Synthesis of caeliferins, elicitors of plant immune responses: accessing lipophilic natural products via cross metathesis

A cross metathesis (CM)-based synthesis of the caeliferins, a family of sulfooxy fatty acids that elicit plant immune responses, is reported. Unexpectedly, detailed NMR spectroscopic and mass spectrometric analyses of CM reaction mixtures revealed extensive isomerization and homologation of starting materials and products. It is shown that the degree of isomerization and homologation in CM strongly correlates with substrate chain length and lipophilicity. Side-product suppression requires appropriate catalyst selection and use of 1,4-benzoquinone as a hydride scavenger.     

Dielectric electrorheological fluids: Theory and experiment

Electrorheological (ER) fluids are a class of materials whose rheological properties are controllable by the application of an electric field. A dielectric electrorheological (DER) fluid is the simplest type of ER fluid, in which the material components follow a linear electrostatic response. We review and discuss the progress of the studies on physics of this type of material. A first-principles theory of DER fluids, along with relevant experimental verifications, are presented in some detail. In particular, the properties presented include static equilibrium structure, shear modulus, static yield stress and its variation with applied electric field frequency, and structure-induced dielectric nonlinearity.     

Effects of fingerprint development reagents on subsequent DNA analysis

A variety of evidences are found at crime scenes. Fingerprint and DNA evidences are especially important in the process of identifying personal sources. Among evidences found at crime scenes, cigarette butts are important because they might contain both fingerprints and DNA. In this study, latent fingerprints were detected in cigarette butts using 1,8‐diazafluoren‐9‐one (DFO) and 1,2‐Indanedione/zinc chloride (1,2‐IND/Zn). Next, DNA extraction and real‐time qPCR were performed to quantify and identify the DNA present. Short tandem repeat (STR) profiling was also performed. The results showed that the quantity of DNA recovered was decreased by 16% in DFO‐treated cigarettes and by 27% in 1,2‐IND/Zn‐treated cigarettes when compared to untreated controls. When the STR profiling results were compared with those of the control sample, DFO, and 1,2‐IND/Zn reagent‐treated DNA samples showed individualized genotyping at several loci. Results of this study showed that when cigarette butts were found, DFO and 1,2‐IND/Zn reagents could be used for DNA profiling after fingerprint identification. However, the effect of DFO on STR profiling was less than that of 1,2‐IND/Zn. Therefore, we recommend the use of DFO for fingerprinting cigarette butts if further DNA processing is planned.     

Kaonic nuclear state search via reaction at rest on He target

Very recently, we have performed a couple of experiments, KEK PS-E549/E570, for the detailed study of the strange tribaryon S⁰(3115) obtained in KEK PS-E471. In contrast to the previous proton spectrum, no narrow (20 MeV) peak structure was found either in the inclusive ⁴He(stopped K⁻, p) or in the semi-inclusive ⁴He(stopped K⁻, pX^±) reaction channel, which is equivalent to the previous E471 event trigger condition. Detailed analysis of the present data and simulation shows that the peak, corresponding to S⁰(3115), has been an experimental artifact. Present analysis does not exclude the possible existence of a much wider structure.     

Adaptive-Repetitive Visual-Servo Control of Low-Flying Aerial Robots via Uncalibrated High-Flying Cameras

This paper presents the design and implementation of an adaptive-repetitive visual-servo control system for a moving high-flying vehicle (HFV) with an uncalibrated camera to monitor, track, and precisely control the movements of a low-flying vehicle (LFV) or mobile ground robot. Applications of this control strategy include the use of high-flying unmanned aerial vehicles (UAVs) with computer vision for monitoring, controlling, and coordinating the movements of lower altitude agents in areas, for example, where GPS signals may be unreliable or nonexistent. When deployed, a remote operator of the HFV defines the desired trajectory for the LFV in the HFV’s camera frame. Due to the circular motion of the HFV, the resulting motion trajectory of the LFV in the image frame can be periodic in time, thus an adaptive-repetitive control system is exploited for regulation and/or trajectory tracking. The adaptive control law is able to handle uncertainties in the camera’s intrinsic and extrinsic parameters. The design and stability analysis of the closed-loop control system is presented, where Lyapunov stability is shown. Simulation and experimental results are presented to demonstrate the effectiveness of the method for controlling the movement of a low-flying quadcopter, demonstrating the capabilities of the visual-servo control system for localization (i.e.,, motion capturing) and trajectory tracking control. In fact, results show that the LFV can be commanded to hover in place as well as track a user-defined flower-shaped closed trajectory, while the HFV and camera system circulates above with constant angular velocity. On average, the proposed adaptive-repetitive visual-servo control system reduces the average RMS tracking error by over 77% in the image plane and over 71% in the world frame compared to using just the adaptive visual-servo control law.     

