Novel Components of the Sex Pheromones Produced by Emerald Moths: Identification,Synthesis, and Field Evaluation

The subfamily Geometrinae (Lepidoptera: Geometridae) includes many species called emerald moths. Based on our recent finding of novel polyenyl compounds, including a double bond at the 12-position from two geometrine species, Hemithea tritonaria and Thalassodes immissaria intaminata, (6Z,9Z,12Z)-6,9,12-trienes and (3Z,6Z,9Z,12Z)-3,6,9,12-tetraenes with a C₁₇–C₂₀ straight chain were synthesized and analyzed by GC-MS. The 6,9,12-trienes, which were prepared by a double Wittig reaction between two alkanals and an ylide derived from (Z)-1,6-diiodo-3-hexene, characteristically produced fragment ions at m/z 79, 150, and M–98. The 3,6,9,12-tetraenes, which were prepared by a coupling between (Z)-3-alkenal and an ylide derived from (3Z,6Z)-1-iodo-3,6-nonadiene, showed fragment ions at m/z 79, 148, and M–96. These diagnostic ions were useful to distinguish these compounds from other known polyenyl pheromones, such as 4,6,9- and 6,9,11-trienes and 1,3,6,9-tetraenes. With reference to the GC-MS data, pheromone extracts of other species in Geometrinae inhabiting the Iriomote Islands were analyzed, and the 6,9,12-trienes were identified in the pheromone gland extracts of Pamphlebia rubrolimbraria rubrolimbraria and Maxates versicauda microptera. Furthermore, a field evaluation of the synthetic polyenes in a mixed forest of Tokyo revealed the following new male attractants for emerald moths: Idiochlora ussuriaria by a C₁₇ 6,9,12-triene and Jodis lactearia by a C₂₀ 3,6,9,12-tetraene, indicating the characteristic chemical structures of Geometrinae pheromones. On the other hand, through reexamination of the pheromone extract of H. tritonaria, (3E,6E)-α-farnesene was identified as an electrophysiologically active component in addition to the C₁₇ 6,9,12-triene. The binary mixture attracted more males than the single component lure baited with the triene in the Iriomote Islands.     

Competing Effects of Radio Frequency Fields on Carbon Nanotube/Resin Systems: Alignment versus Heating

This work shows that radio-frequency (RF) fields can simultaneously align carbon nanotubes (CNTs) dispersed in a resin and induce Joule heating to cure the resin. The timescales of alignment and curing using RF heating are numerically computed and compared at different field strengths in order to determine a temperature where alignment happens before the matrix crosslinks. Composites are experimentally fabricated at the desired target temperature and are optically analyzed and quantified; the CNT network is successfully aligned in the direction of the applied electric field. This methodology can be used to create composites where the local alignment can be varied across the sample. Composites fabricated using RF fields have higher electrical conductivity in the direction of the aligned CNTs than an oven-cured, randomly aligned sample. Also, RF-cured nanocomposites exhibit higher tensile strength and modulus in the direction of alignment compared to an oven-cured sample. Finally, it is further demonstrated how this methodology can be coupled with a direct ink writing additive manufacturing process to induce alignment in any desired direction, even orthogonal to the shear forces in the extrusion direction.     

Molecularly Targeted Agents as Radiosensitizers in Cancer Therapy—Focus on Prostate Cancer

As our understanding of the molecular pathways driving tumorigenesis improves and more druggable targets are identified, we have witnessed a concomitant increase in the development and production of novel molecularly targeted agents. Radiotherapy is commonly used in the treatment of various malignancies with a prominent role in the care of prostate cancer patients, and efforts to improve the therapeutic ratio of radiation by technologic and pharmacologic means have led to important advances in cancer care. One promising approach is to combine molecularly targeted systemic agents with radiotherapy to improve tumor response rates and likelihood of durable control. This review first explores the limitations of preclinical studies as well as barriers to successful implementation of clinical trials with radiosensitizers. Special considerations related to and recommendations for the design of preclinical studies and clinical trials involving molecularly targeted agents combined with radiotherapy are provided. We then apply these concepts by reviewing a representative set of targeted therapies that show promise as radiosensitizers in the treatment of prostate cancer.     

