Sterically-Hindered Molecular p-Dopants Promote Integer Charge Transfer in Organic Semiconductors

Molecular p-dopants designed to undergo electron transfer with organic semiconductors are typically planar molecules with high electron affinity. However, their planarity can promote the formation of ground-state charge transfer complexes with the semiconductor host and results in fractional instead of integer charge transfer, which is highly detrimental to doping efficiency. Here, we show this process can be readily overcome by targeted dopant design exploiting steric hindrance. To this end, we synthesize and characterize the remarkably stable p-dopant 2,2′,2′′-(cyclopropane-1,2,3-triylidene)tris(2-(perfluorophenyl)acetonitrile) comprising pendant functional groups that sterically shield its central core while retaining high electron affinity. Finally, we demonstrate it outperforms a planar dopant of identical electron affinity and increases the thin film conductivity by up to an order of magnitude. We believe exploiting steric hindrance represents a promising design strategy towards molecular dopants of enhanced doping efficiency.     

Amberlyst A21: A reusable solid catalyst for green synthesis of pyran annulated heterocycles at room temperature

Amberlyst A21, a neutral ion-exchange resin and a solid base, can catalyze the three-component reaction of aldehyde and malononitrile with various active methylene compounds at room temperature to synthesize a range of pharmaceutically important pyran annulated heterocycles. Use of the solid base could generate a highly green protocol by eliminating chromatographic purification that involves hazardous organic solvents, and facilitate easy recovery and reusability of the catalyst.     

A green four-component synthesis of zwitterionic alkyl/benzyl pyrazolyl barbiturates and their photophysical studies

A novel series of unsymmetrically substituted alkyl/benzyl pyrazolyl barbiturates incorporating highly biologically active pyrazolone and barbiturate moieties was synthesized by four-component reactions of a mixture of ethyl acetoacetate, hydrazine hydrate, aldehydes and barbituric acid/thiobarbituric acid in ethanol without using a catalyst. The photophysical properties of the newly designed alkyl/benzyl pyrazolyl barbiturates were studied, and good quantum yield of some products indicated a definitive scope in the field of biochemical applications. Single-crystal X-ray crystallographic studies revealed that the newly synthesized compounds exist in zwitterionic form. The zwitterionic nature of the new chimera makes them interesting candidates for drug delivery as zwitterionic drugs are known to have highly water soluble properties, specific protein absorption, slow recognition by immune system, slow blood clearance from body and can constantly diffuse and deposit throughout the physiological pH.     

Transition‐Metal‐Functionalized DNA Double‐Crossover Tiles: Enhanced Stability and Chirality Transfer to Metal Centers

The double crossover junction (DX) is a fundamental building block for generating complex and varied structures from DNA. However, its implementation in functional devices is limited to the inherent properties of DNA itself. Here, we developed design strategies to generate the first metal–DX DNA tiles (DX_M) by site‐specifically functionalizing the tile crossovers with tetrahedral binding pockets that coordinate Cu^I. These DX junctions bind two Cu^I ions independently at distinct sites, display greater thermal stability than native DX tiles upon metalation, and melt in a cooperative fashion. In addition, the right‐handed helical chirality of DNA is transferred to the metal centers. Our tiles display high metal ion selectivity, such that Cu^II is spontaneously reduced to Cu^I in situ. By modifying our design over three generations of tiles, we elucidated the thermodynamic and geometric requirements for the successful assembly of DX_M tiles, which have direct applicability in developing robust, stable DNA‐based materials with electroactive, photoactive, and catalytic properties.     

