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本研究で作製したVolume Phase Holographic (VPH)グレーティングは,レーザを光源とする2光束干渉露光により,干渉縞の光強度分布を記録材料の屈折率変調として3次元的に記録された,ホログラフィック格子である。また,記録材料が干渉縞の間隔より十分大きな厚さを持つため,厚いホログラフィック格子に分類される。厚いホログラフィック格子の再生は,一層の格子による通常の回折とは異なり,結晶を用いたX線回折と同様に,多層格子によるブラッグ回折が生じ,ブラッグ条件を満たす入射により,100%に達す高い回折効率を得ることが出来る。2光束干渉露光法は光源のレーザの波長以下の微細周期格子や曲面状格子の作製も可能であり,ルーリングエンジンなどの機械的格子の作製に比べ高性能な回折格子の作製に適している。しかし,これまでは高解像力と露光量に応じた幅広いダイナミックレンジの屈折率変調量を持ち,さらに処理や取り扱いが容易な優れた記録材料の開発があまり進んでいなかったため,特に大面積を持つ高性能な素子へ適用されていなかった。今回のVPHグレーティングの作製には,日本ペイント(株)により新たに開発された光重合性の高解像・高屈折率変調量を持つ液状の高分子フォトポリマーを記録材料として使用した。その結果,0.03の屈折率変調量により80%の高い回折効率を持つVPHグレーティングを,大面積(110×106mm^2)に渡り,わずか±2%の変動率で作製でき,また高い面精度(rms=0.494λ)を持つこともZygo干渉計測計により確認した。一方,我々は2000年度より国立天文台すばる望遠鏡の観測装置の一つである,微光天体分光撮像装置(FOCAS)搭載用の分光素子Volume Phase Holographic (VPH)グリズムの開発を行ってきている。そこで今回試作した直進波長435nm,波長分解能2300のVPHグレーティングを2つのプリズムと合わせVPHグリズムを完成し,2003年6月にハワイ島に出かけ,すばる望遠鏡FOCASに搭載し,性能評価を目的とした測光標準星の分光観測を行った。性能評価実験により,試作VPHグリズム435は設計波長435nm付近で既存のレプリカタイプのグリズム(分解能1000)より高分解能(2300)で,約2倍の回折効率が得られたことを確認した。本論文では,高効率回折格子として,屈折率変調型のVPHグレーティングの設計・作製プロセスについて述べる。また応用として,天体観測用VPHグリズムの開発を行い,すばる望遠鏡FOCASに搭載し性能評価観測により,優れた性能を持つことが確認された結果について報告する。, We introduce a Volume Phase Holographic (VPH) grating, of which holographic grating is recorded in three dimensions. We fabricated this as a refractive index modulation of record material in the intensity distribution of interference fringes by two beams interference exposure using laser as a light source. Since the record material has sufficient thickness vis-a-vis the interval of interference fringes, it is normally classified as a thick holographic grating. For a thick holographic grating, reproduction process differs from the one by usual one-layer grating diffraction. The Bragg diffraction in a multilayer grating arises as in X-ray diffraction using crystal. Therefore, by the incidence fulfilling the Bragg conditions, nearly perfect diffraction efficiency rate of 100% can be acquired. The two beams interference exposing method is also possible to fabricate the fine periodic grating below the wavelength of the laser of a light source or a curved surface grating. This method is more suitable for fabricating a highly efficient diffractive grating, compared to the fabrication of mechanical gratings such as a ruling engine. However, conventionally there have been several obstacles to its applications. The refractive index modulation has a broad dynamic range, which depends on high resolution power and the exposure volume, and also there is only a slow progress of development of a record material with easier access and use. These factors have hindered its employment to a highly efficient element with a large area, in particular. In this research, we used liquefied high photopolymer with high resolving power and high refractive index modulation of the optical polymerization which was newly developed by Nippon Paint Co., Ltd., for the purpose of fabricating VPH grating as a record material. Consequently, VPH grating was successfully constructed with diffraction efficiency of 80% and refractive-index modulation of 0.026 in the sheer rate of ±2% change over large area (110～106mm^2). High wave front accuracy (rms=0.494λ) was confirmed by using the Zygo interferometer. While undertaking this above-mentioned fabrication and examination