Small amphiphilic organics, coordination extended solids, and constant curvature structures

In this Account, we explore the role constant curvature structures play in amphiphilic small molecule crystals and extended coordination solids. A constant curvature structure is one in which there is a surface or interface that has the same curvature throughout its surface. Simple examples of such structures contain spheres (micelles), columns, or layers. Yet another family are cubic as is found in the gyroid topology. For amphiphilic systems, there are two domains, one generally hydrophobic and the other hydrophilic. We find that the interfaces between these two domains in small molecule structures resemble those in larger scale systems and adopt topologies related to constant curvature structures. The hydrophobic-to-total volume ratio, a molecular parameter, can be used to predict which type of constant curvature structure is adopted. In the case of three coordinate extended solids, constant curvature plays a role both in the extended net topology and in the hydrophobic-to-hydrophilic interface.     

Studies on the Catalysis by Lithium Perchlorate of Reactions of Aromatic Amines with Diethyl Azodicarboxylate and Naphtalen-2-ol with 4-phenyl-1,2,4-triazoline-3,5-dione

The ene-like reaction of naphtalen-1-ylamine and naphtalen-2-ylamine, and pyridin-2-ylamine with diethyl azodicarboxylate (DEAD) as well as that of naphthalen-2-ol with 4-phenyl-1,2,4-trizoline-3,5-dione is catalyzed by lithium perchlorate. Also conversion of ester function of (DEAD) to amide function in reaction with 2-aminopyridine and further rearrangement of ethyl N-pyridyn-2-ylcarbamoylazoformate into ethyl pyridin-2-ylcarbamate are catalyzed by LiClO₄.     

Controlling micro‐ and nanofibrillar morphology of polymer blends in low‐speed melt spinning process. Part II: Influences of extrusion rate on morphological changes of a PLA/PVA blend through a capillary die

The effects of the extrusion rate on the morphological changes of poly(lactic acid) (PLA)/poly(vinyl alcohol) (PVA) blend through a capillary die were investigated. In this study, the extrusion rate or mass flow rate is altered from 0.5 g min^?1 to 2 g min^?1 with an increment of 0.5 g min^?1. The PLA/PVA blend with a composition of 30/70 (wt %) exhibits a particle matrix morphology with dispersed PLA droplets within the PVA matrix. It is found that, the spherical or ellipsoidal dispersed PLA droplets are elongated and coalesced into rod‐like or longer ellipsoidal droplets when they pass through the capillary die. When the extrusion rate increases, the coalescence between the large PLA droplets occurs more intense. However, the changes of the extrusion rate have no strong effect on the coalescence of small droplets having diameter less than about 150 nm. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44257.     

In situ synthesis of zinc oxide/selenium composite for UV blocker application

Development of reliable ultraviolet (UV) blockers is crucial for UV radiation protection applications such as sunscreen and UV-resistant fabric. To date, zinc oxide (ZnO) has been extensively used as a physical UV blocker worldwide but has also been criticized for with its unfavored UV-induced reactive oxygen species (ROS) generation phenomena. As an attempt to suppress the photocatalytic activity of ZnO without compromising its UV absorbance property, amorphous selenium (Se) nanoparticles (NPs) were incorporated to ZnO using a facile and cost-effective coprecipitation method. Additionally, this process also enables an economical synthesis route for harvesting amorphous Se NPs from an aqueous medium. The ZnO–Se composites were thoroughly characterized to confirm its enhanced UV absorptivity combined with high transparency in the visible light range and to understand the interaction between ZnO and Se. Besides, Se-induced photocatalytic activity suppression of ZnO was demonstrated using methylene orange as an indicator. In vitro study revealed that ZnO–Se composite had improved biocompatibility over ZnO but comparable bacteriostasis ability under full-spectrum light irradiation. These results suggest that ZnO–Se composite is a promising UV blocker with advantages of facile synthesis, UV-induced ROS generation diminishment and biocompatibility.     

Highly sensitive electrochemical sensor based on zirconium oxide-decorated gold nanoflakes nanocomposite 2,4-dichlorophenol detection

Journal of Applied Electrochemistry - In this study, a sensitive and selective electrochemical sensor based on a zirconia oxide-decorated gold nanoflake nanocomposite-modified glassy carbon...