Identification of metabolic markers in patients with type 2 Diabetes by Ultrafast gas chromatography coupled to electronic nose. A pilot study

Metabolomics is a potential tool for the discovery of new biomarkers in the early diagnosis of diseases. An ultra-fast gas chromatography system equipped to an electronic nose detector (FGC eNose) was used to identify the metabolomic profile of Volatile Organic Compounds (VOCs) in type 2 diabetes (T2D) urine from Mexican population. A cross-sectional, comparative, and clinical study with translational approach was performed. We recruited twenty T2D patients and twenty-one healthy subjects. Urine samples were taken and analyzed by FGC eNose. Eighty-eight compounds were identified through Kovats's indexes. A natural variation of 30% between the metabolites, expressed by study groups, was observed in Principal Component 1 and 2 with a significant difference (p < 0.001). The model, performed through a Canonical Analysis of Principal coordinated (CAP), allowed a correct classification of 84.6% between healthy and T2D patients, with a 15.4% error. The metabolites 2-propenal, 2-propanol, butane- 2,3-dione and 2-methylpropanal, were increased in patients with T2D, and they were strongly correlated with discrimination between clinically healthy people and T2D patients. This study identified metabolites in urine through FGC eNose that can be used as biomarkers in the identification of T2D patients. However, more studies are needed for its implementation in clinical practice.     

Polymer nanoparticles with a sensitive CO2‐responsive hydrophilic/hydrophobic surface

Poly(methyl methacrylate) (PMMA) nanoparticles with a sensitive CO₂‐responsive hydrophilic/hydrophobic surface that confers controlled dispersion and aggregation in water were prepared by emulsion polymerization at 50 °C under CO₂ bubbling using amphiphilic diblock copolymers of 2‐dimethylaminoethyl methacrylate (DMAEMA) and N‐isopropyl acrylamide (NIPAAm) as an emulsifier. The amphiphilicity of the hydrophobic–hydrophilic diblock copolymer at 50 °C was triggered by CO₂ bubbling in water and enabled the copolymer to serve as an emulsifier. The resulting PMMA nanoparticles were spherical, approximately 100 nm in diameter and exhibited sensitive CO₂/N₂‐responsive dispersion/aggregation in water. Using copolymers with a longer PNIPAAm block length as an emulsifier resulted in smaller particles. A higher concentration of copolymer emulsifier led to particles with a stickier surface. Given its simple preparation and reversible CO₂‐triggered amphiphilic behavior, this newly developed block copolymer emulsifier offers a highly efficient route toward the fabrication of sensitive CO₂‐stimuli responsive polymeric nanoparticle dispersions. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2149–2156     

Atmospheric oxidation chemistry of 1–methoxy 2–propyl acetate initiated by OH radicals: kinetics and mechanisms

Kinetics and mechanism of the gas-phase reaction of CH₃C(O)OCH(CH₃)CH₂OCH₃ (MPA) with OH radicals in the presence of O₂ and NO have been investigated theoretically by performing a high and reliable level of theory, viz., CCSD(T)/6-311?+?G(d,p)//BH&HLYP/6-311++G(d,p)?+?0.9335×ZPE. The calculations predict that the H-abstraction from the ?CH₂?O? position of MPA is the most facile channel, which leads to the formation of the corresponding alkoxy radicals CH₃C(O)OCH(CH₃)C(O ?)HOCH₃ under atmospheric conditions. This activated radicals CH₃C(O)OCH(CH₃)C(O ?)HOCH₃ will undergo further rearrangement, fragmentation and oxidative reactions and predominantly leads to the formation of various products (methyl formate HC(O)OCH₃ and acetic anhydride CH₃C(O)OC(O)CH₃). In the presence of water, acetic anhydride can convert into acetic acid CH₃C(O)OH via the hydrolysis reaction. The calculated total rate constants over the temperature range 263–372?K are used to derive a negative activation energy (E_a= ?5.88 kJ/mol) and an pre-exponential factor (A?=?1.78×10^?12 cm³ molecule^?1 s^?1). The obtained Arrhenius parameters presented here are in strong agreement with the experimental values. Moreover, the temperature dependence of the total rate constant over a temperature range of 263?1000?K can be described by k?=?5.60 × 10^?14×(T/298?K)^3.4×exp(1725.7?K/T) cm³ molecule^?1 s^?1.     

