that a joint analysis of state-trait neural variations and feature reduction reveal general motifs of individual differences, encompassing state-specific and general neural features that exhibit day-to-day variability. The principal neural variations co-vary with the principal variations of behavioral phenotypes, highlighting cognitive function, emotion regulation, alcohol and substance use. Person-specific probability of occupying a particular co-activation pattern is reproducible and associated with neural and behavioral features. This combined analysis of state-trait variations holds promise for developing reproducible neuroimaging markers of individual life functional outcome.

QuNex-An integrative platform for reproducible neuroimaging analytics.

Introduction: Neuroimaging technology has experienced explosive growth and transformed the study of neural mechanisms across health and disease. However, given the diversity of sophisticated tools for handling neuroimaging data, the field faces challenges in method integration, particularly across multiple modalities and species. Specifically, researchers often have to rely on siloed approaches which limit reproducibility, with idiosyncratic data organization and limited software interoperability. Methods: To address these challenges, we have developed Quantitative Neuroimaging Environment & Toolbox (QuNex), a platform for consistent end-to-end processing and analytics. QuNex provides several novel functionalities for neuroimaging analyses, including a "turnkey" command for the reproducible deployment of custom workflows, from onboarding raw data to generating analytic features. Results: The platform enables interoperable integration of multi-modal, community-developed neuroimaging software through an extension framework with a software development kit (SDK) for seamless integration of community tools. Critically, it supports high-throughput, parallel processing in high-performance compute environments, either locally or in the cloud. Notably, QuNex has successfully processed over 10,000 scans across neuroimaging consortia, including multiple clinical datasets. Moreover, QuNex enables integration of human and non-human workflows via a cohesive translational platform. Discussion: Collectively, this effort stands to significantly impact neuroimaging method integration across acquisition approaches, pipelines, datasets, computational environments, and species. Building on this platform will enable more rapid, scalable, and reproducible impact of neuroimaging technology across health and disease.

Simultaneous analysis of multiple pesticide residues in tobacco by magnetic carbon composite-based QuEChERS method and liquid chromatography coupled to quadrupole time-of-flight mass spectrometry.

Magnetic carbon composite (Fe3O4@C) was synthesized and applied as a reversed-dispersive solid-phase extraction sorbent for the simultaneous analysis of 40 pesticide residues in tobacco by ultrahigh-performance liquid chromatography coupled to quadrupole time-of-fight mass spectrometry. Compared to the traditional QuEChERS method, the optimized Fe3O4@C simplified clean-up process and exhibited better clean-up capability than conventional sorbents. The pesticides were qualitatively identified by accurate mass of protonated molecules, fragment ions, isotopic peak clusters, and retention time, and quantitatively determined by matrix-matched external standard method. Good linearity of the proposed method was obtained with R value greater than 0.997 for all target pesticides at concentration levels of 2-200 µg/L. The limit of detection ranged from 0.14 to 2.67 µg/kg. The recoveries and relative standard deviations of all target pesticides at three spiked concentrations of 20, 50 and 200 µg/kg were in the ranges of 80.8%-113.3% and 0.6%-16.3%, respectively. Compared with the reported methods for the analysis of multiple pesticide residues in tobacco, the proposed method has the advantages of simple to operate, high clean-up ability and less time-consuming in clean-up process.

Accuracy improvement of determination of seven minor tobacco alkaloids in mainstream cigarette smoke using analyte protectants by gas chromatography-mass spectrometry.

