Rearrangement during cyclisation of some 3-(2-pyrrolyl) propionic acids and related compounds

Cyclisation of the title compounds leads to mixtures of the expected 4H-cyclopental[b]pyrrol-4-ones (1), the corresponding 6-ones (3) by a single rearrangement, and the cyclopenta[c]pyrrol-4-ones (4) by a double rearrangement, the proportions depending upon the substituents.The ¹H NMR spectra of 2-methyl-4H-cyctopenta[b]thiophen-6-one (3f) shows 6J long range $\text{CH}{}_3\text{CH}{}_2$ coupling, but this is absent in the corresponding pyrroles (3c,d). The ¹³C spectra of 1 and 3 cannot be interpreted on the basis of substituent chemical shifts in pyrroles and thiophens, and are clearly -CH = CH-X (X = NMe, NPh, S) bridged derivatives of cyclopent-2-enone.     

Calculation of harmonic force constants,vibrational frequencies and integrated intensities of some organic molecules using the MINDO—Forces method

The harmonic force constants, vibrational frequencies and integrated intensity ratios of CH₂, H₂O, CH₂O, C₂H₂, CO₂, HCN, CH₃, CH₄, and C₂H₄ have been calculated using the MINDO—FORCES program and the Pulay method for the calculation of the molecular force constants. The results obtained are in general quite satisfactory when compared with available literature values. The results are, however, not as satisfactory in case of molecules containing heteroatoms, due to the neglect of some dipolar repulsion integrals for the heteroatoms by the MINDO/3 method. Calculated integrated intensities for CH₃ and C₂H₄ agree well with experimental results. The calculated integrated intensities for other molecules are obtained for the first time and no comparison with published data is therefore possible.Part of the M.Sc. Thesis of K. H. A. 1978.     

有机分子与聚电解质静电吸附成膜特性研究

选取多种有机分子及聚电解质，采用静电吸附自组装法制备了聚电解质，聚电解质、聚电解质，有机分子、有机分子，有机分子的复合薄膜，讨论了这些体系的静电吸附成膜特性及其成膜机理．     

1,3,3—三甲基—2—[β—（5—取代苯基—2—呋喃基）乙烯基]—3H—吲哚盐的合成

1,3,3- 三甲基-2-[β-(4-取代苯基)乙烯基]-3H-吲哚盐是熟知的聚甲川型染料,常由费歇尔碱与芳香醛制备,也可由该碱的季铵盐一步合成。但这些方法往往需要使用较昂贵的溶剂,有的尚未分出染料纯品.近年来这类染料获得许多新的用途,如作光敏电照相记录材料和电照相增感剂等.本文考察了碘化1,2,3,3-四甲基-3H-吲哚(Ⅰ)与5-取     

Synthetic protocols and building blocks for molecular electronics

Simple and readily accessible aryl bromides are useful building blocks for thiol end-capped molecular wires. Thus, 4-bromophenyl tert-butyl sulfide and 1-bromo-4-(methoxymethyl)benzene serve as precursors for a variety of oligo(phenylenevinylene) and oligo(phenyleneethynylene) wires via efficient synthetic transformations as presented in this paper.     

Skin-like Omnidirectional Stretchable Platform with Negative Poisson's Ratio for Wearable Strain–Pressure Simultaneous Sensor

Conventional elastomeric polymers used as substrates for wearable platforms have large positive Poisson's ratios (≈0.5) that cause a deformation mismatch with human skin that is multidirectionally elongated under bending of joints. This causes practical problems in elastomer-based wearable devices, such as delamination and detachment, leading to poorly reliable functionality. To overcome this issue, auxetic-structured mechanical reinforcement with glass fibers is applied to the elastomeric film, resulting in a negative Poisson's ratio (NPR), which is a skin-like stretchable substrate (SLSS). Several parameters for determining the materials and geometrical dimensions of the auxetic-structured reinforcing fillers are considered to maximize the NPR. Based on numerical simulation and digital image correlation analysis, the deformation tendencies and strain distribution of the SLSS are investigated and compared with those of the pristine elastomeric substrate. Owing to the strain-localization characteristics, an independent strain-pressure sensing system is fabricated using SLSS with a Ag-based elastomeric ink and a carbon nanotube-based force-sensitive resistor. Finally, it is demonstrated that the SLSS-based sensor platform can be applied as a wearable device to monitor the physical burden on the wrist in real time.     