project, we have developed the Volume Phase Holographic (VPH) grism for the instrument of the Subaru Telescope of National Astronomical Observatory of Japan, which is named the Faint Object Camera and Spectrograph (FOCAS) in 2000. We fabricated the VPH grating sandwiched between two prisms and completed the VPH grism with a going-straight wavelength of 435nm and resolving power R (Δλ/λ) of 2300 (0.4" slit). Furthermore, all the authors except one were actually involved in the test experiments, having gone to Hawaii in June 2003, and loaded it onto the FOCAS to observe the photometric standard star (on June 21, 22, 2003). We noted that the VPH grism counted 1.5 to 2 times more photons than the conventional grism (R=1000) at wavelengths ranging from 380 to 430nm. The spectral data of an artificial light source confirmed that the fabricated VPH grism had a resolving power of 2300. In this paper, we report the designing and fabricating process of the VPH grating as refractive index modulation-type grating with high efficiency. For application, as we developed VPH grism for astronomical observation, and equipped one on FOCAS in Subaru Telescope, its remarkable performance was confirmed through the test observation held in Hawaii.

S-ニトロチオールはその高い反応性のため,不安定であり,報告例が数少ない。そこで,不安定化学種の安定化に有効と考えられるかさ高い置換基,2,4,6-トリ-t-ブチルフェニル基(Mes*基)および4-t-ブチル-2,6-ビス[(2,2",6,6"-テトラメチル-m-テルフェニル-2'-イル)メチル]フェニル基(Bmt基)の速度論的安定化の手法を用いて,安定な芳香族S-ニトロチオールを合成した。その構造をX線結晶構造解析より確認し,またその反応性についても検討した。, Kinetically stabilized aromatic S-nitrothiols bearing bulky groups, 2,4,6-tri-t-butylphenyl (Mes*) and 4-t-butyl-2,6-bis[(2,2",6,6"-tetramethyl-m-terphenyl-2'-yl) methyl]phenyl group (Bmt) were prepared by the reaction of the corresponding thiols with t-butyl nitrite. The molecular structure of stable S-nitrothiol BmtSNO2 was established by X-ray crystallographic analysis. The reactions of S-nitorothiols Mes*SNO2 and BmtSNO2 with some nucleophiles and the thermolysis were reported.

インターネットプロトコル(Internet Protocol: IP)トラフィックの爆発的な増加に対応するためには,伝送リンク容量の拡張と同時にパケット転送速度の高速化が必要不可欠であり,光ファイバをベースとして,情報を光でやりとりする大容量フォトニックネットワークの研究開発が進められてきた。さらに,"拡大するデータ帯域の幅に対する柔軟でアクティブな適応力"を持つネットワークを実現するために,ネットワークの機能と構成をダイナミックに進化させるパルス制御技術が注目されている。本論文では,アレイ導波路回折格子(Arrayed-Waveguide Grating: AWG)を用いた「高速パルス制御装置」を初めて提案・構築するとともに,光パルス列を用いたパルス整形の原理確認実験を行い,良好な結果を得たので報告する。この制御装置はモードロックレーザからの高速光パルスをAWGでフーリエ変換し,スペクトル面でMach-Zehnder式アクティブ導波路変調素子を用いて任意の変調を加えた後に再度AWGで逆フーリエ変換して時間波形に変換することを原理としている。パルス制御を支える波形整形技術としてはこれまでに,回折格子・シリンドリカルレンズと液晶空間光変調器を組み合わせた手法,AWGの時空間変換機能を用いて得られた周波数分布を液晶空間光変調器で変調する手法などが検討されている。しかしこれらの手法には変調帯域が狭く,制御する波形特性が一定の関数になり,3次以上の高次位相分散を個別に変調することが難しいなどの課題が残っている。従って,変調するスペクトル分布の空間分解能が液晶空間光変調器の画素サイズに依存することも設計時に考慮しなければならない。本研究で提案した手法では,前述した問題を解決し,AWGの持つナノメートルオーダー間隔で波長スペクトルを生成する能力を保ったまま,導波路領域内で光の振幅と位相を変調し,安定したパルス制御を可能にした。また,周波数面における変調を行うため,AWGの波長チャネル数を増やすことで,手軽にパルス変調帯域を増やすことができる。