Tobacco alkaloids are important precursors of carcinogenic tobacco-specific nitrosamines. Therefore, accurate quantification of tobacco alkaloids is highly important. This study investigates the compensation effects of novel analyte protectants (APs) for matrix effects (MEs) to determine seven minor tobacco alkaloids (nornicotine, myosmine, anabasine, anatabine, nicotyrine, 2,3'-bipyridine, and cotinine) in mainstream cigarette smoke with high accuracy and robustness. By comparing the heights and shapes of the chromatographic peaks before and after the addition of APs to standard solutions prepared in dichloromethane and cigarette smoke solutions, the compensation effects of 12 APs and their combinations on the MEs of seven minor tobacco alkaloids were evaluated, and the best combination of 2-pyridylethylamine (2 mg/mL)+1,2-decanediol (1 mg/mL) was identified. This AP combination could effectively improve the shapes and increase the heights (by 7-371%) of chromatographic peaks for standard solutions prepared in dichloromethane and cigarette smoke solutions. Before the addition of this AP combination, the slope ratios of the calibration curves for two types of standard solutions of the seven target chemicals were 71.4-159.8%, while they were 87.4-105.6% after the addition, indicating that this AP combination reduced the matrix difference between pure solvent and cigarette smoke solution. After adding the AP combination, the standard curves of solutions prepared in dichloromethane showed good linearity (r2 ≥ 0.999), the spiked recoveries were between 80.9% and 119.6%, and the inter- and intraday precisions were between 1.5-9.5% and 3.1-8.5%, respectively. Three commercial cigarette samples and one mixed standard solution were also tested under four different instrument working conditions to verify the long-term accuracy and ruggedness of the approach in routine real-world analysis of the method. The results showed that the RSD values were higher (3.5-25.4%) without the AP combination than that (<6.7%) with the AP combination. Because of its high accuracy, precision, and robustness, this method has good practical prospects.

Robust, comprehensive, sensitive analysis of flavour additives with carboxyl and hydroxyl groups in cigarette smoke combining silylation and gas chromatography-tandem mass spectrometry with an improved backflushing system.

Flavour additives with carboxyl and hydroxyl groups (FACHs), the key ingredients in characteristic flavours, are frequently detected in cigarette smoke. They are attracting increasing attention in regulating the flavour additives used in tobacco to curb youth tobacco use and prevent the use of additives that are harmful. In this study, a highly robust, sensitive, and precise method based on silylation and GC-MS/MS with an improved backflushing system was developed for the simultaneous analysis of 171 FACHs in cigarette smoke. Silylation has been shown to have advantages in terms of high selectivity and sensitivity to chemicals with carboxyl and hydroxyl groups, especially when combined with GC-MS/MS. The extraction and silylation conditions were optimised. Dichloromethane was used as the extraction agent. BSTFA in combination with 1% TMCS and 0.2% TMSI was selected as silylating agent for high silylation efficiency, particularly for hindered analytes. The method has been validated. The limit of detection (LOD) ranged from 0.6 to 332.3 ng/mL. 91.1% out of the analytes in QC samples had precisions lower than 10% during one month run. The improved backflushing system with a fused silica splitter was shown to be crucial in the excellent long-term robustness of the method. The developed method was used to determine flavour additives in 270 practical cigarette smoke samples with reliable results. A total of 154 FACHs were identified with wide-range levels among different cigarette brands.

Selective extraction and determination of aromatic amine metabolites in urine samples by using magnetic covalent framework nanocomposites and HPLC-MS/MS.

Purification and selective enrichment of ultra-low level metabolites in bio-samples is very important for HPLC-MS/MS analysis. A magnetic covalent organic framework (i.e. COFs) (TpPa-1) (i.e. 2,4,6-trihydroxybenzene-1,3,5-tricarbaldehyde-p-phenylenediamine) material was synthesized and used for a magnetic solid phase extraction (MSPE) method in aromatic amine (AA) metabolites (i.e. 1-naphthylamine, 2-naphthylamine, 3-aminobiphenyl and 4-aminobiphenyl) in urine, and then HPLC-MS/MS was employed for analysis. The morphology, pore structure, surface area, chemical composition, magnetic properties, and thermal stability of the synthesized magnetic COFs were characterized with several analysis techniques, such as nitrogen adsorption-desorption isotherms, HRTEM, FTIR, XRD, and so on. MSPE conditions were optimized and analytical performance of the developed method was characterized. The limit of detection (LOD) and limit of quantification (LOQ) of four AAs ranged from 0.01 to 0.07 ng mL-1 and 0.04 to 0.22 ng mL-1, respectively. The recoveries of 1-NA, 2-NA, 3-ABP, 4-ABP were in the range of 81.9-105%, 87.8-102%, 101-120%, 88.3-117%, respectively. Good intra-day and inter-day precision were obtained with RSD of less than 5.8% and 9.9%, respectively. Furthermore, the synthesized magnetic COFs absorbent could be recycled in MSPE at least 5 times. Analytical results of AA metabolites in real urine samples with the developed method showed significant difference (p < 0.01) between smokers and nonsmokers. Thus, urinary AA metabolites could be exposure biomarkers for cigarette smoke.

