<所内学術研究成果報告>D. 「海洋生物の医薬資源開発, 医薬を指向した海洋生物の探索と調査・開発」

海洋はその種100万といわれ, 地上における今もなお未知な世界である。本年度も, この海洋生物から, 医薬資源となりうる有用な生理活性物質を発見し, 構造を明らかにし, 生物活性を検討することを目的として研究を行った。この研究を始めてから11年を経過した。そこで, 本年度は, 新しい生物の採集を中止し, 今までの生物成分のまとめを行った。特に, 日本産ナマコ類成分, 沖縄と真鶴で採集した日本産フサコケムシ成分, および深海巻貝2種の成分研究を完成した

D. 海洋生物の医薬資源開発-医薬を指向した海洋生物の有用物質の探索

海洋生物はその種100万といわれ、地上における今もなお未知な世界である。本年度も、この海洋生物から、医薬資源となりうる有用な生理活性物質を発見し、構造を明らかにし、生物活性を検討することを目的として研究を行った。この研究を始めてから10年になった。本年度採集した生物は、27種であり、今までに309件を採取している。採集生物リストをTableに示した。バイオアッセイを指標に今まで、海草、アカフジツボ、クダウミヒドラ、スポンジ、エボヤ、ユーレイボヤ、イソギンチャク、群体ボヤ、オオワレカラ、コケムシ類等につき有用成分の探索を行った。特に、付着生物コケムシ(Bryozoa)類の各種の成分に注目し、各地で採集したフサコケムシBugula neritina、ホソフサコケムシTricellaria occidentalis及びアメリカフロリダ産コケムシAmathia convolutaの活性成分を検討し、有益な知見と新しい化学物質を単離・構造決定した。すなわち、昨年度報告したconvolutamine AとF以外にconvolutamie Gを、さらにlutamide C以外にlutamide AとB及びconvolutamydine Eの単離を行い、構造決定した。さらに、昨年から始めたこれら有用な天然物の全合成研究に成果が見られ、3種のconvolutamine類A、CとF及び2種のlutamide類AとCの計5種の天然物の全合成を完成させた。この成果には、さらにanalogsの全合成を含み、化合物の構造とその活性との相関に研究が発展している。これらの結果は、日本化学会第76回春季年会(1\u27999/3)で口頭発表し、次いでその後の成果を加え、第19回メディシナルケミストリーシンポジウム第8回日本薬学会医薬化学部会年会(1\u27999/11)で口頭発表した。これらの成果と深海生物研究の成果を学術論文として投稿し、一部掲載が完了している。本年度大槌湾で採集した生物は16種、山田湾では9種を採取した。ホソフサコケムシは採取したが、フサコケムシは見られなかった。コケムシとしては、ほかにアミコケムシとウデコブコケムシを採集した。ウデコブコケムシの量が最も多かった。本年、深海生物としてパプアニューギニア産の巻き貝2種を加えることができた

Study on the Growth and Root Strength of Lagerstroemia subcostata Koehne Vegetation Stake

