Sensitivity in Supramolecular Architectures of Polyaromatic Salts Containing Two Singly‐Pimerized Bipyridines

Three novel supramolecular arrays of zigzag polyaromatic salts are reported. Both the conformation and disposition of the dications are subjected to various noncovalent interactions. Thus, the presence or absence of the π‐π interacting enclathrated molecules, the efficient packing and the involved hydrogen bonding interactions of anions, as well as the increased hydrophobic property of the dications themselves exert influence.     

Thermal Degradation Behavior and Kinetic Analysis of Biodegradable Polymers Using Various Comparative Models, 1

Thermal degradation behavior of a biodegradable polymer (PBS) has been investigated by conventional and MTGA methods. The kinetic parameters of degradation were calculated by a general analytical solution and by the Coats‐Redfern, Ozawa, Horowitz‐Metzger, and MTGA methods. The results reveal that the reaction mechanism at lower temperature is probably the F1 model through the reaction of random chain cleavage via cis‐elimination. However, the reaction mechanism at higher temperature is likely to be D1 model because of the dominant diffusion control effect.

     

Spectroscopic study on the zinc-contaminated soils for the determination of zinc speciation

The purpose of this paper reported the zinc species in the highly contaminated soils from metallurgical area around Erh-Jen River in the southern of Taiwan. FTIR and XPS were used to investigate the zinc species in the contaminated soils. Through a FTIR analysis, appreciable of zinc bound by organic matter was found and their bonding structure consisted of antisymmetric and symmetric stretchings, Zn-HSsym and Zn-HSasym. With XPS analysis, the Angstrom scale depth scan was surveyed for investigation the zinc speciation. No signal of zinc was detected in the depth of 900A for the larger particle contaminated soils whereas the detectable signal of zinc was determined in the XPS experiment. With further regression and fitting results, the major zinc species presented in the surface of larger and fine particle contaminated soils consisted of reductive and oxidative zinc species. In the deeper depth of contaminated soils, an inverse spinel zinc ferrite was found in the case of larger particle soil. No inverse spinel zinc ferrite was detected in the case of fine particle soil and could be attributed to the relatively small particle size.     

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.     

Crosslinkable high dielectric constant polymer dielectrics for low voltage organic field‐effect transistor memory devices

I n this study, we successfully synthesized water/methanol soluble random copolymers with a high dielectric constant, poly(n‐(hydroxymethyl) acrylamide‐co‐5‐(9‐(5‐(diethylamino)pentyl)?2‐(4‐vinylphenyl)?9H‐fluorene(P(NMA‐co‐F6NSt)), which contained chemical crosslinkable segment (NMA) and hole trapping building block (F6NSt). The feeding molar ratios of two monomers (NMA:F6NSt) were set as 100:0, 95:5, 80:20, and 67:33 for the copolymers of P1 , P2 , P3, and P4 , respectively. The crosslinked P(NMA‐co‐F6NSt) thin film could serve as both dielectric and charge storage layers in organic field‐effect transistor (OFET) memory device and exhibited high k (i.e., 4.91–6.47) characteristics, leading to a low voltage operation and a small power consumption. Devices based on the P1 ‐ P4 dielectrics showed excellent insulating properties and good charge storage performance under a low operating voltage in a range of ±5V because of tightly network structures and well‐dispersed trapping cites. In particular, P3 ‐based memory device exhibited a large memory window of 4.13 V with stable data retention stability over 10⁴ s, a large on/off ratio of 10⁴, and good endurance characteristics as high as 200 cycles. The above results suggested that a high‐performance OFET memory device could be facilely achieved using the novel crosslinkable high‐k copolymers. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3224–3236     

Applicability of the Levich Equation for a Two-Phase Solution in the Rotating Disk Electrode System