, An explosive increase in Internet Protocol (IP) traffic demands high-capacity photonic network based on a fiber transmission part and signal processing in the optical domain. Accordingly there is an increasing need for high-speed and active traffic control function that has a reconfigurable network structure to provide an individual user with optimum data rate. Among potential instruments, a pulse shaping is regarded as of high utility to realize the traffic control. We proposed and designed a new pulse synthesizer using a phase and attenuation tunable high-resolution arrayed waveguide grating (AWG). In this paper, we present the configuration and function of AWG synthesizer combined with a mode-locked Laser diode (MLLD) and planar lightwave cuicuit (PLC), along with demonstration of real-time variable rate pulse trains generation and pulse re-shaping. The optical pulse synthesizer consists of AWG with tunable attenuators, optical phase shifters, and a mirror, which are all integrated by PLC technology. Optical pulse or pulse trains input from an in/out port and divided into spacing spectral components. Amplitude and optical carrier phase are tuned by attenuators and phase shifters, respectively. It has been reported that some techniques were estabilished to synthesize and shape short pulses by use of optical pulse shaping method employing Fourier-Transformed Hologram with various devices such as diffraction grating, lenses and liquid-crystal spatial light modulator (SLM). Pulse shaping system is also under examination, equipped with frequency resolved optical grating using the parallel aligned nematic liquid crystal SLM. However, these methods are left with some issues to be grappled such as a narrow spectral range, similar wave forms of pulse or pulse train and a resulting design restriction of SLM pixel pitch. Moreover, there is difficulty to be overcome in modulating higher order phase dispersion in optical fiber. As a possible solution to those tasks, our proposed method enabled the modulation of a spectrum distribution in waveguide by use of Mach- Zehnder interferometer attenuation and phase shifter, keeping a small wavelength space of AWG constant. This facilitates the manner of decreasing modulation resolving power and bandwidth simply by means of the number increase of the AWG.

High-resolution ^1H NMR spectroscopy of fresh and intact saliva was measured aimed at elucidating the intra/inter variance of healthy young females. Saliva was used as a model system of "drug response" to internal hormones as exemplified by the menstrual cycle. 30 volunteers aged 20 to 24 were recruited and divided into two groups who showed high- or low-basal body temperature at the first stage. Saliva of both temperature stages was collected for the same subject 5 times a day. The ^1H NMR spectral pattern exhibited quite a large variance for each sample. The signal intensities were slowly increased but remained within a reasonable range for 4 hours after sampling, followed by a conspicuous signal enhancement for more than 2 days. The intensities did not change if the macromolecules were removed by ultra-centrifuge. The result suggested that the macromolecules in saliva underwent the irreversible denaturation, releasing the bound small molecules. Thus the signal intensities may vary depending on the delay time after sampling when the samples were centrifuged. The pH titration revealed that apparent pKa of some acids shifts more than 0.5 along with varied Hill coefficient, which suggested that the observed small molecules make a rapid chemical exchange between bound and free states in solution. The presence of dynamic magnetic exchange was verified observing the double-quantum filtered spectra. The simultaneous observation of single and double quantum spectra was explored.