Electrical and Thermal Transport Properties of n-type Bi6Cu2Se4O6 (2BiCuSeO + 2Bi2O2Se)

New thermoelectric materials, n-type Bi₆Cu₂Se₄O₆ oxyselenides, composed of well-known BiCuSeO and Bi₂O₂Se oxyselenides, are synthesized with a simple solid-state reaction. Electrical transport properties, microstructures, and elastic properties are investigated with an emphasis on thermal transport properties. Similar to Bi₂O₂Se, it is found that the halogen-doped Bi₆Cu₂Se₄O₆ possesses n-type conducting transports, which can be improved via Br/Cl doping. Compared with BiCuSeO and Bi₂O₂Se, an extremely low thermal conductivity can be observed in Bi₆Cu₂Se₄O₆. To reveal the origin of low thermal conductivity, elastic properties, sound velocity, Grüneisen parameter, and Debye temperature are evaluated. Importantly, the calculated phonon mean free path of Bi₆Cu₂Se₄O₆ is comparable to the interlayer distance for BiO─CuSe and BiO─Se layers, which is ascribed to the strong interlayer phonon scattering. Contributing from the outstanding low thermal conductivity and improved electrical transport properties, the maximum ZT ≈0.15 at 823 K and ≈0.11 at 873K are realized in n-type Bi₆Cu₂Se_3.2Br_0.8O₆ and Bi₆Cu₂Se_3.6Cl_0.4O₆, respectively, indicating the promising thermoelectric performance in n-type Bi₆Cu₂Se₄O₆ oxyselenides.     

Evaluation of Charged Defect Energy in Two-Dimensional Semiconductors for Nanoelectronics: The WLZ Extrapolation Method

Defects play a central role in controlling the electronic properties of two-dimensional (2D) materials and realizing the industrialization of 2D electronics. However, the evaluation of charged defects in 2D materials within first-principles calculation is very challenging and has triggered a recent development of the WLZ (Wang, Li, Zhang) extrapolation method. This method lays the foundation of the theoretical evaluation of energies of charged defects in 2D materials within the first-principles framework. Herein, the vital role of defects for advancing 2D electronics is discussed, followed by an introduction of the fundamentals of the WLZ extrapolation method. The ionization energies (IEs) obtained by this method for defects in various 2D semiconductors are then reviewed and summarized. Finally, the unique defect physics in 2D dimensions including the dielectric environment effects, defect ionization process, and carrier transport mechanism captured with the WLZ extrapolation method are presented. As an efficient and reasonable evaluation of charged defects in 2D materials for nanoelectronics and other emerging applications, this work can be of benefit to the community.     

Recent Advances in Spatial Self-Phase Modulation with 2D Materials and its Applications

In recent years, spatial self-phase modulation (SSPM) with two-dimensional (2D) materials has attracted the attention of many researchers as an emerging and ubiquitous nonlinear optical effect. In this review, the state of the art of 2D material-based SSPM is summarized. SSPM measures or tunes the nonlinearity of 2D materials, and it is also an effective approach to study the band structure of 2D materials. Several modified forms of SSPM, such as high-order, white-light-excited, vector field excited, and optically nonlinearly enhanced SSPM are also presented. Subsequently, the physical origin of the SSPM formation mechanism is compared and analyzed. Furthermore, the applications of SSPM with 2D materials, including passive photonic devices, generation of Bessel beams, and identifying the mode of the orbital angular momentum, are listed. Finally, several urgent problems of the SSPM with 2D materials, potential applications, and prospects for future development are presented.     

