Doped nanomaterial facilitates 3D printing target plate for rapid detection of alkaloids in laser desorption/ionization mass spectrometry.

This work aims to rapidly detect toxic alkaloids in traditional Chinese medicines (TCM) using laser desorption ionization mass spectrometry (LDI-MS). We systematically investigated twelve nanomaterials (NMs) as matrices and found that MoS2 and defect-rich-WO3 (D-WO3) were the best NMs for alkaloid detection. MoS2 and D-WO3 can be used directly as matrices dipped onto conventional ground steel target plates. Additionally, they can be conveniently fabricated as three-dimensional (3D) NM plates, where the MoS2 or D-WO3 NM is doped into resin and formed using a 3D printing process. We obtained good quantification of alkaloids using a chemothermal compound as an internal standard and detected related alkaloids in TCM extracts, Fuzi (Aconiti Lateralis Radix Praeparata), Caowu (Aconiti Kusnezoffii Radix), Chuanwu (Aconiti Radix), and Houpo (Magnoliae Officinalis Cortex). The work enabled the advantageous "dip and measure" method, demonstrating a simple and fast LDI-MS approach that achieves clean backgrounds for alkaloid detection. The 3D NM plates also facilitated mass spectrometry imaging of alkaloids in TCMs. This method has potential practical applications in medicine and food safety. Doped nanomaterial facilitates 3D printing target plate for rapid detection of alkaloids in laser desorption/ionization mass spectrometry.

Thermal desorption bridged the gap between dielectric barrier discharge ionization and dried plasma spot samples for sensitive and rapid detection of fentanyl analogs in mass spectrometry.

The urgent threat of new psychoactive substances worldwide promotes rapid detection and identification demand for public security. Ambient ionization mass spectrometry (AIMS) has become mainstream among various detection techniques. Still, scant successful applications have been fulfilled toward dried blood spot (DBS) or plasma spot (DPS) as an easy-to-implement sampling format in AIMS. This work bridged the gap between dielectric barrier discharge ionization mass spectrometry (DBDI-MS) and DPS/DBS samples by thermal desorption (TD) assistance. It made the impossible mission of direct DBDI-MS measurement on DPS/DBS samples containing fentanyl analogs (FTNs) possible. Guided by finite element simulations and a customized three-dimensional printing interface, we constructed a semi-covered flat-TD surface for sufficient desorption and ionization of FTNs from DPS/DBS samples without any sample pretreatment or sample separation. We successfully quantified eight FTNs in DPS samples using deuterated fentanyl as internal standard by triple quadrupole tandem mass spectrometry (MS/MS) and proved its practical applicability in the fentanyl-exposed rat plasma samples. This DBDI-TD-MS method also fits well with DBS samples, and it only took 20 s to analyze each sample. Further, based on summarized fragmentation characteristics of twenty FTNs, we established a backbone alerting ion-guided screening rule for suspect screening of FTNs in DPS samples via quadrupole time-of-flight MS/MS and built a chemometric approach for convenient mutual verification of screening "unknown" artificial samples. We hope this ideal DBDI-TD-MS method finds its valuable role in national security, doping control, and public health for routine large-scale analysis or on-site detection.

High-Throughput Single-Cell Immunoassay in the Cellular Native Environment Using Online Desalting Dual-Spray Mass Spectrometry.

Single-cell mass spectrometry (MS) remains challenging in the analysis of cells in the native environment due to the severe ion suspension from nonvolatile salts. Synchronous desalting and ionization would be ideal to both ensure the native environment and remove the salt interference. Here, a novel dual-spray ionization technique combining electrospray and nanoelectrospray ionization (ESI-nESI) was developed, enabling highly efficient online desalting during the ionization process. In situ detection of cell surface proteins from the intact cells in phosphate buffer saline (PBS) was achieved by dual ESI-nESI MS with the help of an MS-based immunoassay using rhodamine-based mass tags. These mass tags were confirmed to be highly competitive during desalting, which improved the protein detection sensitivity to a single-cell level. Through the combination of the single-cell immunoassay with ESI-nESI MS, the important surface protein markers, cancer antigen 125, in two cancer cell lines (OVCAR-3 and MCF-7) suspended in the PBS buffers were screened in a high-throughput cytometric mode, along with some proposed cellular endogenous lipids. The ESI-nESI MS system is promising for multidimensional organic mass cytometric analysis in the cellular native environment for clinical use and many basic biology researches.