The mass-transter characteristics of a two-phase system formed by mixing a fixed quantity (20 v/v%) of organic solvent with an aqueous ferricyanide electrolyte solution in an RDE system were studied. The Levich eqution, I₁ = 0.62 nFAC_bD^2/3v^?1/6_ω^1/2, was found to be applicable to the two-phase system with only a minor modification in the angular velocity (ω) at Reynolds numbers between 3–5 × 10⁴. The experimental results indicate that the interfacial tension is the most important variable for the two-phase system. One group of organic solvents with smaller interfacial tension, such as benzene or toluene, needs a modification of the Levich equation by replacing the observed angular velocity (ω_o) with the true angular velocity (ω_t) which was observed to be 1.1 times the observed angular velocity. For the other group with larger interfacial tension, such as n-hexane or cyclohexane, there is no need to modify the observed angular velocity. In other words, the Levich equation may be expressed as I₁ = 0.65 nFAC_bD^2/3v^?1/6ω^1/2 for two-phase solution if the interfacial tension is smaller than 37.0 dyne/cm.     

One‐Pot Synthesis of Highly Substituted Polyheteroaromatic Compounds by Rhodium(III)‐Catalyzed Multiple C?H Activation and Annulation

A new method for the synthesis of highly substituted naphthyridine‐based polyheteroaromatic compounds in high yields proceeds through rhodium(III)‐catalyzed multiple C H bond cleavage and C C and C N bond formation in a one‐pot process. Such highly substituted polyheteroaromatic compounds have attracted much attention because of their unique π‐conjugation, which make them suitable materials for organic semiconductors and luminescent materials. Furthermore, a possible mechanism, which involves multiple chelation‐assisted ortho C H activation, alkyne insertion, and reductive elimination, is proposed for this transformation.     

On-chip temperature gradient interaction chromatography

This paper reports the first integrated microelectromechanical system (MEMS) HPLC chip that consists of a parylene high-pressure LC column, an electrochemical sensor, a resistive heater and a thermal-isolation structure for on-chip temperature gradient interaction chromatography application. The separation column was 8 mm long, 100 microm wide, 25 microm high and was packed with 5 microm sized, C18-coated beads using conventional slurry-packing technique. A novel parylene-enhanced, air-gap thermal isolation technology was used to reduce heater power consumption by 58% and to reduce temperature rise in the off-column area by 67%. The fabricated chip consumed 400 mW when operated at 100 degrees C. To test the chromatography performance of the fabricated system, a mixture of derivatized amino acids was chosen for separation. A temporal temperature gradient scanning from 25 to 65 degrees C with a ramping rate of 3.6 degrees C/min was applied to the column during separation. Successful chromatographic separation of derivatized amino acids was carried out using our chip. Compared with conventional temperature gradient HPLC system which incorporates "macro oven" to generate temporal temperature gradient on the column, our chip's thermal performance, i.e., power consumption and thermal response, is greatly improved without sacrificing chromatography quality.     

Selective benzylic lithiation of N-Boc-2-phenylpiperidine and pyrrolidine: expedient synthesis of a 2,2-disubstituted piperidine NK1 antagonist

Unlike the lithiation of N-Boc-2-alkylpiperidines, which occurs at the 6-position, N-Boc-2-phenylpiperidine and N-Boc-2-phenylpyrrolidine can be lithiated exclusively at the 2-position. The tertiary carbanions can be trapped with a variety of electrophiles. This chemistry was used for the synthesis of a potent NK₁ ligand (K_i = 0.3 nM). The bioactive configuration at the piperidine quaternary center was determined by X-ray analysis to be (S).     

New benzo[b]furans as electroluminescent materials for emitting blue light

[structure: see text] New functionalized mono- and bis-benzo[b]furan derivatives were synthesized and developed as blue-light emitting materials. They possessed a CN, CHO, CH=CHPh, CH=CPh(2), or CH=CHCOOH group at the C4-position. Two benzo[b]furan nuclei in bis-benzo[b]furan derivatives were connected by a divinylbenzene bridge. With good volatility and thermal stability, bis-benzo[b]furan 7a was fabricated as a device. It emitted blue light with brightness 53430 cd/m(2) (at 15.5 V) and high maximum external quantum efficiency 3.75% (at 11 V).