Urinary exposure marker discovery for toxicants using ultra-high pressure liquid chromatography coupled with Orbitrap high resolution mass spectrometry and three untargeted metabolomics approaches

Human biomonitoring is the assessment of actual internal contamination of chemicals by measuring exposure markers, chemicals or their metabolites, in human urine, blood, serum, and other body fluids. However, the metabolism of chemicals within an organism is extremely complex. Therefore, the identification of metabolites is often difficult and laborious. Several untargeted metabolomics methods have been developed to perform objective searching/filtering of accurate-mass-based LC-MS data to facilitate metabolite identification. In this study, three metabolomics data processing approaches were used for chemical exposure marker discovery in urine with an LTQ-Orbitrap high-resolution mass spectrometry (HRMS) dataset; di-isononyl phthalate (DINP) was used as an example. The data processing techniques included the SMAIT, mass defect filtering (MDF), and XCMS Online. Sixteen, 83, and 139 probable DINP metabolite signals were obtained using the SMAIT, MDF, and XCMS procedures, respectively. Fourteen probable metabolite signals mined simultaneously by the three metabolomics approaches were confirmed as DINP metabolites by structural information provided by LC-MS/MS. Among them, 13 probable metabolite signals were validated as exposure-related markers in a rat model. Six (m/z 319.155, 361.127, 373.126, 389.157, 437.112 and 443.130) of the 13 exposure-related DINP metabolite signals have not previously been reported in the literature. Our data indicate that SMAIT provided an efficient method to discover effectively and systematically urinary exposure markers of toxicant. The DINP metabolism information can provide valuable information for further investigations of DINP toxicity, toxicokinetics, exposure assessment, and human health effects.     

On the method of directly defining inverse mapping for nonlinear differential equations

In scientific computing, it is time-consuming to calculate an inverse operator \(\mathcal {A}^{-1}\) of a differential equation \(\mathcal {A}\phi = f\), especially when \(\mathcal {A}\) is a highly nonlinear operator. In this paper, based on the homotopy analysis method (HAM), a new approach, namely the method of directly defining inverse mapping (MDDiM), is proposed to gain analytic approximations of nonlinear differential equations. In other words, one can solve a nonlinear differential equation \(\mathcal {A}\phi = f\) by means of directly defining an inverse mapping \(\mathcal J\), i.e. without calculating any inverse operators. Here, the inverse mapping \(\mathcal {J}\) is even unnecessary to be explicitly expressed in a differential form, since “mapping” is a more general concept than “differential operator”. To guide how to directly define an inverse mapping \(\mathcal {J}\), some rules are provided. Besides, a convergence theorem is proved, which guarantees that a convergent series solution given by the MDDiM must be a solution of problems under consideration. In addition, three nonlinear differential equations are used to illustrate the validity and potential of the MDDiM, and especially the great freedom and large flexibility of directly defining inverse mappings for various types of nonlinear problems. The method of directly defining inverse mapping (MDDiM) might open a completely new, more general way to solve nonlinear problems in science and engineering, which is fundamentally different from traditional methods.     

A Mixed‐Ligand Approach for a Gigantic and Hollow Heterometallic Cage {Ni64RE96} for Gas Separation and Magnetic Cooling Applications

Nanosized aggregations of metal ions shielded by organic ligands possessing both exquisite structural aesthetics and intriguing properties are fundamentally interesting. Three isostructural gigantic transition‐metal–rare‐earth heterometallic coordination cages are reported, abbreviated as {Ni₆₄RE₉₆} (RE=Gd, Dy, and Y) and obtained by a mixed‐ligand approach, each possessing a cuboidal framework made of 160 metal ions and a nanosized spherical cavity in the center. Along with the structural novelty, these hollow cages show highly selective adsorptions for CO₂ over CH₄ or N₂ at ambient temperatures. Moreover, the gadolinium analogue exhibits large magnetocaloric effect at ultralow temperatures.     