Effects of cooling rate and post-heat treatment on properties of ZnO thin films deposited by sol-gel method

Sol-gel spin-coated ZnO thin films are cooled with different rates after the pre-heat treatment. Atomic force microscopy (AFM), X-ray diffraction (XRD), Raman, and photoluminescence (PL) were carried out to investigate the effects of the cooling rate during pre-heat treatment on structural and optical properties of the ZnO thin films. The ZnO thin films cooled slowly exhibit mountain chain structure while the ones cooled rapidly have smooth surface. The ZnO thin films cooled rapidly have higher c-axis orientation compared to the ones cooled slowly. The narrower and the higher near-band-edge emission (NBE) peaks are observed in the ZnO thin films cooled rapidly.     

True nature of active layers in organic solar cells fabricated by sequential casting of donor and acceptor layers

The operation characteristics of nominal bilayer (BL) organic solar cells (OSCs), the active layers (ALs) of which consisted of sequentially casted bottom P3HT donor and top ICBA acceptor layers, resembled those of OSCs with bulk heterojunction (BHJ) ALs. Optical analysis and device simulations showed that such resemblance can be attributed to a similarity in the micromorphology of ALs; as‐deposited BL‐type ALs transformed spontaneously into BHJ‐type ALs. The inclusion of P3HT nanowires (NWs) in the donor layers resulted in different AL micromorphology and consequently a larger power conversion efficiency. Separate assessment of the exciton generation and charge–carrier transport and/or extraction showed that the contribution of P3HT NWs was more prominent in optical effects.

     

Sonolytic degradation of hazardous organic compounds in aqueous solution

Benzene, chlorobenzene, 1,2-, 1,3-, 1,4-dichlorobenzene, biphenyl, and polychlorinated biphenyls such as 2-, 4-chlorobiphenyl and 2,2′-dichlorobiphenyl in aqueous solutions have been subjected to sonolysis with 200 kHz ultrasound at an intensity of 6 W cm⁻² under an argon atmosphere. 80–90% of initial amount of these compounds were degraded by 30–60 min of sonication when the initial concentrations were 10–100 μmol l⁻¹. The degradation rate of these compounds increased with increase in their vapor pressures. In all cases of sonolysis of chlorinated organic compounds, an appreciable amount of liberated chloride ion was observed.     

Hydration of nitriles: an examination in terms of No Barrier Theory

Nitriles pose an interesting problem to the explanatory powers of organic chemistry because, despite the favorable overall thermodynamics of hydrolysis to the corresponding amides, the reactions are inherently slow. The rate determining step is hydration of the nitrile to give the imidic acid, which quickly tautomerizes to the amide. In terms of Marcus Theory, the intrinsic barriers for acid and base‐catalyzed hydration are higher for nitriles than for amides, which are themselves slow reactions. It is remarkable that hydration of a nitrile, for which the free energy change is close to zero except for polyhaloacetonitriles, is much slower than hydration of an amide, which is energetically unfavorable. This can be explained by No Barrier Theory in terms of the high energetic cost of the geometrical distortions in “one thing at a time” corner species. There are no experimental equilibrium constants for this initial hydration step, so we have determined them computationally. The free energy change for the initial hydration is small; it is the fast and energetically downhill second step, tautomerization to the amide, which makes the overall hydrolysis of nitrile to amide thermodynamically favorable. Very few of the pK_a values needed in the acid and base‐catalyzed mechanisms are known, so we used linear free energy relations and treat the parent pK_a values as adjustable parameters. This procedure leads to pK_a values in accord with expectation based on such data as are available and permits calculation of rate constants in satisfactory agreement with experiment. Copyright © 2013 John Wiley & Sons, Ltd.     

Effects of ultrasound on the formation of alpha-benzoylbenzyl cyanide from benzyl cyanide and alkylphenyl ketone from alpha-alkylbenzyl cyanide by potassium superoxide in the presence of crown ether

Ultrasound accelerates the formation of alpha-benzoylbenzyl cyanide and benzoic acid in the reaction of benzyl cyanide with potassium superoxide in the presence of 18-crown-6. Similarly, 4-methylbenzyl cyanide, 4-methoxybenzyl cyanide and 4-chlorobenzyl cyanide gave the corresponding alpha-(4-methylbenzoyl)-4-methylbenzyl cyanide, alpha-(4-methoxybenzoyl)-4-methoxybenzyl cyanide and alpha-(4-chlorobenzoyl)-4-chlorobenzyl cyanide in 25-43% isolated yields under the same reaction conditions. Benzoic, p-toluic, 4-methoxybenzoic and 4-chlorobenzoic acids were also formed in these reactions. No reaction was observed when the mixture was simply stirred. Reflux instead of sonication gave lower yields of the products. However, alpha-alkylbenzyl cyanide produced a high yield of the phenylalkyl ketones when stirred. Interestingly, the corresponding benzoic acid was not formed in these reactions. Possible mechanisms for the formation of alpha-benzoylbenzyl cyanide from benzyl cyanide and phenylalkyl ketones from alpha-alkylbenzyl cyanide are also proposed.