The Lagerstroemia subcostata Koehne vegetation stake which was selected in the study is often used in the staking and wattling method of vegetation engineering. The planting datum were collected from the greenhouse in National Chung Hsing University and Feng Shui Ping was compared to the growth datum in Nantou Puli No.96 landslides' area. To probe into the growth condition of the vegetation stake at tree-crown and roots, the root strength and the method improving survival rate are used by correlating analysis, regression and Chi-Square Test. The results obtained would be referable for advantage of the staking and wattling method. Results obtained are summarized as follows: Before staking the Lagerstroemia subcostata Koehne vegetation stake, the stakes were dealed with drying, water and auxin.The survival rate of the stakes dealed with water reached to 23.08% after eigth months. The investigatation datum from Nantou Puli No.96 landslides' area used by statistics analysis test to reveal that the survival rate was distinct affected by the vegetation stake with different diameters. There was high bud rate in vegetation stake with the diameter from six to nine centmeters. According to the root distribution datum of the Lagerstroemia subcostata Koehne vegetation stake, the root type belongs to PH-type. It would be helpful for Lagerstroemia subcostata Koehne vegetation stake to grow and expand or increasing the absorption of water with thin and extremely thin roots. There are 84.67% roots centered on 0-20cm layer if root distribution is divided into two layers (0-20cm and 20-40cm). From the results of root mechanical experiment, we got the regression equations of root tensile strength on root diameter are shown as (1), the regression equations of the length of tree-crown on root shear strength are shown as (2). The maximum value of net photosynthetic on the Lagerstroemia subcostata Koehne vegetation stake appeared at am11:00 and pm 13:00.The Pearson Correlation Index is 0.942 between net photosynthetic and conductance, the value revealed high correlation. (1) The regression equations of root diameter on root tensile strength are shown as following: F = -2.17+3.33D+1.72D2 R2＝0.937 0.23≦D≦8.82 F: root tentile strength (kg) D: root diameter (mm) (2) The regression equations of the length of tree-crown on root shear strength are shown as following: S= -503.911 +10.862 * L R2＝0.916 28≦L≦250 S: root shear strength (kg/m2) L: length of tree-crown (cm)本研究選取水土保持植生工法中之打樁編柵常使用的九芎植生木樁，整理位於中興大學水土保持學系溫室及草屯風水坪水土保持戶外教室之栽植資料，並比較南投埔里九十六林班崩塌地之野外生長調查結果，分別利用相關分析、迴歸分析以及卡方考驗等統計分析分法，來探討植生木樁地上部與地下部之生長情形、根系之力學效應以及提昇成活率之可行方式，俾提供打樁編柵施工效益之參考。所得結果摘要如下： 九芎植生木樁在打摏前分別利用乾燥處理、浸水處理及浸開根素處理三種方式，經過八個月後之調查結果，以打樁前利用浸水處理之方式可以達到較高之成活率23.08%。 由南投埔里九十六林班崩塌地之野外九芎植生木樁萌芽調查資料，應用統計分析方法檢定結果顯示，使用不同植生木樁之樁徑，對其成活率有顯著之影響，其中又以樁徑界於6公分至9公分間之植生木樁有較高之萌芽率。 根據九芎植生木樁根系調查結果，其根系之型態屬於平行與水平型(PH-type)，初期根系多為細根至極細根，可增加其對水分之吸收以及根系之向外延伸；將根系分佈之調查分為地面向下0∼20cm及20∼40cm兩層，其中有84.69％之根量集中於0∼20cm此層。另由根系力學試驗結果，根段拉力與根徑之迴歸方程式如(1)所示。利用地上部之樹冠長對九芎植生木樁根系之剪力增強迴歸結果如(2)所示。 九芎植生木樁之淨光合成率分別在上午十一時及下午一時達最大值。以統計分析作淨光合成率與氣孔導度兩者之相關性分析，Pearson相關達0.942**，顯示具高度相關性。 (1)九芎植生木樁根徑對根段拉力之迴歸方程式 F = -2.17+3.33D+1.72D2 R2＝0.937 0.23≦D≦8.82 F：九芎植生木樁根段拉力值(kg) D：九芎植生木樁根徑(mm) (2)九芎植生木樁剪力增強與樹冠長之迴歸方程式 S= -503.911 +10.862 * L R2＝0.916 28≦L≦250 S：九芎植生木樁剪力增強(kg/m2) L：九芎植生木樁樹冠長(cm)中文摘要--------------------------------------------- Ⅰ ABSTRACT--------------------------------------------- Ⅲ 表次------------------------------------------------- Ⅴ 圖次------------------------------------------------- Ⅵ 壹、前言--------------------------------------------- 1 貳、前人研究----------------------------------------- 2 一、植物根系型態與生長之研究--------------------- 2 二、植物根系力學之研究--------------------------- 5 三、植物生理反應特性之研究----------------------- 14 參、試驗材料、項目與方法----------------------------- 17 一、試驗地點之選定------------------------------- 17 二、試驗地栽植情況及植物------------------------- 20 三、試驗地栽植情況介紹--------------------------- 22 四、試驗項目及方法------------------------------- 24 肆、結果與討論--------------------------------------- 34 一、植物根系、地上部生長與土壤特性分析----------- 34 二、不同處理之萌芽率及其與直徑之關係------------- 44 三、根段拉力強度試驗----------------------------- 51 四、九芎植生木樁剪力增強之推估------------------- 54 五、植體生理特性分析----------------------------- 58 伍、結論--------------------------------------------- 63 陸、參考文獻----------------------------------------- 65 附 錄------------------------------------------------ 70 附錄一、九芎植生木樁冠幅與根冠迴歸統計----------- 70 附錄二、埔里九十六林班崩塌地九芎植生木樁不同樁徑 分組對成活與否之卡方檢定----------------- 71 附錄三、九芎植生木樁根段拉力試驗數據------------- 72 附錄四、九芎植生木樁剪力增強計算表--------------- 75 附錄五、九芎植生木樁剪力增強推估多變量敘述統計--- 77 附錄六、相關氣象資料----------------------------- 8

