Detection of sulfur mustard simulant by trisaryl phosphoric triamide-based resin using a quartz crystal microbalance sensor.

Chemical warfare agents (CWAs) pose a persistent threat to human safety, and bis(2-chloroethyl) sulfide, or sulfur mustard (SM) is one of the most dangerous substances and is able to cause serious harm. Detecting SM gas is vital, but current methods have high-temperature requirements and limited selectivity, mainly because of the lack of CWA receptor development, and this makes them challenging to use. To address this issue, we present a trisaryl phosphoric triamide-based resin receptor that preferentially interacts with a SM simulant 2-chloroethyl ethyl sulfide (2-CEES) through dipole interactions.

Supramolecular Phthalimide Networks Via Tandem Diels-Alder Reaction-Aromatization Using Biomass-Derived Furanic Dienes.

The design and synthesis of phthalimide derivatives are important goals for applications in fields such as pharmaceutical science and optoelectronics. In the present study, a facile and convenient synthetic pathway (no heat or acid/catalyst needed) is devised to produce phthalimides from a biomass-derived furan by directly introducing an N-carbamate group at the C-2 position of the furan ring via thermal Curtius rearrangement. The electron-donating N-carbamate group increases the energy level of the highest occupied molecular orbital of the furan diene, resulting in a significant increase of the rate of the Diels-Alder reaction with maleimide compared to the conventional furfuryl furan.

Aqueous lubrication and wear properties of nonionic bottle-brush polymers.

The usage of aqueous lubricants in eco-friendly bio-medical friction systems has attracted significant attention. Several bottle-brush polymers with generally ionic functional groups have been developed based on the structure of biological lubricant lubricin. However, hydrophilic nonionic brush polymers have attracted less attention, especially in terms of wear properties.

-Triflyl Phosphoric Triamide: A High-Performance Purely Organic Trifurcate Quartz Crystal Microbalance Sensor for Chemical Warfare Agent.

G-, V-, and A-series nerve agents are extremely toxic organophosphorus chemical warfare agents (CWAs) that incorporate P═O functional groups. Their colorless, tasteless, and odorless nature makes rapid and efficient detection challenging. Here, we report an unprecedented N-triflyl phosphoric triamide () receptor, which is a new class of triple hydrogen bonding donor molecular sensors for CWA recognition via noncovalent host-guest-type interactions.

Self-Healable and Recyclable Biomass-Derived Polyurethane Networks through Carbon Dioxide Immobilization.

Due to growing environmental issues, research on carbon dioxide (CO) use is widely conducted and efforts are being made to produce useful materials from biomass-derived resources. However, polymer materials developed by a combined strategy (i.e.

High-Temperature Skin Softening Materials Overcoming the Trade-Off between Thermal Conductivity and Thermal Contact Resistance.

The trade-off between thermal conductivity (κ) and thermal contact resistance (R ) is regarded as a hurdle to develop superior interface materials for thermal management. Here a high-temperature skin softening material to overcome the trade-off relationship, realizing a record-high total thermal conductance (254.92 mW mm K ) for isotropic pad-type interface materials is introduced.

Microcrystal Electron Diffraction Elucidates Water-Specific Polymorphism-Induced Emission Enhancement of Bis-arylacylhydrazone.

Aggregation-induced emission (AIE) phenomena have gained intense interest over the last decades because of its importance in solid-state emission. However, the elucidation of a working mechanism is difficult owing to the limited characterization methods on solid-state molecules, further complicated if dynamic structural changes occur. Here, a series of bis-arylacylhydrazones () were synthesized, for which their AIE properties are only turned on by the reversible adsorption of water molecules.

Additive-free photo-mediated oxidative cyclization of pyridinium acylhydrazones to 1,3,4-oxadiazoles: solid-state conversion in a microporous organic polymer and supramolecular energy-level engineering.

We discovered the efficient catalyst-free, photo-mediated oxidative cyclization reaction of bis--pyridinium benzoyl hydrazone (BH1) to 2-pyridinium-5-phenyl-1,3,4-oxadiazoles. This photoreaction is remarkable because it does not require additives (, bases, strong oxidants, or photocatalysts), which are essential in previous reports, and proceeds very effectively even with solid-state microporous organic polymers. Interestingly, we found that the inclusion complexation of BH1 with cucurbit[7]uril (CB7) interferes with the photo-induced electron transfer from BH1 to molecular oxygen through modification of the LUMO energy level, thus inhibiting the photo-medicated oxidative cyclization.