Flexible Transparent Bifunctional Capacitive Sensors with Superior Areal Capacitance and Sensing Capability based on PEDOT:PSS/MXene/Ag Grid Hybrid Electrodes

Flexible transparent supercapacitors (FTSs) have aroused considerable attention. Nonetheless, balancing energy storage capability and transparency remains challenging. Herein, a new type of FTSs with both excellent energy storage and superior transparency is developed based on PEDOT:PSS/MXene/Ag grid ternary hybrid electrodes. The hybrid electrodes can synergistically utilize the high optoelectronic properties of Ag grids, the excellent capacitive performance of MXenes, and the superior chemical stability of PEDOT:PSS, thus, simultaneously demonstrating excellent optoelectronic properties (T: ≈89%, R_s: ≈39 Ω sq⁻¹), high areal specific capacitance, superior mechanical softness, and excellent anti-oxidation capability. Due to the excellent comprehensive performances of the hybrid electrodes, the resulting FTSs exhibit both high optical transparency (≈71% and ≈60%) and large areal specific capacitance (≈3.7 and ≈12 mF cm⁻²) besides superior energy storage capacity (P: 200.93, E: 0.24 µWh cm⁻²). Notably, the FTSs show not only excellent energy storage but also exceptional sensing capability, viable for human activity recognition. This is the first time to achieve FTSs that combine high transparency, excellent energy storage and good sensing all-in-one, which make them stand out from conventional flexible supercapacitors and promising for next-generation smart flexible energy storage devices.     

A Dual-Mode Electrochromic Platform Integrating Zinc Anode-Based and Rocking-Chair Electrochromic Devices

The complementary electrochromic device, where the optical transmittance changes upon the flow of cations back and forth between anodic and cathodic electrodes, operates in a rocking-chair fashion if it can inherently self-discharge. Herein, the first demonstration of a dual-mode electrochromic platform having self-coloring and self-bleaching characteristics is reported, which is realized by sandwiching zinc metal within a newly-designed Prussian blue (PB)-WO₃ rocking-chair type electrochromic device. It is demonstrated that the redox potential differences between the zinc metal and the WO₃/PB electrodes endow the self-color-switching of these electrodes. By employing a hybrid electrolyte of Zn²⁺/K⁺, it is further shown that the colored PB-WO₃ rocking-chair device is capable of spontaneously bleaching when the anodic and cathodic electrodes are coupled. This dual-mode light-control strategy enables the electrochromic devices to exhibit four distinct optical states with the highest optical contrast of 72.6% and fast switching times (<5 s for the bleaching/coloration processes). Furthermore, the built-in voltage of the dual-mode electrochromic devices not only promotes energy efficiency, but also augments the bistability of the devices. It is envisioned that the broad implication of the present platform is in the development of self-powered smart windows, colorful displays, optoelectronic switches, and optical sensors.     

Piezoelectric Sensors Operating at Very High Temperatures and in Extreme Environments Made of Flexible Ultrawide-Bandgap Single-Crystalline AlN Thin Films

Extreme environments are often faced in energy, transportation, aerospace, and defense applications and pose a technical challenge in sensing. Piezoelectric sensor based on single-crystalline AlN transducers is developed to address this challenge. The pressure sensor shows high sensitivities of 0.4–0.5 mV per psi up to 900 °C and output voltages from 73.3 to 143.2 mV for input gas pressure range of 50 to 200 psi at 800 °C. The sensitivity and output voltage also exhibit the dependence on temperature due to two origins. A decrease in elastic modulus (Young's modulus) of the diaphragm slightly enhances the sensitivity and the generation of free carriers degrades the voltage output beyond 800 °C, which also matches with theoretical estimation. The performance characteristics of the sensor are also compared with polycrystalline AlN and single-crystalline GaN thin films to investigate the importance of single crystallinity on the piezoelectric effect and bandgap energy-related free carrier generation in piezoelectric devices for high-temperature operation. The operation of the sensor at 900 °C is amongst the highest for pressure sensors and the inherent properties of AlN including chemical and thermal stability and radiation resistance indicate this approach offers a new solution for sensing in extreme environments.     

3D Printable One-Part Carbon Nanotube-Elastomer Ink for Health Monitoring Applications

3D printing of conductive elastomers is a promising route to personalized health monitoring applications due to its flexibility and biocompatibility. Here, a one-part, highly conductive, flexible, stretchable, 3D printable carbon nanotube (CNT)-silicone composite is developed and thoroughly characterized. The one-part nature of the inks: i) enables printing without prior mixing and cures under ambient conditions; ii) allows direct dispensing at ≈100 µm resolution printability on nonpolar and polar substrates; iii) forms both self-supporting and high-aspect-ratio structures, key aspects in additive biomanufacturing that eliminate the need for sacrificial layers; and iv) lends efficient, reproducible, and highly sensitive responses to various tensile and compressive stimuli. The high electrical and thermal conductivity of the CNT-silicone composite is further extended to facilitate use as a flexible and stretchable heating element, with applications in body temperature regulation, water distillation, and dual temperature sensing and Joule heating. Overall, the facile fabrication of this composite points to excellent synergy with direct ink writing and can be used to prepare patient-specific wearable electronics for motion detection and cardiac and respiratory monitoring devices and toward advanced personal health tracking and bionic skin applications.