Iron Oxychloride/Bovine Serum Albumin Nanosheets as Chemodynamic Therapy Agents

Iron oxychloride (FeOCl) is known for reactive oxygen species (ROS) generation through Fenton chemistry. The activity of FeOCl is preserved in the slightly acidic pH value of the tumor microenvironment (pH 6.5−6.9). Such property can be advantageous in biobased systems, where ROS generation can be modulated in slightly acidic conditions, which is characteristic of the solid tumor microenvironment. In the present study, BSA-stabilized FeOCl nanosheets (NSs) are synthesized and characterized by transmission electron microscope, Fourier transform infrared spectroscopy, zeta potential analysis, dynamic light scattering, and UV–vis spectroscopy. The morphology of the nanoparticles is flake-like, and their hydrodynamic diameter is around 200 nm. MTT, apoptosis assay, and trypan blue staining evaluate the toxicity of FeOCl NSs toward the 4T1 cell line. It is found that the toxicity of the NSs is higher in physiological conditions of solid tumors (pH 6.5, H₂O₂ 100 × 10⁻⁶ m ) than in the conditions of healthy organs (pH 7.4). Specifically, cancer cells are in their late apoptotic stage by more than eight times higher at pH 6.5 than pH 7.4. The toxicity results are in agreement with the in vitro catalytic assay of the NSs. Therefore, the FeOCl NSs can be the building blocks for constructing chemodynamic therapy agents.     

Integrated photonic crystal spectrometers for sensing applications

A combination of negative refraction and diffraction compensation in a superprism-based photonic crystal structure is used to demonstrate a compact on-chip photonic crystal spectrometer. This structure provides strong dispersion and signal isolation, which are essential for forming an efficient and compact spectrometer. Performance of these spectrometers as spectral pattern detectors is discussed. The experimental results show that a PC structure with 80 μm × 220 μm dimension can locate a single spectral feature with better than 10 pm accuracy over a bandwidth of 50 nm around 1550 nm center wavelength at an output signal-to-noise ratio of 13 dB.     

A relationship between three analytical approaches to nonlinear problems

In this work, the relationship between three analytical techniques is demonstrated. The direct relationship between the variational approach (VA) and the Hamiltonian approach (HA) is illustrated for a first approximation, and subsequently the relationship between the variational approach and the harmonic balance method (HBM) is concluded. Moreover, the relationship between HA and VA is investigated for higher order solutions.     

Nonlinear Oscillations Analysis of the Elevator Cable in a Drum Drive Elevator System

This paper aims to investigate nonlinear oscillations of an elevator cable in a drum drive. The governing equation of motion of the objective system is developed by virtue of Lagrangian's method. A complicated term is broached in the governing equation of the motion of the system owing to existence of multiplication of a quadratic function of velocity with a sinusoidal function of displacement in the kinetic energy of the system. The obtained equation is an example of a well-known category of nonlinear oscillators, namely, non-natural systems. Due to the complex terms in the governing equation, perturbation methods cannot directly extract any closed form expressions for the natural frequency. Unavoidably, different non-perturbative approaches are employed to solve the problem and to elicit a closed-form expression for the natural frequency. Energy balance method, modified energy balance method and variational approach are utilized for frequency analyzing of the system. Frequency-amplitude relationships are analytically obtained for nonlinear vibration of the elevator's drum. In order to examine accuracy of the obtained results, exact solutions are numerically obtained and then compared with those obtained from approximate closed-form solutions for several cases. In a parametric study for different nonlinear parameters, variation of the natural frequencies against the initial amplitude is investigated. Accuracy of the three different approaches is then discussed for both small and large amplitudes of the oscillations.     

An output-feedback adaptive actuator failure compensation controller for systems with unknown state delays

This paper presents an output-feedback adaptive controller for a class of linear systems with unknown time-varying state delay and in the presence of actuator failures. We consider a common type of actuator failure in which some unknown system inputs may be stuck at some unknown fixed values and at unknown time instants. The adaptive controller is designed based on SPR–Lyapunov approach for relative degree one and two cases. Closed-loop system stability and asymptotic output tracking are proved using suitable Lyapunov–Krasovskii functional for each case. Simulation results are provided to demonstrate the effectiveness of the proposed results.