Development and validation of a reversed‐phase HPLC method for CYP1A2 phenotyping by use of a caffeine metabolite ratio in saliva

CYP1A2 is important for metabolizing various clinically used drugs. Phenotyping of CYP1A2 may prove helpful for drug individualization therapy. Several HPLC methods have been developed for quantification of caffeine metabolites in plasma and urine. Aim of the present study was to develop a valid and simple HPLC method for evaluating CYP1A2 activity during exposure in xenobiotics by the use of human saliva. Caffeine and paraxanthine were isolated from saliva by liquid‐liquid extraction (chlorophorm/isopropanol 85/15v/v). Extracts were analyzed by reversed‐phase HPLC on a C₁₈ column with mobile phase 0.1% acetic acid/methanol/acetonitrile (80/20/2 v/v) and detected at 273nm. Caffeine and paraxanthine elution times were <13min with no interferences from impurities or caffeine metabolites. Detector response was linear (0.10–8.00µg/ml, R²>0.99), recovery was >93% and bias <4.47%. Intra‐ and inter‐day precision was <5.14% (n=6). The limit of quantitation was 0.10µg/ml and the limit of detection was 0.018±0.002µg/mL for paraxanthine and 0.032±0.002µg/ml for caffeine. Paraxanthine/caffeine ratio of 34 healthy volunteers was significantly higher in smokers (p<0.001). Saliva paraxanthine/caffeine ratios and urine metabolite ratios were highly correlated (r=0.85, p<0.001). The method can be used for the monitoring of CYP1A2 activity in clinical practice and in studies relevant to exposure to environmental and pharmacological xenobiotics. Copyright © 2015 John Wiley & Sons, Ltd.     

Effect of chemical parameters on pyrene degradation in soil in a pulsed discharge plasma system

Degradation of pyrene in soil in a net-to-net pulsed discharge plasma (PDP) system was reviewed. Effect of main chemical parameters, including air flow rate, pyrene concentration, initial pH and soil moisture content on pyrene degradation was examined. The obtained results show that 87.9% of pyrene could be removed under the condition of 60 min reaction; increasing of air flow rate within 1 L min⁻¹ was favorable for degradation; pyrene removal was decreased with the increase of initial pyrene concentration; oxidation of pyrene was more evident in acidic soil; enhancement of soil moisture content has no benefit on pyrene degradation.     

Fluorescence properties of riboflavin-functionalized mesoporous silica SBA-15 and riboflavin solutions in presence of different metal and organic cations

Riboflavin was covalently linked to mesoporous SBA-15 silica surface via grafting technique. Then fluorescence properties of the system obtained were analyzed in the presence of several metal and organic cations. Both quenching and strengthening of fluorescence as well as significant changes in the maximum fluorescence wavelength were observed. The results were compared with absorption and fluorescence data obtained for riboflavin water solutions.     

Design and development of a two‐dimensional system based on hydrophilic and reversed‐phase liquid chromatography with on‐line sample treatment for the simultaneous separation of excreted xenobiotics and endogenous metabolites in urine

In the present work we describe a two‐dimensional liquid chromatographic system (2D‐LC) with detection by mass spectrometry (MS) for the simultaneous separation of endogenous metabolites of clinical interest and excreted xenobiotics deriving from exposure to toxic compounds. The 2D‐LC system involves two orthogonal chromatographic modes, hydrophilic interaction liquid chromatography (HILIC) to separate polar endogenous metabolites and reversed‐phase (RP) chromatography to separate excreted xenobiotics of low and intermediate polarity. Additionally, the present proposal has the novelty of incorporating an on‐line sample treatment based on the use of restricted access materials (RAMs), which permits the direct injection of urine samples into the system. The work is focused on the instrumental coupling, studying all possible options and attempting to circumvent the problems of solvent incompatibility between the RAM device and the two chromatographic columns, HILIC and RP. The instrumental configuration developed, RAM‐HILIC‐RPLC‐MS/MS, allows the simultaneous assessment of urinary metabolites of clinical interest and excreted compounds derived from exposure to toxic agents with minimal sample manipulation. Thus, it may be of interest in areas such as occupational and environmental toxicology in order to explore the possible relationship between the two types of compounds. Copyright © 2015 John Wiley & Sons, Ltd.