Octopus-Inspired Assembly of Nanosucker Arrays for Dry/Wet Adhesion

The octopus is capable of adhering to slippery, rough, and irregular surfaces in the marine intertidal zone because of its periodic infundibulum-shaped suckers on the arms. Here, we present a scalable self-assembly technology for fabricating adhesion materials that mimic octopus sucker functionality. By utilizing spin-coated two-dimensional colloidal crystals as templates, non-close-packed nanosucker arrays are patterned on silicone substrates. The resulting nanosuckers can be deformed to exhibit great adhesive capacities on both microrough and flat surfaces in dry and wet environments. This indicates a probable biomimetic solution to the challenge of wound care

尋跡自走車

[[abstract]]1.顧名思義就是無人操縱車輛。 2.車輛可以依照程式的指令，配合感測器的感測，引導車輛前進、後退、轉彎、停止，以達到自動行走的目的。 3.我們以 89C51 單晶片來製作智慧型自走車，藉由程式化的控制流程、方法與策略，完成能沿軌道(只需一條黑色的膠帶)自行前進的自走車。 4.如果無軌道，還可以利用控制器來控制車輛 。 5.自走車可以聽一般的哨音啟動電路，頻率約2KHz

Macroporous photonic crystal-based anti-ultraviolet and anti-near-infrared materials by doctor blade coating