Microwave-assisted synthesis of 3D Bi2MoO6 microspheres with oxygen vacancies for enhanced visible-light photocatalytic activity.

Oxygen vacancies (OVs) defects in metal oxide-based photocatalysts play a crucial role in improving the charge carrier separation efficiencies to enhance the photocatalytic performances. In this work, OVs were introduced in 3D Bi2MoO6 microspheres through a facile and fast microwave-assisted method via the modulation of tetramethylethylenediamine (TMEDA). EPR, Raman and XPS results demonstrated that large amounts of oxygen vacancies were formed on the surface of BMO microspheres. The photocatalytic properties of the samples were studied by degradation of tetracycline (TC) under visible light. The optimal Bi2MoO6 with OVs exhibited optimum photocatalytic activity, and the degradation rate was 7.0 times higher than that of pristine Bi2MoO6. This enhancement can be attributed to the 3D structure furnishing more surface active sites and suitable OVs defects favoring the electron-hole separation. Moreover, the defective Bi2MoO6 microspheres exhibit high stability because the photocatalytic activity remains almost unchanged after 5 cycles, making them favorable for practical applications. Finally, a possible visible light photocatalysis mechanism for the degradation of TC was tentatively proposed.

Mass, Size, and Density Measurements of Microparticles in a Quadrupole Ion Trap.

The physical properties of microparticles, such as mass, size, and density, are critical for their functions. The comprehensive characterization of these physical parameters, however, remains a fundamental challenge. Here, we developed a particle mass spectrometry (PMS) methodology for determining the mass, size, and density of microparticles simultaneously. The collisional cross-section (CCS) and mass spectrometry (MS) measurements were performed in a single quadrupole ion trap (QIT), and the two modes can be switched easily by tuning the electric and gas hydrodynamic fields of the QIT. The feasibility of the method was demonstrated through a series of monodispersed polystyrene (PS) and silica (SiO2) particle standards. The SiO2/polypyrrole core-shell particles were also successfully characterized, and the measured results were verified by using conventional methods.

Hybrid methods of surface plasmon resonance coupled to mass spectrometry for biomolecular interaction analysis.

Combining mass spectrometry (MS) with surface plasmon resonance (SPR) makes it possible to identify the chemical structures of the interacting molecules studied by SPR. Different approaches for coupling surface plasmon resonance sensors to mass spectrometry were developed. This article aims to summarize the established approaches and their applications to study biomolecular interactions. Three representative interactions were reviewed: protein-protein interactions, enzyme-substrate/inhibitor interactions, and protein-small molecule interactions.

N-Phenyl-2-naphthylamine as a Novel MALDI Matrix for Analysis and in Situ Imaging of Small Molecules.

Due to its strong ultraviolet absorption, low background interference in the small molecular range, and salt tolerance capacity, N-phenyl-2-naphthylamine (PNA) was developed as a novel matrix in the present study for analysis and imaging of small molecules by matrix-assisted laser desorption/ionization mass spectrometry time-of-fight (MALDI-TOF MS). The newly developed matrix displayed good performance in analysis of a wide range of small-molecule metabolites including free fatty acids, amino acids, peptides, antioxidants, and phospholipids. In addition, PNA-assisted LDI MS imaging of small molecules in brain tissue of rats subjected to middle cerebral artery occlusion (MCAO) revealed unique distributions and changes of 89 small-molecule metabolites including amino acids, antioxidants, free fatty acids, phospholipids, and sphingolipids in brain tissue 24 h postsurgery. Fifty-nine of the altered metabolites were identified, and all the changed metabolites were subject to relative quantitation and statistical analysis. The newly developed matrix has great potential application in the field of biomedical research.