Simultaneous determination of four fluorescent whitening agents (including trans and cis isomers) in facial mask by dispersive solid‐phase extraction combined with ultra high performance liquid chromatography and diode array detection

A novel ultra high performance liquid chromatography with diode array detection method, based on the dispersive solid‐phase extraction by using polymer weak anion exchange as the sorbent, was established for the simultaneous determination of fluorescent whitening agents 85, 28, 351, and 71 in facial mask. The amounts of polymer weak anion exchange, adsorption time, and volume of elution solvent in the dispersive solid‐phase extraction technology were optimized, and the developed method was validated in terms of the method limit of detection, method limit of quantitation, linear range, recovery, accuracy, and precision. Results indicated that the standard curves were linear over the selected concentration ranges of 0.05–100 mg/L for four target analytes, with determination coefficients greater than 0.999. The method limits of quantitation of the target analytes were in the range of 0.6–2.8 mg/kg. Recoveries were calculated at the concentrations of 1.0–30 mg/kg spiked in negative samples and the values were between 89.3 and 102% with an RSD of 2.5–5.1% for intraday precision and 3.8–5.0% for interday precision. The method was successfully applied to analyze 20 facial mask samples and fluorescent whitening agent 85 was detected in one sample with the concentration of 4.7 mg/kg.     

First separation of four aromatic acids and two analogues with similar structures and polarities from Clematis akebioides by high‐speed counter‐current chromatography

In this paper, we report an efficient method by high‐speed counter‐current chromatography for the first separation of four aromatic acids and two analogs with similar structures and polarities from Clematis akebioides. First, the ethyl acetate extract was treated by silica gel column chromatography to enrich the target compounds. And then the fraction with target compounds were purified by high‐speed counter‐counter chromatography using a two‐phase solvent system consisting of chloroform/acetonitrile/water (10:6:4, v/v). The results showed high‐speed counter‐current chromatography could be a powerful technology for the separation of compounds with similar structures and polarities. Besides, it was found acetonitrile could be a good methanol substitute when a chloroform/methanol/water system could not provide a good separation factor. This study provides a reference for the separation of compounds from Clematis akebioides.     

1,3-methoxy rearrangement of masked o-benzoquinones: a novel synthesis of p-quinol ethers

p-Quinol ethers are valuable synthons in synthetic organic chemistry. MOBs 1a-1i can be converted to p-quinol ethers 2a-2i in a highly efficient manner via 1,3-methoxy migration catalyzed by Lewis acids. The migration was found to be reversible and dependent on the electronic effect of substituent R3 of MOBs.     

Novel oxazabicycles as a new class of photochromic colorants

A new photochromic colorant with an oxazabicyclic moiety has been synthesized by an efficient method. It turns pale red upon UV irradiation and undergoes reverse reaction while being heated. This work may open an exciting new avenue for future development of the photochromic dyes with novel molecular structures.     

A CNT-like coordination tube with cyano-bridges

Reaction of K2[Ru(bipy)(CN)4] with MnCl2 produces a novel bimetallic compound {Mn(H2O)2[Ru(bipy)(CN)4]} (bipy = 2,2'-bipydine), exhibiting a CNT-like structure bridged by cyanide groups and high thermal stability, which has been first observed in coordination polymers.     

Polarized photon-pairs heterodyne polarimetry for ultrasensitive optical activity detection of a chiral medium

A polarized photon-pairs heterodyne polarimetry is proposed in order to measure in an ultrasensitive manner the circular birefringence of a chiral medium via optical rotation detection. A balanced detector is integrated into this polarimeter. Thus, shot-noise-limited detection by this polarimeter can be achieved. Experimentally, the detection sensitivity for the circular birefringence of a glucose-water solution up to partial differential |n(r) - n(l)| = 2 x 10(-11) at 10 mg/dL is verified. To our knowledge, this is the highest sensitivity ever measured of a chiral liquid solution based on single traveling sample cell geometry. Finally, when compared to a fiber loop ring-resonator in the frequency domain for a chiral liquid, this polarimeter shows an order of 10(4) enhancement on the sensitivity of natural optical activity measurement.