Four-Channel Monitoring System with Surface Acoustic Wave Sensors for Detection of Chemical Warfare Agents.

Recently, efforts have been made to adapt surface acoustic waves (SAWs) for use in chemical sensors for detection of chemical warfare agents (CWAs). In this study, a four-channel real-time CWA detection system was constructed using four 250-MHz SAW sensors. Each system consists of three different chemical sensors and one reference sensor.

Improved Performance of Surface Acoustic Wave Sensors by Plasma Treatments for Chemical Warfare Agents Monitoring.

The effects of a plasma treatment on the sensing performance of surface acoustic wave (SAW) sensors to detect chemical warfare agents (CWAs) were investigated. SAW sensors designed for an operating frequency of 250 MHz were fabricated using lift-off techniques followed by the deposition of a very thin thiourea (TU) layer as a sensing film on the sensing area of the SAW sensor. To achieve some advantages from the plasma treatment on the surface, such as cleaning, surface activation and modification, a post-plasma treatment was performed on the sensing layer and the sensing performance of the SAW sensor was measured by a comparison with the measured responses, providing different simulant gases through the gas feeding system.

Solid-State Emissive Metallo-Supramolecular Assemblies of Quinoline-Based Acyl Hydrazone.

Development of fluorescence-based sensory materials for metal elements is currently in the mainstream of research due to the simplicity and usability of fluorescence as a method of detection. Herein, we report a novel ""-quinoline-based acyl hydrazone-named bQH that could be synthesized by a facile, low-cost method through simple condensation of hydrazide with an aldehyde. This acyl hydrazone showed emissive properties through Zn selective binding, especially in its solid-state, as shown by experiments such as UV-Vis, photoluminescence (PL), nuclear magnetic resonance (NMR), and inductively-coupled plasma-optical emission spectroscopies (ICP-OES), and energy-dispersive X-ray spectroscopy (EDS) mapping.

Hyper-Cross-Linked Polymer on the Hollow Conjugated Microporous Polymer Platform: A Heterogeneous Catalytic System for Poly(caprolactone) Synthesis.

This work shows that the shape-controlled microporous organic polymer (MOP) can be utilized for the morphological engineering of another class of MOP materials. The morphology of a hyper-cross-linked polymer (HCP) was successfully engineered on the hollow conjugated microporous polymer (CMP). Through the postsynthetic modification of HCP bearing BINOLs (HCP-B) on the hollow CMP-like material (H-CMPL), the HCP bearing BINOL phosphoric acid (HCP-BP) was engineered on the H-CMPL platform.

Reversible Assembly of Terpyridine Incorporated Norbornene-Based Polymer via a Ring-Opening Metathesis Polymerization and Its Self-Healing Property.

We induced a terpyridine moiety into a norbornene-based polymer to demonstrate its self-healing property, without an external stimulus, such as light, heat, or healing agent, using metal⁻ligand interactions. We synthesized terpyridine incorporated norbornene-based polymers using a ring-opening metathesis polymerization. The sol state of diluted polymer solutions was converted into supramolecular assembled gels, through the addition of transition metal ions (Ni, Co, Fe, and Zn).

Binding thiourea derivatives with dimethyl methylphosphonate for sensing nerve agents.

In an effort to develop efficient substrates to sense organophosphonate nerve agents, we used the density-functional theory calculations to determine binding energies and geometries of 1 : 1 complexes formed between dimethyl methylphosphonate (DMMP) and 13 thiourea derivatives (TUn), including four newly-synthesized ones (n = 10-13). The four new thiourea derivatives have a 3,5-bis-(trifluoromethyl)phenyl group as one -substituent and an alkylphenyl group with zero to three methylene linkages as the other -substituent. The calculated geometries show that intermolecular double H-bonding is the most important factor influencing the formation of stable complexes at the molecular level.

Copper-Catalyzed Aza-Michael Addition of 2-Aminobenzoate to β-Substituted α,β-Unsaturated Ketones: One-Pot Synthesis of 3-Carbonyl-2-Substituted Quinolin-4(1H)-ones.

We present a new and straightforward one-pot process for the synthesis of 3-carbonyl-4-quinolone derivatives through highly efficient Cu-catalyzed aza-Michael addition of 2-aminobenzoates to β-substituted α,β-unsaturated ketones/cyclization/mild oxidation reactions. A broad range of new versatile 3-carbonyl-quinolin-4(1H)-ones is prepared from readily available chemicals under mild reaction conditions with short reaction times, producing good to excellent yields (up to 99%).