In this article, we report a roll-to-roll compatible bottom-up self-assembly approach to fabricate double-multilayer macroporous polymer photonic crystals consisting of a multilayer of three-dimensional (3D) hexagonal close-packed (HCP) 200 nm spherical pores and a multilayer of 3D HCP 500 nm spherical pores. Both optical measurements and theoretical predictions reveal that the as-prepared polymer film exhibits anti-ultraviolet and anti-near-infrared properties caused by the Bragg's diffractive of incident ultraviolet radiation and near-infrared radiation from the crystalline lattice of air cavities in the polymer film. The changes in the atmospheric composition and depletion of the stratospheric ozone during the past decades lead to an increase in solar ultraviolet (UV) and near-infrared (NIR) radiation dosage.1–3 Prolonged human exposure to solar UV radiation causes deleterious health effects on the skin, eye and immune system.4,5 The solar NIR rays generate radiant heat and are trapped inside buildings, resulting in a drastic increase of cooling loads.6–8 However, most commercial polymers and glasses have poor UV and NIR reflectance quality.9,10 With a considerable interest, many studies have been recently reported on the preparation of UV-shielding or NIR-shielding materials via the structural design of polymer molecules, or addition of inorganic nanoparticles to polymeric matrix.10–14 Unfortunately, the structural design of polymer molecules may cause changes in mechanical properties, causing huge inconvenience in polymer manufacturing.10,11 Composites consisting of inorganic fillers provide attractive properties like resistance against UV radiation and NIR radiation.12–14 However, it is still a challenge to achieve a homogeneous dispersion of the incorporated fillers in most polymeric matrices. The aggregation of inorganic nanoparticles with different refractive indices relative to the polymer results in light scattering, leading to translucent composite materials. Photonic crystals are composed of periodic dielectric structures that provide a powerful platform for developing optical filters for prohibiting the propagation of a select frequency range of light.15 Compared to the complex photolithography process, photonic crystals can be simply fabricated by colloidal self-assembly technologies.16,17 Nonetheless, most self-assembly technologies have optical properties dominated by defects and cannot be favorable for industrial-scale mass fabrication.18,19 To resolve the scale-up issue of current bottom-up self-assembly technologies, a roll-to-roll compatible doctor blade coating technology has recently been developed to fabricate three-dimensional colloidal crystal-polymer composites in a single step.20 This methodology is based on unidirectional shear aligning concentrated colloidal suspension, inspired by a spin-coating self-assembly technology.21,22 After selectively removing colloidal crystals in the composite, the templating macroporous polymer films exhibit uniform diffractive colors. Here, we demonstrate that dual-doctor blade coated double-multilayer macroporous photonic crystals with a combination of anti-ultraviolet and anti-near-infrared properties can be fabricated. The schematic illustration of the dual-doctor blade coating procedure for fabricating double-multilayer macroporous photonic crystals is displayed in Fig. 1. A 500 nm silica colloidal crystal-ETPTA (ethoxylated trimethylolpropane triacrylate) polymeric composite is doctor blade coated on an ETPTA wetting layer coated glass substrate (see supplementary material23). In a typical coating process, the 500 nm silica particles are dispersed in an ETPTA monomer to prepare for colloidal suspension with a particle volume fraction of 75%. An immobilized razor blade applies a uniform shear force to align silica microspheres when the substrate is moved at 1 mm/min. The monomer is photo-polymerized to form a 500 nm silica colloidal crystal-ETPTA polymeric composite. The substrate is subsequently doctor blade coated with a 200 nm silica colloidal crystal-ETPTA polymeric composite. The templating silica particles can be removed by etching in a 1 vol. % hydrofluoric acid aqueous solution. The resulting double-multilayer polymer film consisting of three-dimensional crystalline arrays of 500 nm air cavities and 200 nm air cavities can then be peeled off from the glass substrate to create self-standing macroporous polymer photonic crystals

Self-assembled dual-sided hemispherical nano-dimple-structured broadband antireflection coatings

