Cell‐Selective,Apoptosis‐inducing Rhodium(III) Crown Thiaether Complexes

Half‐sandwich rhodium(III) polypyridyl (pp) complexes with the metal atom capped by the facial crown thiaether 1,4,7‐trithiacyclononane [9]aneS₃ represent a promising class of apoptosis‐inducing potent cytostatic agents. The necrotic damage caused by the complexes is negligible. In vitro cytotoxicity assays with the human cancer cell lines MCF‐7 and HT‐29 and immortalized HEK‐293 cells indicate that the dicationic κ²N(imino) complexes [([9]aneS₃)RhCl(pp)]²⁺ are much more active than monocationic complexes [([9]aneS₃)RhCl₂(L)]⁺ (L=imidazole, CH₃CN). Whereas the κ²N(amino) complex [([9]aneS₃)RhCl(piperazine)]²⁺ is inactive, replacing piperazine with the structurally analogous κ²S (thiaether) ligand 1,4‐dithiane restores cytotoxicity as evidenced by IC₅₀ values in the range 8.1‐11.6 μM . Spectroscopic (CD, UV/Vis, NOESY) and viscosity measurements indicate that the active dppz complex 8 (IC₅₀ values: 4.7–8.9 μM ) exhibits strong intercalative binding towards DNA whereas the even more potent bipyrimidine complex 9 (IC₅₀ values: 0.6–1.9 μM ) causes no alteration of the duplex B conformation. Weaker intercalative binding is observed for the dpq complex 7 . A comparative annexin V–propidium iodide binding assay with lymphoma (BJAB) cells and healthy leukocytes demonstrates that the cytotoxic activity of complex 8 and particularly complex 9 is highly selective towards the malignant cells.     

Effect of natural oils on the thermal stability and degradation kinetics of recycled polypropylene wood flour composites

Recycled polypropylene was reinforced with wood fibers that were non‐treated and treated with different natural oils (hexanoic, octanoic, decanoic and dodecanoic acids). The thermal properties, morphology, kinetics and thermodynamic parameters were investigated. The use of natural oils as coupling agents clearly improved the interfacial adhesion with the matrix and increased the thermal stability of the composites. Octanoic acid improved the thermal stability of the composite the most compared with the other evaluated natural oils. The improvement caused by this natural oil is similar to that promoted by the addition of PPgMA. The thermal stability of the composite was affected by the boiling temperature and the chain length of the acid used. POLYM. COMPOS., 35:1935–1942, 2014. © 2014 Society of Plastics Engineers     

Ammonium Perchlorate,Friend or Foe?

In part 1 of this paper, it was demonstrated that a nitroglycerine and polyethylene glycol based propellant containing ammonium perchlorate degraded at a slower rate at temperatures of 80 °C or less compared with the other two energetic materials studied which did not have this oxidizer present. It was suggested that ammonium perchlorate might act as an oxygen inhibitor reducing the oxidation rate of the polyethylene glycol binder which decreases the rate of propellant decomposition. In part 2, the specific interaction between ammonium perchlorate, nitroglycerine and polyethylene glycol is reported. It has been shown that at temperatures lower than 90 °C, if there is any uncured and unstabilised PEG present, nitroglycerine rapidly degrades in the presence of ammonium perchlorate but this is prevented if stabiliser is added. In addition, ammonium perchlorate initially appears to hinder acid hydrolysis of nitroglycerine which also slows down the degradation of polyethylene glycol based propellants. However, in the long term at low temperatures, or short term at higher temperatures, AP accelerates the decomposition of NG.     