Functional Porous Carboxymethyl Cellulose/Cellulose Acetate Composite Microspheres: Preparation, Characterization, and Application in the Effective Removal of HCN from Cigarette Smoke.

To selectively reduce the yield of hydrogen cyanide (HCN) in the cigarette smoke, functional porous carboxymethyl cellulose/cellulose acetate (CMC/CA) composite microspheres were prepared via the double emulsion-solvent evaporation method. Cupric ions, which have a high complexing ability toward HCN, were introduced to the CMC/CA composite microspheres during the fabrication process via an in situ ion cross-link method. The microspheres were characterized using nitrogen adsorption, mercury intrusion porosimetry, and scanning electron microscopy (SEM). The microspheres have a predominantly macroporous structure indicating weak physisorption properties, but sufficient functional cupric ion groups to selectively adsorb HCN. With these CMC/CA microspheres as filter additives, the smoke yield of HCN could be reduced up to 50%, indicating the great potential of these microspheres as absorbents for removing HCN from cigarette smoke.

Investigation on the structures and magnetic properties of carbon or nitrogen doped cobalt ferrite nanoparticles.

Carbon or nitrogen doped cobalt ferrite nanoparticles were synthesized in the air by a facile calcination process. X-ray diffraction, mapping, X-ray photoelectron spectroscopy, and mössbauer spectra results indicate that the nonmetal elements as the interstitial one are doped into cobalt ferrite nanoparticles. The morphologies of doped cobalt ferrite nanoparticles change from near-spherical to irregular cubelike shapes gradually with the increased carbon or nitrogen concentration, and their particles sizes also increase more than 200 nm. Furthermore, the saturation magnetization of carbon doped cobalt ferrite is improved. Although the saturation magnetization of N-doped cobalt ferrite is not enhanced obviously due to the involved hematite, they also do not drop drastically. The results reveal an approach to synthesize large scale ferrite nanoparticles, and improve the magnetic properties of ferrite nanoparticles, and also provide the potential candidates to synthesis co-doped functional magnetic materials.

High saturation magnetization of γ-Fe2O3 nano-particles by a facile one-step synthesis approach.

We have demonstrated the synthesis of γ-Fe2O3 nano-particles through a facile and novel calcination process in the air. There is no pH regulation, gas atmosphere, additive, centrifugation or other complicated procedures during the preparing process. A detailed formation process of the nano-particles is proposed, and DMF as a polar solvent may slower the reaction process of calcination. The structures, morphologies, and magnetic properties of γ-Fe2O3 nano-particles were investigated systematically, and the pure γ-Fe2O3 nano-particles obtained at 200 °C display uniform morphology good magnetic property. The saturation magnetization of obtained pure γ-Fe2O3 is about 74 emu/g, which is comparable with bulk material (76 emu/g) and larger than other results. In addition, the photocatalytic activity for degradation of methylene blue is also studied, which shows proper photocatalytic activity.

A novel method to fabricate CoFe2O4/SrFe12O19 composite ferrite nanofibers with enhanced exchange coupling effect.

Nanocomposite of CoFe2O4/SrFe12O19 has been synthesized by the electrospinning and calcination process. A novel method that cobalt powder was used to replace traditional cobalt salt in the precursor sol-gel for electrospinning was proposed. The crystal structures, morphologies, and magnetic properties of these samples have been characterized in detail. Moreover, when the average crystallite size of the hard/soft phases reached up to an optimal value, the CoFe2O4 have an enhanced saturation magnetization of 62.8 emu/g and a coercivity of 2,290 Oe. Significantly, the hysteresis loops for the nanocomposites show a single-phase magnetization behavior, and it has been found that the exchange coupling interaction strongly exists in the CoFe2O4/SrFe12O19 magnetic nanocomposite nanofibers.

Width-controlled M-type hexagonal strontium ferrite (SrFe12O19) nanoribbons with high saturation magnetization and superior coercivity synthesized by electrospinning.