メチルセルロース水溶液は, ゼラチンなどで見られるゾルーゲル転移とは逆に, 温度の上昇によってゲル化する物理ゲルとして大変興味深い物質である。また, モノマー中に親水基と疎水基を持つため, 両親媒性分子の性質を有すると考えられ, 凝集過程においてもその特徴が反映されると予想される。そこで, ゾル, ゲル, 相分離の各相を保つ温度において, 親水性ガラス基板上で溶媒を蒸発させた時の各乾燥膜の形成過程と結晶形状の比較検討を, 透過型偏光顕微鏡, AFM, MDG広角X線散乱などを用いて行った。その結果, 自己組織化により高分子鎖を折りたたみながら乾燥膜を形成するが, 膜周辺と膜中心部とでは繊維軸の配向が異なることが示唆された。, Methyl cellulose aqueous solution is an interesting material, which shows the reverse sol-gel transition temperature dependence with the gelatin. We have derived phase diagrams for aqueous solution methyl cellulose. Then, based on this phase diagram, we examined how physical gel like the methyl cellulose aqueous solution shows the selfassembly in drying process at the temperature which keeps each condition, such as the sol, gel and phase separtaion state. Comparison examination of crystalline morphology of each drying film formed under the abovementioned condition was tried using polarizing microscope (OM), WAXS, AFM. For around the spreading droplet, there is a thin film made by solvent evaporation. The any thin films obtained regardless of drying conditions of sol and/or gel, showed the Maltese cross and the birefringent pattern like negative spherulites at the OM observation. Furthermore, it was indicated by WAXS using MDG that the crystalline morphology of the droplet, which was formed under the condition of gel, is fold chain crystal.

近年の情報技術の発展と共に実時間処理が可能なさまざまな高性能記録材料の開発が進められている。その代表的な材料が液晶である。この液晶の高分子複合体と有機感光体とを組み合わせた新しいタイプのアナログ静止画像用の入力記録媒体としてエルグラフィ素子が開発されている。このエルグラフィ素子は現像処理が不要で, 高解像度, メモリ性があり, 撮影後瞬時に可視化でき, 電圧の印加条件の変化による2値画像処理化, 熱処理による書き換えが可能などの優れた特徴を持っている。 一方著者らは光学式のハイブリッドな顔画像認識システムを構築し, 認識速度7 face/s. 本人拒否率0.3%, 他人受け入れ率O%の低いエラー率を持つ実用可能な装置の小型化を実現している。しかしこのハイブリッドシステムは信号の制御は容易であるが, 入力・参照画像においてコンピュータのメモリから液晶画像へ表示する際に, 電気・光信号変換に33msの時間を有しており, システムの高速演算のボトルネックになっている。我々はこれらの問題解決に向けて, 同時並列な画像を入力するための光デュプリケートシステムと参照画像の光速読み出しの多重光メモリシステムについて検討を行ってきている。 本論文では, 全光認識システムの光並列画像入力部分として, エルグラフィ素子を用いたデュプリケートシステムを提案し, その有効性を実験により確認した。まず光並列画像入力としてLEDを用いたデュプリケート光学系を構築し, 光学伝達関数(Modulation Transfer Function : MTF)による評価を加え, 理論上のカットオフ周波数とほぼ同一の22.51p/mmを検出した。 これらの結果に基づき, 2値化顔画像の表示を行い, エルグラフィ素子の液晶と感光体との組み合わせの割合の最適化と撮影条件を決定した。さらに, 画像を記録したエルグラフィ索子を用いデュプリケート画像を表示し, これを用いたシミュレーションによる相関演算実験により, その有効性を示した。, With recent and rapid advancement of the information technology, developments of various recording materials for real-time procession are under way. This is exemplified in the field of liquid crystal technology. Combined with this, electro-photography has been used to research and development of elgraphic devices as a new type of input recording media for analogue images. This device merits attention for its non- developing procession, high resolution, and a large quantity of memory capacity. Other features are possible instant visualization after photoshooting, binary image-processing by changing voltage conditions, rewritability by use of heat-processing. In parallel with this research and development, a hybrid optical face-recognition system has been constructed. It has been proved by a number of evaluative experiments that our system is rigorous with the recognition speed of 7 faces per second, the false non-match rate 0.3%, and the false match rate 0%. The compact device for a practical use is already materialised. While this hybrid system facilitates the control of signals, it requires 33ms for exchanging electric and optical signals in the process of obtaining input images from the memory and projecting reference images on the crystal liquid display. Higher speed is desirable for further improvement of the system. Seeking to tackle this speed issue, we have been conducting several researches using an optical duplicate system designed to input correlational images and a multiple optical memory system for high-speed reference images reading. In this paper, a duplicate system with Elgraphy devices is proposed. The devices are equipped at the input end of an all-optical recognition system. The validity and its higher performance are then examined through experiments and will be presented. In brief, this research is conducted in following procedures: Designing the duplicate optical system employing LED as input devices for parallel optical images. Successively, experimenting on this system, we assess the performance by MTF, and demonstrate the obtained value, 22.5 1p/mm is nearly equal to the value of the cut-off frequency in theory. Based on these results, we display binarized facial images, followed by optimazing crystal liquid of the Elgraphy elements and determining the photo-shooting conditions. Lastly, duplicate images are exhibited using the memory-storing elgraphy elements. By way of simulation based on correlation experiments, the validity is proven to be significant.