Utilizing a Mini-Humidifier To Deposit Matrix for MALDI Imaging.

MALDI mass spectrometry imaging (MALDI-MSI) is a powerful tool to study endogenous metabolites. The process of matrix deposition is crucial for a high-quality imaging result. Commercial instruments for matrix deposition are expensive. Low-cost methods like airbrushing will generate matrix crystals that are too large for high-spatial-resolution imaging. Sublimation may cause some compounds to go undetected because of the lack of solvent. Herein, we utilized a mini-humidifier, costing less than 5 dollars, to deposit matrix for MALDI-MSI. Compared with Imageprep, a commercialized instrument, our device based on the humidifier provided higher sensitivity and much smaller matrix crystals with diameters of less than 10 µm. High-quality ion images with 10 µm spatial resolution were obtained using our method. The enhancement of sensitivity by the humidifier could provide a sufficient amount of ions to perform tandem mass imaging. We also performed MALDI-MS/MS imaging to separate two lipids in mouse brain.

Laser Cleavable Probes-Based Cell Surface Engineering for in Situ Sialoglycoconjugates Profiling by Laser Desorption/Ionization Mass Spectrometry.

Cell-surface sialoglycoconjugates (sialoglycoproteins and sialoglycolipids) play important roles in cell-cell interactions and related tumor metastasis process. Although there have been some analytical methods to evaluate the sialoglycoconjugates, an effective method providing both qualitative and quantitative information is still deficient. Here we establish an extraction-free, sensitive, and high-throughput platform to realize in situ detection of the cell-surface sialoglycoconjugates on various cell lines, e.g., cancer and normal cells by laser desorption/ionization mass spectrometry (LDI MS). In this proposal, azide groups were introduced into the ends of cell-surface sialoglycoconjugates by the biorthogonal method, and then the sialoglycoconjugates were armed with a laser-cleavable probe (Tphsene) through click chemistry. We can easily get the probes signal under laser irradiation, which reflected the presence of cell-surface sialoglycoconjugates. Different cell lines were discriminated simultaneously, and the LDI relative quantification agreed with fluorescent results. Besides, a linear quantitation relationship in the range of 100 fmol to 100 pmol was obtained with a designed and synthesized internal standard (phTsane) added. A detection limit of 5 fmol was obtained with good reproducibility. Based on the quantitative and high-throughput ability, we conducted pharmacodynamics study of drug (tunicamycin) on cancer cells. In addition, we found the tag was safe from sweet-spot effect of matrix adding. The simultaneous detection of sialoglycoconjugates and metabolites was therefore achieved. We believe that this laser cleavable probes-based cell-surface engineering for sialoglycoconjugates platform means great significance to diagnosis, prognosis, and therapeutic purposes. Besides, this strategy can be applied to other glycoconjugates which is hard to detect and the related disease processes when more corresponding chemically modified sugar substrates and exact biorthogonal reactions are developed.

Improved ciprofloxacin removal by a Fe(VI)-Fe3O4/graphene system under visible light irradiation.

In this paper, Fe3O4/graphene (Fe3O4/GE) nanocomposites were prepared by a co-precipitation method and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and UV-vis diffuse reflectance spectra (UV-vis DRS). The composites were used in combination with Fe(VI) to construct a Fe(VI)-Fe3O4/GE system in order to degrade ciprofloxacin (CIP) in simulated water samples. The photocatalytic properties of Fe(VI)-Fe3O4/GE were evaluated under visible light irradiation. The concentration of CIP in solution was detected by high performance liquid chromatography (HPLC). A series of results showed that Fe(VI), as a good electron capture agent, could significantly improve the treatment performance. Major determining factors during CIP degradation were also investigated, in which solution pH of 9, Fe(VI) to Fe3O4/GE dosage ratio of 1:25 and GE content in the Fe3O4/GE nanocomposites of 10 wt% were found to be the best experimental conditions. The results demonstrated that the Fe(VI)-Fe3O4/GE system could offer an alternative process in water treatment in addition to the current Fe(VI)-UV/TiO2 process.

