The use of MM/QM calculations of 13C and 15N chemical shifts in the conformational analysis of alkyl substituted anilines

The calculation of the ¹³C and ¹⁵N NMR chemical shifts by a combined molecular mechanics (Pcmodel 9.1/MMFF94) and ab initio (GIAO (B3LYP/DFT, 6-31 + G(d)) procedure is used to investigate the conformations of a variety of alkyl substituted anilines. The ¹³C shifts are obtained from the GIAO isotropic shielding (Ciso) with separate references for sp³ and sp² carbons (δc = δref − Ciso). The ¹⁵N shifts are obtained similarly from the GIAO isotropic shielding (Niso) with reference to the ¹⁵N chemical shift of aniline. Comparison of the observed and calculated shifts provides information on the molecular conformations. Aniline and the 2,6-dialkylanilines exist with a rapidly inverting symmetric pyramidal nitrogen atom. The 2-alkylanilines have similar conformations with the NH₂ group tilted away from the 2-alkyl substituent. The N,N-dialkylanilines show more varied conformations. N,N-dimethylaniline has a similar structure to aniline, but N-ethyl, N-methylaniline, N,N-diethylaniline, and N,N-diisopropylaniline are conformationally mobile with two rapidly interconverting conformers. In contrast, the anilines substituted at C₂ and the nitrogen atom exist as one conformer where the steric interaction between the C₂ substituent and the N substituent determines the conformation. In 2-methyl-N-methylaniline, the nitrogen atom is pyramidal as usual with the N-methyl opposite to the 2-methyl, but in 2-methyl-N,N-dimethyl aniline, the NMe₂ group is now almost orthogonal to the phenyl plane. This is also the case with 2-methyl-N,N-diethylaniline and 2,6-diisopropyl-N,N-dimethylaniline. The comparison of the observed and calculated ¹⁵N chemical shifts confirms the above findings, in particular the pyramidal conformation of aniline and the above observations with respect to the conformations of the N,N-dialkylanilines.     

The effects of ring substituents in aniline on the reactivity of PANI with hydrogen tetrachloroaurate and the dispersion of gold nanoparticles

As expected from theoretical predictions, the polymerization of aniline was affected by the substituent group on the benzene ring. The rate of the polymerization varied as poly(2‐chloroaniline) (PANICl) < < poly(2‐methylaniline) (PANIMe) < polyaniline (PANI). While the rate of polymerization was determined largely by electronic effects of the substituent groups, the reactivity of the polymers was determined by the steric effects. The order of the rate of reaction of the polymers with AuCl₄⁻ was PANIMe < PANICl < < PANI. The amount of Au incorporated into the polymer matrix followed a similar trend. However, the size of the gold nanoparticles did not differ greatly. Gold nanoparticles dispersed on PANICl and PANIMe were more stable in acidic media than those on PANI. Copyright © 2015 John Wiley & Sons, Ltd.     

Room‐temperature Suzuki–Miyaura cross‐coupling reaction with α‐diimine Pd(II) catalysts

An α‐diimine Pd(II) complex containing chiral sec‐phenethyl groups, {bis[N,N′‐(4‐methyl‐2‐sec‐phenethylphenyl)imino]‐2,3‐butadiene}dichloropalladium (rac‐ C1 ), was synthesized and characterized. rac‐ C1 was applied as an efficient catalyst for the Suzuki–Miyaura cross‐coupling reaction between various aniline halides and arylboronic acid in PEG‐400–H₂O at room temperature. Among a series of aniline halides, rac‐ C1 did not catalyze the cross‐coupling of aniline chlorides and fluorides but efficiently catalyzed the cross‐coupling of aniline bromides and iodides with phenylboronic acid. The catalytic activity reduced slightly with increasing steric hindrance of the aniline bromides. The complexes {bis[N,N′‐(4‐fluoro‐2,6‐diphenylphenyl)imino]‐2,3‐butadiene}dichloropalladium and {bis[N,N′‐(4‐fluoro‐2,6‐diphenylphenyl)imino]acenaphthene}dichloropalladium were also found to be efficient catalysts for the reaction. Copyright © 2015 John Wiley & Sons, Ltd.     

Isomeric Effects on Structures and Properties of Polyaminophenols Synthesized in Basic Medium

The oxidative chemical polymerizations of three isomers of aminophenol, ortho, meta, and para (PoAP, PmAP, PpAP) were performed in aqueous NaOH using ammonium persulfate (APS) as oxidant. Solubility tests for the synthesized polymers were performed in various solvents and it was found that all three polymers are soluble in DMSO and DMF. PpAP is soluble in aqueous strong acid, as well as in base, but PoAP is soluble in acid, whereas PmAP is soluble in base. The difference in their solubility is due to their structural difference, which can be supported by the proposed mechanisms of polymerizations. The film casting from the DMF or DMSO solution of PoAP and PpAP is difficult due to the presence of quinone impurity while casting of PmAP film from DMSO solution is possible. The intrinsic viscosities of the polymers were determined from the DMSO solution. The polymers were characterized by UV-VIS, FTIR and¹H-NMR spectroscopy and elemental analyses. From structural analysis, it is found that PoAP and PpAP do not contain π -electron conjugation due to ether linkage in the backbone chain. So, PoAP and PpAP do not show any conductivity like sulfuric acid doped PmAP.     