Width-controlled M-type hexagonal SrFe12O19 nanoribbons were synthesized for the first time via polyvinylpyrrolidone (PVP) sol assisted electrospinning followed by heat treatment in air, and their chemical composition, microstructure and magnetic performance were investigated. Results demonstrated that as-obtained SrFe12O19 nanoribbons were well-crystallized with high purity. Each nanoribbon was self-assembled by abundant single-domain SrFe12O19 nanoparticles and was consecutive on structure and uniform on width. PVP in the spinning solution played a significant influence on the microstructure features of SrFe12O19 nanoribbons. With PVP concentration increasing, the ribbon-width was increased but the particle-size was reduced, which distributed on a same ribbon were more intensive, and then the ribbon-surface became flat. The room temperature magnetic performance investigation revealed that considerable large saturation magnetization (Ms) and coercivity (Hc) were obtained for all SrFe12O19 nanoribbons, and they increased with the ribbon-width broadening. The highest Ms of 67.9 emu · g(-1) and Hc of 7.31 kOe were concurrently acquired for SrFe12O19 nanoribbons with the maximum ribbon-width. Finally, the Stoner-Wohlfarth curling model was suggested to dominate the magnetization reverse of SrFe12O19 nanoribbons. It is deeply expected that this work is capable of opening up a new insights into the architectural design of 1D magnetic materials and their further utilization.

Efficient photocatalytic degradation of acid fuchsin in aqueous solution using separate porous tetragonal-CuFe2O4 nanotubes.

To develop a new promising magnetic photocatalyst, homogeneous tetragonal-CuFe2O4 (t-CuFe2O4) nanotubes were successfully synthesized via the electrospinning technique followed by heating treatment. The detailed investigation of chemical phase and microstructure reveals that the obtained samples are inversely spinel CuFe2O4 nanotubes with an average diameter of about 272±2nm, which are assembled by numerous CuFe2O4 single crystal nanoparticles with regular polyhedron structure and possess a very outstanding porous feature. Furthermore, element mapping, UV-vis adsorption spectrum, N2 adsorption-desorption isotherm, and magnetic hysteresis loop indicate that these t-CuFe2O4 nanotubes have uniform component distribution, strong light response in the range of 200 nm-800 nm, considerable specific surface area of 12.8 m(2)/g and porosity of 15.5 nm, and enough magnetization of about 18 emu/g. Therefore, the t-CuFe2O4 nanotubes show an excellent catalytic activity and durability for the photodecomposition of acid fuchsin dye in aqueous solution under a simulated sunlight source. Furthermore, these CuFe2O4 nanotubes could be acted as an eco-friendly and recyclable photocatalyst because they can be efficiently separated from the residual solution. Finally, a mechanism is presented for the significant photocatalytic performance of the porous CuFe2O4 nanotubes.

Hierarchical SrTiO3/NiFe2O4 composite nanostructures with excellent light response and magnetic performance synthesized toward enhanced photocatalytic activity.

Being capable of gathering advanced optical, electrical and magnetic properties originating from different components, multifunctional composite nanomaterials have been of concern increasingly. Herein, we have successfully demonstrated the preparation of SrTiO3/NiFe2O4 porous nanotubes (PNTs) and SrTiO3/NiFe2O4 particle-in-tubes (PITs) via a single-spinneret electrospinning and a side-by-side-spinneret electrospinning, respectively. The products were characterized by using scanning electron microscopy, transmission electron microscopy, X-ray diffraction, UV-visible diffuse reflectance spectra and a vibrating sample magnetometer in detail. The results indicate that SrTiO3/NiFe2O4 PNTs are the heterojunction nanotubes by connecting perovskite SrTiO3 and spinel NiFe2O4 nanoparticles, but SrTiO3/NiFe2O4 PITs are the self-assembled core/shell structures by embedding SrTiO3 nanoparticles into NiFe2O4 nanotubes. Compared with pure SrTiO3 nanofibers, the two SrTiO3/NiFe2O4 composites exhibit a powerful light response and excellent room temperature ferromagnetism. The magnetic separations directly reveal that such amazing recycling efficiencies of about 95% for SrTiO3/NiFe2O4 PNTs and about 99.5% for SrTiO3/NiFe2O4 PITs are obtained. Furthermore, both the magnetic composites perform considerable photocatalytic activity in the degradation of rhodamine B. We propose that Kirkendall-diffusion and phase-separation are probably responsible for the formation of SrTiO3/NiFe2O4 PITs, and this work could provide a feasible way to assemble the core/shell structures of different materials.