Construction of magnetically separable NiAl LDH/Fe3O4-RGO nanocomposites with enhanced photocatalytic performance under visible light.

Magnetic NiAl layered doubled hydroxide (LDH)/Fe3O4-RGO composites were successfully synthesized via a simple hydrothermal route. The as-prepared samples were well characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM). The results showed that NiAl LDH nanoplatelets and Fe3O4 nanoparticles sized around 15 nm were uniformly anchored on the surface of graphene sheets. The NiAl LDH/Fe3O4-RGO25 photocatalyst was employed to degrade ciprofloxacin (CIP) in an aqueous solution under visible light irradiation. It exhibited enhanced photocatalytic activity compared to pure NiAl LDH, the degradation rate of the as-prepared NiAl LDH/Fe3O4-RGO25 was 1.5 and even 3 times faster than that of NiAl LDH/RGO25 and pure NiAl LDH, respectively. This enhancement of photocatalytic activity is attributed to the addition of graphene and Fe3O4 NPs, which both efficiently promote the separation of charge carriers and improve the optical absorption properties, synergistically facilitating the photocatalysis process. Furthermore, the NiAl LDH/Fe3O4-RGO25 photocatalyst was magnetically separable and exhibited stable catalytic activity, which is beneficial to its practical application.

[Chinese herbal medicine enhances sexual function and c-Fos/nNOS expression in the nucleus accumbens of orchidectomized rats].

RESULTS: There was a decrease in accessory genital organ weight, plasma testosterone, and sexual behavior, as well as a low number of c-Fos-positive cells and a large nNOS-positive cell area in orchidectomized rats. Administration of the herbal medicine increased accessory genital organ weight, testosterone level, mating behavior, and c-Fos-positive cell number, while it decreased the nNOS-positive cell area in orchidectomized rats. CONCLUSION: An increase of plasma testosterone after administration of "kidney-nourishing" herbal medicine might contribute to the elevated sexual function and activity in orchidectomized rats. In addition, a central nervous system mechanism, such as the functional alteration of NAc, might be involved. Abstract OBJECTIVE: To determine whether the central nervous system is involved in the effect of Chinese herbal medicine on sexual function recovery in orchidectomized rats. METHODS: Orchidectomized rats were administered intragastrically with a decoction of "kidney-nourishing" Chinese herbal medicine once per day for 28 days. Accessory genital organ weight, plasma testosterone, and mating behavior were investigated. The expression of c-Fos and neuronal nitric oxide synthase (nNOS) in neuronal cells in the nucleus accumbens (NAc) was analyzed by immunohistochemistry.

Imidazolium-based mass tags for protein biomarker detection using laser desorption ionization mass spectrometry.

Novel imidazolium-based mass tags (IMTs) were designed, synthesized and applied to simultaneous in situ analysis of multiple biomarkers on less than 10 cells. The high sensitivity, flexible extensibility and excellent distinguishability of IMTs open new avenues for designing common mass tag templates suitable for mass spectrometric immunoassay and provide an ideal option for multiplex-sensitive detection at the cellular scale.

Remediation of petroleum-contaminated soil by ball milling and reuse as heavy metal adsorbent.