超高压液相色谱荧光检测法快速测定水中痕量苯胺与联苯胺

建立了直接进样/超高压液相色谱荧光检测法快速分析水中苯胺和联苯胺的新方法。通过研究流动相、水样pH值、水样电导率和滤器材质的影响,确定了最优化的实验方案。水样直接通过0.22μm微孔滤膜(聚四氟乙烯材质)过滤,以乙腈-3.85 g/L醋酸铵(25∶75)为流动相,荧光检测器(苯胺λex/λem=232nm/329 nm,联苯胺λex/λem=292 nm/383 nm)在0.8 min内完成分析。苯胺和联苯胺在1.0～100.0μg/L范围内线性关系良好,相关系数均大于0.999,仪器精密度(n=10)分别为0.4%和0.5%,方法检出限(S/N=3)分别为0.023μg/L和0.024μg/L,方法定量下限(S/N=10)为0.078μg/L和0.079μg/L,方法回收率为86%～106%。该方法具有前处理简单、方法检出限低、分析速度快等优点,适用于水体中苯胺和联苯胺的快速检测。     

Nano‐hydroxyapatite Surfaces Grafted with Electroactive Aniline Tetramers for Bone‐Tissue Engineering

An electroactive amino/carboxyl‐capped aniline tetramer (AT) is covalently grafted to the surface of hydroxyapatite (HA) nanoparticles to generate novel electroactive HA‐AT nanoparticles. The amount of AT ranges from 16.5 to 34.0 wt% and is characterized by thermogravimetric analysis (TGA). The HA‐AT nanoparticles are characterized by Fourier transform IR (FTIR) spectroscopy, X‐ray photoelectron spectroscopy (XPS), X‐ray diffraction, and scanning electron microscopy (SEM). For the excellent electroactivity of HA‐AT, the mixture of HA‐AT and PLA shows much better adhesion ability and proliferation ability than that of HA and a PLA matrix. At a 15 wt% AT grafting amount, the matrix shows the best biocompatibility.

     

The Sensitized Solid‐Phase Electrochemiluminescence of Electrodeposited Poly‐Luminol/Aniline on AuAg/TiO2 Nanohybrid Functionalized Electrode for Flow Injection Analysis

In this study, a copolymer of luminol with aniline is electrochemically deposited onto the AuAg/TiO₂ nanohybrid functionalized indium tin oxide coated glass. It is used as a reagentless electrochemiluminescent (ECL) electrode for flow‐injection‐analysis (FIA). The properties of this solid phase ECL electrode are characterized by cyclic voltammetry, electrochemical impedance spectroscopy and scanning electron microscopy etc. It has stronger ECL emission, sensitive response for target analytes and excellent stability. The so‐prepared ECL electrode shows sensitive response to reactive oxygen species thereafter to be applied for determination of hydrogen peroxide with FIA mode. Under optimized conditions, a mass detection limit of 0.822 pg of hydrogen peroxide was obtained. Thus the hydrogen peroxide residues in samples were detected with satisfactory result.     

Optical and Electrochemical Combination Sensor with Poly‐Aniline Film Modified Gold Surface and Its Application for Dissolved Oxygen Detection

Poly‐aniline (PAn) film can be oxidized by contacting oxygen in an electron‐transfer reaction and its redox state, for instance the open circuit potential and the dielectric constant, is quantitatively related to oxygen concentration. This feature may contribute to an improved application of dissolved oxygen (DO) detection with the combined optical and electrochemical sensor. In this paper, PAn is used as a sensing surface to detect DO by the combination sensor composed of electrochemistry and total internal reflection imaging ellipsometry (EC‐TIRIE). Results demonstrate that both optical and electrical signals show a logarithmic correlation with DO concentration (0–20 ppm). Compared with the results obtained only with the gold surface, both the optical and electrical signals of the EC‐TIRIE sensor for DO detection are amplified with the PAn modified gold surface.     

Nitration of Ethyl Carbamates of Phenylenediamines and Aniline

The methyl and ethyl carbamates of aniline and the diethyl dicarbamates of 1,2‐, 1,3‐, and 1,4‐phenylenediamine were prepared. Nitration of the carbamates gave ring mono‐, di‐, or trinitro‐derivatives in good yield.     

In situ measurements of oligoaniline conductance: Linking electrochemistry and molecular electronics

The single-molecule conductance of a dithiolated aniline trimer has been measured under potential control and also under an inert solvent. In each experiment, two sets of currents are found, differing by a factor 4, and these are tentatively assigned to differing connections to the electrodes (e.g., on-top vs. hollow sites). The conductances peak (to 17 ± 1.6 and 5.8 ± 0.85 nS) between the first and second oxidations of the molecule and change smoothly with surface potential. There is no evidence for a coexistence of oxidized and reduced molecules. Measurements made at a fixed surface potential as a function of tip to substrate bias show a peak current at 0.1 V followed by a region of negative differential resistance. This is accounted for semi-quantitatively by modification of the local potential by the applied bias altering the oxidation state of the molecule under the probe. Measurements made in toluene are Ohmic, indicating that the tip does not alter the oxidation state of the molecule in the absence of screening ions. We discuss the role of gap geometry and bonding in these processes.