Differential resistance feedback control of a self-sensing shape memory alloy actuated system

There is a growing trend towards miniaturization, and with it comes an increasing need for miniature sensors and actuators for control. Moreover situations occur wherein implementation of external physical sensor is impossible, here self-sensing lends its hand appropriately. Though self-sensing actuation (SSA) is extensively studied in piezoelectric, exploring this property in shape memory alloy is still under study. A simple scheme is developed which allows differential resistance measurement of antagonistic shape memory alloy actuated wires to concurrently sense and actuate in a closed loop system. The usefulness of the proposed scheme is experimentally verified by designing a one link manipulator arm and is performed in a real time tracking control. In a practical implementation of the self-sensing actuator a newly proposed signal processing electronic circuit is used for direct differential resistance feedback control upto a bandwidth of 1.8 Hz. The control design uses fuzzy PID which requires no detailed information about the constitutive model of SMA. At an operating frequency of 1 Hz, the result of the self-sensing feedback control with an angular tracking accuracy of ±0.06° over a movement range of ±15° is demonstrated.     

Hydrothermal degradation of adsorbed sulfur mustard on activated carbon

Thermal and hydrothermal degradations of adsorbed sulfur mustard (HD) on activated carbon particles from a chemical protective over-garment were studied. Carbon loaded with 5 wt.% HD was heated in a closed reactor at temperatures up to 160 °C for 0.5–6 h and analyzed by solid-state ¹³C MAS NMR. On dry carbon at room temperature, HD was stable for months. On a thoroughly pre-wetted carbon, adsorbed HD partially degraded to thiodiglycol (TDG) and TDG-sulfoxide (TDG-SO) within 2–3 months. Heating dry HD-loaded carbon to 160 °C caused partial degradation within 4 h to 1,4-thioxane, along with 1,4-dithiane and vinyl sulfides. Complete degradation within 2.5 h to the same products occurred upon hydrothermal treatment of the HD-loaded carbon, using a water/carbon ratio of 0.3:1. With higher water/carbon ratios of 0.6:1–5:1 at temperatures of 120 °C and above, adsorbed HD hydrolyzed rapidly within 0.5 h. The latter reaction led to the formation of TDG concurrent with either thioxane (at 160 °C) or TDG-SO and TDG-dimer (at 120 °C). The mechanisms of the observed degradation processes are discussed.     

Enhancement of the Performance of Low-Efficiency HVAC Filters Due to Continuous Unipolar Ion Emission

Our novel concept utilizing continuous emission of unipolar ions, which has been recently proven to enhance the efficiency of facepiece respirators, was applied to conventional HVAC filters. Laboratory study demonstrated that the air ion emission in the vicinity of a low-efficiency HVAC filter significantly improves its performance. For example, the collection efficiency of two commercial HVAC filters challenged with 1μm PSL particles jumped from 5–15% (measured with no ion emission) to 40–90% (when the ion output rate was ～ 10¹² e^?/sec). The enhancement effect depends on the filter type and, generally, on the distance from the ion emitter to the filter surface. The results were explained as follows. The air ions with high mobility are deposited on the fibers forming a macroscopic electric field, which shield out some incoming unipolarly charged particles due to repelling forces. The field estimate has shown that this explanation is feasible. The enhancement effect seems to have a good potential to be employed in industrial and residential ventilation systems as it enhances the aerosol collection efficiency of a low-efficiency HVAC filter while not affecting its pressure drop.     

Mechanism of hydrogen production in [Fe–Fe]-hydrogenases: A quantum mechanics/molecular mechanics study

[Fe–Fe]-hydrogenases are a class of metalloenzymes that catalyze the production of H₂ from two protons and two electrons. Crystal structures for [Fe–Fe]-hydrogenases found in two species – Clostridium pasteurianum (CpI) and Desulfovibrio desulfuricans (DdH) – show very similar active sites. However, the catalytic mechanism has not as yet been fully clarified. We employed density functional theory (DFT) within a QM/MM method to investigate proposed mechanisms of hydrogen production by DdH and CpI hydrogenases and their dependence on the protein environment of the active sites. For each mechanism investigated, we found only minor differences between the CpI and DdH hydrogenases in terms of the intermediate active site structures, although one mechanism follows a lower energy path for DdH hydrogenase, while the other mechanism follows a lower energy path for the CpI hydrogenase. We note, however, that the high activation energy we calculated for a step unique to one of the mechanisms might preclude it, making the energy-path comparison for the two mechanisms unnecessary.