A simple mechanochemical (MC) method is used to treat petroleum-contaminated soil and prepare a heavy metal adsorbent in one step. XRD, Raman, FT-IR, VSM, BET, and XPS were used to characterize the adsorbent. After MC treatment, the dissolved total petroleum hydrocarbons of the adsorbent is less than 1 mg·L-1, and a porous structure and carbonization phenomenon are evident. The specific surface area and cumulative void volume increase, and the adsorption pore size decreases. On the surface of soil, the percentages of iron oxides, carbonates, CO, -C-O-H, -COOH, and π unsaturated bonds increase. The Langmuir model shows that the maximum adsorption capacity of Pb2+, Cu2+, Cd2+, and Zn2+ are 338.58, 51.61, 32.34, and 25.05 mg·g-1, respectively. The pseudo-second-order kinetic model fits the Pb adsorption process, indicating the domination of chemical adsorption. GC-MS shows that petroleum hydrocarbons are completely degraded. The Tessier continuous extraction result shows that heavy metals are bound to carbonate, iron manganese oxide, and organic matter. The MC treatment achieves deep cleanup and resource utilization of petroleum-contaminated soil through the formation of amorphous carbon, carbonates, and iron oxides on the surface of soil particles. The material is magnetic and can be recycled when used in wastewater treatment.

Photo-Fenton superwettable NiFe2O4/TA/PVDF composite membrane for organic pollutant degradation with successively oil-in-water separation.

With regard to the treatment of multicomponent wastewaters, to construct multifunctional super-wetting membranes is highly attractive in current decade. In this work, a low-cost and novel NiFe2O4/TA/PVDF composite membrane was fabricated via a facile in-situ deposition method under vacuum system. In which, photo-response NiFe2O4 nanoparticles were immobilized on the surface of flexible PVDF base membrane via hydrophilic tannic acid (TA) as the binder. The resulting composite membrane exhibited a special superwettability of superamphilicity in air and underwater superoleophobicity with a nanoscale rough surface structure. One the one hand, NiFe2O4/TA/PVDF membrane can be used a reusable catalyst in Photo-Fenton degradation of organic dyes with high efficiency. On the other hand, the composite membrane can effectively separate emulsified oils from representative oil-in-water emulsions with excellent separation efficiency all above 99 % and relatively high flux (880-1525 Lm-2h-1 bar-1). More importantly, NiFe2O4/TA/PVDF composite membrane showed satisfactory processing efficiency, anti-fouling property and excellent reusability in deal with the mixed organic pollutants (water-insoluble emulsified oils and water-soluble organic dyes) existed in one aqueous system, which followed the procedure of initially photo-Fenton degradation of organic dyes emulsion and successively separation the remaining emulsion over the recovered membrane. This successful development of high-performance NiFe2O4/TA/PVDF composite membrane will provide a new candidate for both oil/water separation and organic wastewater treatment, as well as promote the utilization of spinel ferrites in the construction of multifunctional membrane for environmental purification.

Bifunctional NiAlFe LDH-coated membrane for oil-in-water emulsion separation and photocatalytic degradation of antibiotic.

A new NiAlFe layered double hydroxide/polydopamine/polyvinylidene fluoride (NiAlFe LDH/PDA/PVDF) membrane was fabricated by in-situ growth of LDH on the PDA modified PVDF membrane. The as-prepared membrane possesses a nano/microscale rough structural surface and displays the superior wettability of superhydrophilicity in air and underwater superoleophobicity. Combining the favourable features of superwettability and hierarchical rough structure, the NiAlFe LDH/PDA/PVDF membrane could effectively separate a series of oil-in-water emulsions with high efficiency (>99%) and high permeation flux (925-1913 L m-2 h-1 bar-1). Besides, owing to the light harvest ability of NiAlFe LDH, the relevant membrane also can be applied as a photocatalysis paper for the light-driven treatment of antibiotic residue in aqueous solution. In which, NiAlFe LDH/PDA/PVDF membrane can effectively degrade typical antibiotic tetracycline within 20 min under UV light irradiation, exhibiting excellent photocatalytic activity. In addition, cyclic experiments demonstrate that NiAlFe LDH/PDA/PVDF membrane has excellent stability and reusability both in oil-in-water emulsion separation and photocatalytic reaction. In general, the findings of this research demonstrate that photo-response LDH modified membranes have potential multiple applications in wastewater treatment.

Synthesis of Porphyrin Zr-MOFs for the Adsorption and Photodegradation of Antibiotics under Visible Light.

