Phenylmethanesulfonyl fluoride pretreatment stabilizes plasma lipidome in lipidomic and metabolomic analysis

Though it is standard practice to test the stability of analytes in the matrix for routine bioanalytical method, stability evaluation is always impractical and skipped in untargeted lipidomic and metabolomic analysis because analytes in these studies are enormous, diverse and sometimes unknown. Lipidome represents a major class of plasma metabolome and shows great potential to be diagnostic and prognostic biomarkers. However, lipidome also faces stability problems because plasma contains kinds of lipid degradation enzyme. Here, using liquid chromatography time of flight mass spectrometry based lipidomic methodology, plasma levels of various lipids including triglyceride (TG), diglyceride (DG), free fatty acid (FFA), phosphatidylethanolamine (PE) phosphatidylcholine (PC), lyso-phosphatidylcholine (LPC), lyso-phosphatidylethanolamine (LPE), and sphingomyelin (SM) were dynamically determined within 4 h at ambient temperature. In mouse and rat plasma, the levels of most TG, DG, PC and PE species significantly decreased with respect to time, whereas those of LPC, LPE and FFA significantly increased with respect to time. However, such changes did not occur in human plasma, thus indicating hepatic lipase and esterase might involve in the species-specified degradation of lipid classes in plasma. Phenylmethanesulfonyl fluoride (PMSF) pretreatment prevented such lipidome instability in mouse plasma. The results suggested the instability of plasma lipidome should be highly concerned, and the enhancement of ex vivo stability of plasma lipidome could enable more reliable clinical translation of lipidomic data for biomarker discovery.     

The Cu-MOF-199/single-walled carbon nanotubes modified electrode for simultaneous determination of hydroquinone and catechol with extended linear ranges and lower detection limits

A novel electrochemical sensor based on Cu-MOF-199 [Cu-MOF-199 = Cu₃(BTC)₂ (BTC = 1,3,5-benzenetricarboxylicacid)] and SWCNTs (single-walled carbon nanotubes) was fabricated for the simultaneous determination of hydroquinone (HQ) and catechol (CT). The modification procedure was carried out through casting SWCNTs on the bare glassy carbon electrode (GCE) and followed by the electrodeposition of Cu-MOF-199 on the SWCNTs modified electrode. Cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM) were performed to characterize the electrochemical performance and surface characteristics of the as-prepared sensor. The composite electrode exhibited an excellent electrocatalytic activity with increased electrochemical signals towards the oxidation of HQ and CT, owing to the synergistic effect of SWCNTs and Cu-MOF-199. Under the optimized condition, the linear response range were from 0.1 to 1453 μmol L⁻¹ (R_HQ = 0.9999) for HQ and 0.1–1150 μmol L⁻¹ (R_CT = 0.9990) for CT. The detection limits for HQ and CT were as low as 0.08 and 0.1 μmol L⁻¹, respectively. Moreover, the modified electrode presented the good reproducibility and the excellent anti-interference performance. The analytical performance of the developed sensor for the simultaneous detection of HQ and CT had been evaluated in practical samples with satisfying results.     

Surface-enhanced Raman spectroscopy based on conical holed enhancing substrates

In this contribution, surface-enhanced Raman spectroscopy (SERS) based on conical holed glass substrates deposited with silver colloids was reported for the first time. It combines the advantages of both dry SERS assays based on plane films deposited with silver colloids and wet SERS assays utilizing cuvettes or capillary tubes. Compared with plane glass substrates deposited with silver colloids, the conical holed glass substrates deposited with silver colloids exhibited five-to ten-folds of increase in the rate of signal enhancement, due to the internal multiple reflections of both the excitation laser beam and the Raman scattering photons within conical holes. The application of conical holed glass substrates could also yield significantly stronger and more reproducible SERS signals than SERS assays utilizing capillary tubes to sample the mixture of silver colloids and the solution of the analyte of interest. The conical holed glass substrates in combination with the multiplicative effects model for surface-enhanced Raman spectroscopy (MEM_SERS) achieved quite sensitive and precise quantification of 6-mercaptopurine in complex plasma samples with an average relative prediction error of about 4% and a limit of detection of about 0.02 μM using a portable i-Raman 785H spectrometer. It is reasonable to expect that SERS technique based on conical holed enhancing substrates in combination with MEM_SERS model can be developed and extended to other application areas such as drug detection, environmental monitoring, and clinic analysis, etc.     