低分子のチオール類は揮発性が高くまた空気中で酸化されやすい。そこで5,5'-ジチオビス(2-ニトロ安息香酸; Ellman試薬)を用いてチオールを誘導体化したのち, キャピラリー電気泳動によりチオール類の分解・検出を行った。SH基を有する化合物にEllman試薬を過剰に加えると, 混合ジスルフィドとチオレートアニオンが生成するが, 電気泳動を行うことにより, 一部重複していた各成分のピークの分離が可能となった。泳動液は80μMテトラデシルアンモニウムブロミド(TTAB)を含む10mMリン酸二水素ナトリウム溶液を用いた。 TTAB溶液を添加することで, キャピラリー内壁の電荷を制御し電気浸遠流を減少させることにより各成分の持つ構造の違いによる泳動時間の差が明確になり分離が完全になった。キャピラリーは内径0.075mm, 全長500mm(有効長378mm)の溶融シリカ管を用いた。試料は落差10mmで30秒間キャピラリー内に注入し印加電圧十30kVにて泳動を行った。キャピラリー周囲は25℃に保った。検出にはEllman試薬を用いて誘導化したチオール類の吸収極大波長である357nmを用いた。エタンチオール, 1-プロパンチオール, 1-ブタンチオールを短時間で分離・検出できた。, The determination and detection of low molecular weight thiols by capillary electrophoresis (CE) system has been studied. Though electrophoresis of thiols has to be carried out at low pH due to their instability, each migration time of thiols was fairly long and the separation of thiols wasn't completely. We examined to derivatize thiols with 5,5'-dithiobis (2-nitorobenzoic acid) which has been used as the photometric reagent for the determination of thiols, usually called as Ellman's reagent. In this study, ethanethiol, 1-propanethiol and 1-butanethiol were investigated to be separated by CE with UV detection. Running buffer was prepared to be pH 7.4 containing 1OmM disodium hydrogenphosphate and 80μM tetradecyltrimethylammonium bromide. Ethanethiol, 1-propanethiol and 1-butanethiol were prepared as a 0.5mM solution in lOmM sodium phosphate buffer (pH=7.4). The applied voltage was set at +30kV. The detection of derivatized rhiols was measured at 357 nm. These thiols were separated each other in 18min.

より住みよい生活環境を騒音の観点から検討する目的で, 一般住宅におはる床材料の吸音率測定を10^2～10^4Hz程度の可聴周波数領域で行った。カーペットはウール, ポリエステルなど, 周波数が高くなると吸音率が顕著に増大した。これに比べて畳は周波数依存性が小さく, 低周波ではカーペットより吸音率が高いことがわかった。また, 一般的な広さでは居室面積による吸音率の違いは見られなかったが, 室内にベッドなどの家具があると高音域での吸音率が高くなること, カーペットを敷いた室内では吸音率が高く, 防音効果が高いことが明らかにされた。, To investigate the conditions for better living from a viewpoint of noise reduction, we measured the acoustic absorption coefficients of flooring materials in an audible frequency range from 10^2 to 10^4 Hz. Either wool or polyester carpets showed a distinct rise in absorption coefficients with an increase in frequency. On the other hand, the acoustic absorption of tatami showed a weaker frequency dependence and at low frequencies became higher than that of carpets. In the case of ordinary size, the room area produced no effect on the acoustic adsorption. Such furniture as beds was found to increase acoustic absorption coefficients at high frequencies.