A non-lithography-based approach is developed in this study for assembling monolayer close-packed hemispherical nano-dimple arrays on both sides of a PET film by a scalable Langmuir-Blodgett technology. The resulting gratings greatly suppress specular reflection and therefore enhance specular transmission for a broad range of visible wavelengths, resulting from a gradual change in the effective refractive index at air/PET interface. The experimental results reveal that the antireflection properties of the as-fabricated coatings are affected by the size of the nano-dimples. Moreover, both optical performances of single-sided and dual-sided nano-dimple-structured coatings have been investigated in this study. Natural nanostructures, with unique functionalities, have provided a vast range of inspirations for practical applications.1–4 For example, cicada wings are highly transparent and exhibit less than 1% reflectance over the visible spectrum, owing to the presence of hexagonal arrays of sub-200 nm conical structures on their wings.5,6 The cone arrays with a period smaller than the propagating wavelength leads to a gradient index of refraction across the interface between air and wing, substantially suppressing Fresnel's reflection.7,8 Biomimicry of the cicada wing design onto material surfaces is extensively used as an antireflection coating in optical and optoelectronic applications, including displays, solar cell systems, and vehicle dashboards.9,10 Comparing to traditional quarter-wavelength antireflection coatings, multilayer antireflection coatings, as well as porous antireflection coatings, biomimetic subwavelength conical-structured coatings give rise to a gradual change in refractive index rather than a sudden one, and display great broadband antireflection properties over a wide range of angles of incidence.11–13 However, the coatings are often composed of fragile high-aspect-ratio surface geometries and the fabrication procedures usually require complex preparation schemes.14 Moreover, current top-down lithographic technologies (e.g., photolithography, nanoimprint lithography, and laser interface lithography) for fabricating cicada-wing antireflection coatings are expensive and exhibit limited control over pattern spatial homogeneity and reproducibility.15–17 In contrast, self-assembled colloidal crystals have been used as etching masks during a reactive ion etching process to template nanostructure arrays, offering a less expensive and simpler methodology in fabricating cicada-wing gratings.18–21 Unfortunately, bottom-up self-assembly technologies are mostly used in laboratory-scale and it is challenging to scale up these processes.22–24 Recently, plasmonic antireflection coatings consisting of a subwavelength metal array and a dielectric cover layer by combination of lithography and metal deposition are designed and fabricating, showing a broadband reduction of reflection.25–28 However, the reactive ion etching process is relatively expensive and highly labor-intensive, and also requires clean room conditions.29,30 In this research, we developed a Langmuir-Blodgett-like approach to assemble large-area nano-dimple-structured antireflection coatings in a roll-to-roll compatible manner. Monodispersed silica spheres with diameters of 155 nm and 70 nm were synthesized by the Stöber method.31 The synthesized Stöber silica spheres were purified in absolute ethanol by repeated centrifugation/re-dispersion cycles to remove impurities, following by re-dispersing in non-volatile ethoxylated trimethylolpropane triacrylate (ETPTA) monomers with 1 vol. % Darocur 1173 as photoinitiator. The silica particle volume fraction was controlled to be 22.5 vol. %. Figure 1 presents a schematic illustration of the fabrication procedure for creating dual-sided hemispherical nano-dimple-structured antireflection coatings. The as-prepared silica/ETPTA suspension was added dropwise, while the ETPTA monomer-covered silica spheres spread rapidly and formed two-dimensional colloidal monolayers at the deionized water surface. A poly(ethylene terephthalate) (PET) film pre-immersed in deionized water was vertically withdrawn at a rate of ∼5 cm/min by using a double-sided tape attached to a syringe pump. The floating ETPTA monomer-covered silica colloidal monolayers were uniformly transferred onto both sides of the PET substrate. The capillary action enables the ETPTA monomers to flow and fill the empty space between the silica colloidal crystals and the PET substrate. The sample was then transferred to a pulsed UV curing system to photo-polymerize ETPTA monomers under UV radiation. The silica spheres partially embedded in ETPTA polymeric matrices were finally removed by wet etching in a 2 vol. % hydrofluoric acid aqueous solution to pattern periodic nano-dimple structures

Self-Assembled Hierarchical Arrays for Colored Retroreflective Coatings

This study reports a self-assembly technology for fabricating retroreflection coatings with hierarchical nano-/microstructures, which are inspired by the binary periodic structures found in the compound eyes of insects. Silica colloidal crystals of adjustable thicknesses are assembled on encountering glass microbeads using a Langmuir-Blodgett-like approach in a layer-by-layer manner. The as-assembled hierarchical structures exhibit a brilliant color caused by Bragg diffraction from the crystalline lattice of silica colloidal crystals on glass microbeads. The resultant coating is capable of reflecting light in the opposite direction of the incident light. Moreover, the dependence of the silica particle size, the colloidal crystal thickness, and the incident angle on the retroreflective properties are investigated in this study

Self-Assembled Curved Macroporous Photonic Crystal-Based Surfactant Detectors

Surfactants are extensively used as detergents, dispersants, and emulsifiers. Thus, wastewater containing high-concentration surfactants discharged to the environment pose a serious threat to the ecosystem. Unfortunately, conventional detection methods for surfactants suffer from the use of sophisticated instruments and cannot perform detections for various surfactants by a single analysis. The article reports the development of simple and sensitive surfactant detection using doctor-blade-coated three-dimensional curved macroporous photonic crystals on a cylindrical rod. The photonic crystals exhibit different hydrophobicities at various angular positions after surface modification. The penetration of aqueous surfactant solutions in the interconnected macropores causes red-shift as well as reduction in amplitude in the optical stop bands, resulting in surfactant detection with visible readout. The correlation between the surface tension, as well as the solution-infiltrated angular position, and the concentration of aqueous surfactant solutions has also been investigated in this study