An effective colorimetric and ratiometric fluorescent probe for bisulfite in aqueous solution

We have developed the first two-photon colorimetric and ratiometric fluorescent probe, BICO, for the detection of bisulfite (HSO₃⁻) in aqueous solution. The probe contains coumarin and benzimidazole moieties and can detect HSO₃⁻ based on the Michael addition reaction with a limit of detection 5.3 × 10⁻⁸ M in phosphate-buffered saline solution. The probe was used to detect bisulfite in tap water, sugar and dry white wine. Moreover, test strips were made and used easily. We successfully applied the probe to image living cells, using one-photon fluorescence imaging. BICO overcomes the limitations in sensitivity of previously reported probes and the solvation effect of bisulfite, which demonstrates its excellent value in practical application.     

The Aerobic Oxidation and C=C Bond Cleavage of Styrenes Catalyzed by Cerium(IV) Ammonium Nitrate (CAN)

The CAN‐catalyzed aerobic oxidation severed the C=C bond selectively through the single electron transfer mechanism, giving a green method to decompose olefins. Compared with the literature reported examples, this method required simple catalyst, cheap, abundant and clean oxidant and was very safe to operate due to the mild conditions.     

Fabrication of the Monolithic Fiber for the Solid Phase Micro‐extraction of Malachite Green

A monolithic fiber of molecularly imprinted polymer (MIP) was prepared by in situ polymerization within the capillary with an inner diameter of 530 µm. It was carried out in 8 min by microwave irradiation using malachite green (MG) as a template molecule, α‐methacrylic acid (MAA) as a functional monomer, acetonitrile (ACN) as a porogenic solvent, ethylene dimethacrylate (EDMA) as a crosslinker, azodiiso‐butyronitrile (AIBN) as a thermal initiator. The resulted MIP fibers were pushed out from the capillary, eluted and inserted in the capillary again, which successfully used for the solid phase microextraction (SPME) procedure. The factors affecting the extraction of MG, such as the molar ratio of template/monomer (MG/MAA), concentration of NaCl, extraction and desorption time, and extraction and desorption solvents were investigated in detail. The selectivity of the MIP fibers was compared using MG analogues crystal violet (CV) and non‐analogue Sudan II. It was also employed for the pretreatment of trace MG in the fish feed followed by high‐performance liquid chromatography (HPLC) detection. Under the optimal conditions, the linear range of MG was 10‐600 μg/L, the detection limit (LOD) was 1.23 μg/L and the recovery of spiked fish feed sample was 88.7～113.9%.     

Experimental Investigation on Binary Phase Diagram of the Thermotropic Phase Transitions Compounds (n‐CnH2n+1R3)2ZnCl4

The thermotropic phase transitions compounds (n‐C_nH_2n+1R₃)₂ZnCl₄ as well as a series of their binary mixtures were prepared by a solution reflux method from their ethanol solutions. The experimental subsolidus binary phase diagram of [n‐C₁₈H₃₇N(CH₃)₃]₂ZnCl₄‐[n‐(C₁₈H₃₇)₂N(CH₃)₂]₂ZnCl₄ is constructed over the entire composition range by differential scanning calorimetry(DSC) and X‐ray. Experi‐ mental results indicate one stable intermediate phase [n‐C₁₈H₃₇N(CH₃)₃] [n‐(C₁₈H₃₇)₂N(CH₃)₂]ZnCl₄ at W_C18C3Zn %=59.75 %, and two invariant three phase equilibria, which shows two eutectoid temperatures: Te₁ at 310±1 K for eutectoid point W_C18C3Zn %=36.24 %, Te₂ at 313±1 K for eutectoid point W_C18C3Zn %=80.17 %. These three noticeable solid‐solution ranges are α‐phase at the left, ?‐phase at the right, and ψ‐phase in the middle of the phase diagram. It is (n‐C_nH_2n+1R₃)₂ZnCl₄ systems as phase change materials that are characterized the phase transition temperatures T in the range of 310 to 340 K, the transition enthalpies ΔH in the range of 38.40 and 168.72 J/g between two polymorphic forms.     

Reactions of a,ß‐unsaturated N‐benzenesulfonyl Imine – N‐[(2E)‐3‐phenyl‐2‐propen‐1‐ylidene]benzenesulfonamide with Methyllithium

α,β‐Unsaturated N‐benzenesulfonyl imine 1 was treated with 1.1 eq methyllithium to afford 1,2‐addition adduct as a sole product. However, when compound 1 was treated with 2 eq MeLi, 1,2‐addition product, benzenesulfonamide derivative 3 and 2H‐1,2‐benzothiazine 1,1‐dioxide derivatives 4 and 5 were isolated.