The release of antibiotics into the water environment can pose a serious threat to human and ecological health, so it is of great significance to effectively remove antibiotics from wastewater. In this work, porphyrinic zirconium metal-organic framework material, PCN-224, was first explored for the adsorption removal of antibiotics from water using tetracycline (TC) and ciprofloxacin (CIP) as examples. We prepared a series of PCN-224 with different particle sizes (150 nm, 300 nm, 500 nm, and 6 µm). Benefiting from the huge surface area (1616 m2 g-1), the 300 nm-PCN-224 sample had the best adsorption properties for TC and CIP. Remarkably, it exhibits fast removal rates and high adsorption capacities of 354.81 and 207.16 mg g-1 for TC and CIP, respectively. The adsorption of TC and CIP in 300 nm-PCN-224 is consistent with the pseudo-second-order kinetic model and Langmuir isotherm model, which indicates that the adsorption can be regarded as homogeneous monolayer chemisorption, and the adsorption is exothermic, which has been confirmed by thermodynamic studies. Under visible-light irradiation, 300 nm-PCN-224 exhibited high photocatalytic activity for TC and CIP. The adsorption studies confirmed that the adsorption of adsorbates takes place via the formation of hydrogen bonding, π-π interactions, and electrostatic attraction. In addition, the adsorbent can be simply regenerated by photocatalysis under visible light, and the adsorption-desorption efficiency is still above 85% after repeated use five times. The work of MOFs to remove antibiotics from water shows that MOFs have great potential in this field and are worthy of further study.

MALDI-TOF/TOF tandem mass spectrometry imaging reveals non-uniform distribution of disaccharide isomers in plant tissues.

Mass spectrometry imaging (MSI) is a powerful technique for investigating the biomolecular locations within tissues. However, the isomeric compounds are rarely distinguished due to inability of MSI to differentiate isomers in the probing area. Coupling tandem mass spectrometry with MSI can facilitate differentiating isomeric compounds. Here MALDI-TOF/TOF tandem mass spectrometry imaging approach was applied to probing the spatial distributions of isomeric disaccharides in plant tissues. First, MS/MS imaging analysis of disaccharide-matrix droplet spots demonstrated the feasibility of distinguishing isomeric species in tissues, by measuring the relative intensity of specific fragments. Then, tandem MS imaging of disaccharides in onion bulb tissues indicated that sucrose and other unknown non-sucrose disaccharides exhibit heterogeneous locations throughout the tissues. This method enables us to image disaccharide isomers differentially in biological tissues, and to discover new saccharide species in plant. This work also emphasizes the necessity of considering isobaric compounds when interpreting MSI results.

Microwave Solvothermal Synthesis of Three-Dimensional Bi2MoO6 Microspheres with Enhanced Photocatalytic Activity.

In this study, three-dimensional (3D) Bi2MoO6 microspheres were successfully fabricated by a facile, rapid, and mild microwave solvothermal strategy for the first time. The resultant 3D Bi2MoO6 microspheres exhibited superior adsorption capacity and photocatalytic efficiency in the degradation of the representative antibiotic ciprofloxacin under visible light, for which the reaction kinetic rate constant is 7.5 times as high as that of the as-synthesized zero-dimensional Bi2MoO6 nanoparticles. The 3D hierarchical porous structure and the high Brunauer-Emmett-Teller surface area providing abundant reactive sites mainly contributed to the enhanced photocatalytic activity. The results highlight the feasibility of 3D Bi2MoO6 microspheres as an efficient visible-light-responsive photocatalyst for antibiotic removal in an aqueous system.

Tracing and elucidating visible-light mediated oxidation and C-H functionalization of amines using mass spectrometry.

The co-existing mechanism of visible light mediated direct oxidation and C-H functionalization of amines was investigated by capturing all the intermediates using online mass spectrometry. The two-step dehydrogenation of amine involving a proton coupled electron transfer (PCET) process was revealed for the first time.