Three-Dimensional Electroconductive Hyaluronic Acid Hydrogels Incorporated with Carbon Nanotubes and Polypyrrole by Catechol-Mediated Dispersion Enhance Neurogenesis of Human Neural Stem Cells.

Electrically conductive hyaluronic acid (HA) hydrogels incorporated with single-walled carbon nanotubes (CNTs) and/or polypyrrole (PPy) were developed to promote differentiation of human neural stem/progenitor cells (hNSPCs). The CNT and PPy nanocomposites, which do not easily disperse in aqueous phases, dispersed well and were efficiently incorporated into catechol-functionalized HA (HA-CA) hydrogels by the oxidative catechol chemistry used for hydrogel cross-linking. The prepared electroconductive HA hydrogels provided dynamic, electrically conductive three-dimensional (3D) extracellular matrix environments that were biocompatible with hNSPCs.

Tuning Sensory Properties of Triazole-Conjugated Spiropyrans: Metal-Ion Selectivity and Paper-Based Colorimetric Detection of Cyanide.

Tuning the sensing properties of spiropyrans (SPs), which are one of the photochromic molecules useful for colorimetric sensing, is important for efficient analysis, but their synthetic modification is not always simple. Herein, we introduce an alkyne-functionalized SP, the modification of which would be easily achieved via Cu-catalyzed azide-alkyne cycloaddition ("click reaction"). The alkyne-SP was conjugated with a bis(triethylene glycol)-benzyl group (EG-BtSP) or a simple benzyl group (BtSP), forming a triazole linkage from the click reaction.

Structural Effect of Thioureas on the Detection of Chemical Warfare Agent Simulants.

The ability to rapidly detect, identify, and monitor chemical warfare agents (CWAs) is imperative for both military and civilian defense. Since most CWAs and their simulants have an organophosphonate group, which is a hydrogen (H)-bond acceptor, many H-bond donors have been developed to effectively bind to the organophosphonate group. Although thioureas have been actively studied as an organocatalyst, they are relatively less investigated in CWA detection.

Chemically Driven, Water-Soluble Composites of Carbon Nanotubes and Silver Nanoparticles as Stretchable Conductors.

In the past decade, hybrid materials for highly stretchable, conductive electrodes have received tremendous attention in the fields of emerging wearable electronic, optoelectronic, and sensing devices. Here, we present a previously unrecognized aqueous route to producing stretchable conductors composed of silver nanoparticles (AgNPs) and single-walled carbon nanotubes (SWNTs) embedded in a polyurethane (PU) matrix, in contrast to ones dispersed in toxic organic solvents reported to date. The intact chemical interaction between one-dimensional SWNTs, for endowing the capability of establishing conductive pathways even in stretching conditions, and AgNPs, for enabling high conductivity of the composites, is achieved in an aqueous medium with an anionic polyelectrolyte, poly(acrylic acid), that undergoes pH-dependent conformational evolution.

Growth kinetics of plasma-polymerized films.

The growth kinetics of polymer thin films prepared by plasma-based deposition method were explored using atomic force microscopy. The growth behavior of the first layer of the polythiophene somewhat differs from that of the other layers because the first layer is directly deposited on the substrate, whereas the other layers are deposited on the polymer itself. After the deposition of the first layer, each layer is formed with a cycle of 15 s.

Antiproliferative and Apoptosis-Inducing Activities of 4-Isopropyl-2,6-bis(1-phenylethyl)phenol Isolated from Butanol Fraction of Cordyceps bassiana.

The Cordyceps species have been widely used for treating various cancer diseases. Although the Cordyceps species have been widely known as an alternative anticancer remedy, which compounds are responsible for their anticancer activity is not fully understood. In this study, therefore, we examined the anticancer activity of 5 isolated compounds derived from the butanol fraction (Cb-BF) of Cordyceps bassiana.

Long dsRNA-mediated RNA interference and immunostimulation: a targeted delivery approach using polyethyleneimine based nano-carriers.

RNA oligonucleotides capable of inducing controlled immunostimulation combined with specific oncogene silencing via an RNA interference (RNAi) mechanism provide synergistic inhibition of cancer cell growth. With this concept, we previously designed a potent immunostimulatory long double stranded RNA, referred to as liRNA, capable of executing RNAi mediated specific target gene silencing. In this study, we developed a highly effective liRNA based targeted delivery system to apply in the treatment of glioblastoma multiforme.