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To clarify the relation between neuronal protection against ischaemia and calcium/calmodulin-dependent protein kinase II (CaM kinase II) activity, we investigated temporal alterations of the kinase activity in the hippocampus after transient forebrain ischaemia under neuroprotective conditions, employing the gerbil bilateral carotid artery occlusion model. The hippocampal CA1 neuronal density at 2 hours after 5 minutes of forebrain ischaemia was 214.7 +/- 25.8/mm (mean +/- S.D.), and did not differ from the control significantly; however, it decreased to 11.7 +/- 4.2/mm at 7 days after the ischaemia. The neuronal density at 7 days after the ischaemia was 185.1 +/- 18.5 under the hypothermic conditions, 128.7 +/- 19.6 with the brief ischaemic pretreatment, 65.0 +/- 13.4 with administration of MK-801, and 20.5 +/- 4.2 with the repetitive hyperthermic pretreatment, respectively. The Ca2+/calmodulin-dependent activity of CaM kinase II in the hippocampal cytosolic fraction was decreased to 47.5% of the control value at 2 hours after the ischaemia, when CA1 neuronal death was not observed. In contrast, the activity was 98.8% of the control under the hypothermic conditions, 91.4% with the brief ischaemic pretreatment, 71.2% with administration of MK-801, and 47.9% with the repetitive hyperthermic pretreatment, respectively. These results indicated that the preservation of the Ca2+/calmodulin-dependent activity of cytosolic CaM kinase II after ischaemia parallelled the neuroprotective effect in the gerbil hippocampus. Thus, it is suggested that the preservation of the activity may be involved in the mechanism of neuronal protection against ischaemia.

A survey and inventory of tree canopy bio-diversity for cryptogams (myxomycetes, macrofungi, mosses, liverworts, lichens and ferns) in the Great Smoky Mountains National Park resulted in the discovery of an undescribed myxomycete species. This taxon is classified in the order Physarales, family Di-dymiaceae and genus Diachea. A combination of morphological characteristics distinguishes Diachea arboricola H.W. KellerM. Skrabal sp. nov. from all other species in the genus: peridium iridescent gold to silvery gray; stalk reddish orange above and whitish below, filled with crystals; capillitial threads stiff, dichotomously branched and arising from the tip of the columella; spore ornamentation uniformly covering the entire spore surface, appearing spiny with light microscopy, with scanning electron microscopy as vertical processes with capitate, clustered, spike-like tips. This type of spore ornamentation has not been found in any other Diachea species. Diachea arboricola is known only from the tree canopy, ranging in height from roughly 3 to 21 m, on three tree species, Fraxinus americana, Juniperus virginiana and Quercus alba. Observations of plasmodial growth and fruiting body development are described based on moist chamber cultures. Tree canopy observations in situ suggest that the plasmodium of this species migrates over extensive vertical areas of tree bark. Ecological factors are discussed that include pH of bark substrata. The species description is based on abundant sporangia from 17 different collections. A key to the species of Diachea is provided to aid in the identification of this taxon.

There is an emerging concept, the validity of which remains to be proven, that preferential expression of selective adhesion molecules on particular T cell subsets may result in tissue-specific migration. L-selectin, cutaneous lymphocyte-associated Ag (CLA), and integrin alpha4beta7 are proposed to be involved in selective migration of T cell subsets into peripheral lymph nodes, skin, and gastrointestinal mucosa, respectively. Adult T cell leukemia (ATL) is associated with lymphoid infiltration of tissues and secondary lymphoid organs. To clarify the role of these putative homing molecules in vivo, we assessed their expression on circulating ATL cells from patients with lymph node, skin, and gut involvement. L-selectin expression was significantly higher on peripheral ATL cells in patients with lymphadenopathy than in patients without it. CLA was highly expressed on peripheral ATL cells compared with normal T cells: its expression was also significantly higher on peripheral ATL cells from patients with skin involvement compared with cells from patients without it. beta7 was particularly highly expressed on peripheral ATL cells from patients with gastrointestinal involvement. In summary, the differential expression of beta7 and beta1 on peripheral ATL cells correlates with the presence of gastrointestinal involvement. Similarly, the presence of skin involvement is associated with the expression of CLA(high)beta7low on peripheral ATL cells. These results, which are consistent with the molecules CLA and alpha4beta7 mediating preferential T cell migration to the skin and gastrointestinal mucosa, respectively, may allow for a refinement of the classification of lymphoid neoplasms on the basis of differential expression of homing molecules.

The theory of the gamma-laser launching by means of the quadrupole spin echo technique is constructed. The general steps of the development of the pulsed gamma-laser dynamics are shown. Numerical estimations are made for /sup 103/Rh.

Many neurosurgeons prefer to use intraoperative computed tomographic (CT) scanning, when possible, to check whether there is residual lesion or unexpected bleeding. We report a practical intraoperative CT imaging system using a high-speed CT scanner installed in the operating room along with a digitally controlled neurosurgical operating table. We designed a rail-track system to mobilize the CT gantry. The gantry is fixed onto a motorized carrier that can be moved smoothly on a rail-track embedded in the floor and with a maximum reach of 2.85 m from the room's wall to the operating table. The longitudinal motion of the operating table is easily adjusted by a foot switch from manual control to automatic control directly from the CT scanner's computer like an ordinary CT scanner bed in increments of 2, 5 or 10 mm during CT scanning. Either a carbon-made radiolucent head frame or carbon-made head plate is used as a headrest. Using this CT scanner system, pre- and intraoperative CT scannings were performed on 46 patients with brain tumors, cervical lesions or other intracranial lesions. We could operate on the patient with enough working space between the mobile CT gantry and the operating table for microneurosurgery. We could obtain intraoperative CT imaging of a patient on the operating table while the surgical wound remained open, the surgical drapes kept in place, and the surgical position unchanged, saving time in intraoperative CT scanning and preparation for further surgery when needed. This intraoperative CT imaging system installed in the operating room should be useful for neurosurgery.

Arts and Culture Education develops students' sense of taste, creativity, and aesthetic tastes in art, develops ethics, social awareness and cultural awareness of students in social life, and a love of Indonesian culture. One of the cultural art materials learned for the Upper Middle School level about two-dimensional art. But students in class X IIS 1 of SMA Negeri 1 Labuhan Deli increased the difficulty of learning two-dimensional art results to be low. Therefore this research was conducted which was intended to improve student learning outcomes using the Role Playing model. This research is a classroom action research (CAR) conducted in two cycles. The data collection technique used is a test of learning outcomes. Analysis of the data used is the equation of individual absorption and the percentage of classical absorption. The results of the study prove that an increase in student learning outcomes using role playing models in two-dimensional art material at SMAN 1 Labuhan Deli. This study suggests that teachers use learning models that support student learning outcomes, one of which is role playing models that has various advantages and uniqueness . Keywords: fine art, role playing. Abstrak Pendidikan Seni Budaya berfungsi mengembangkan kepekaan rasa, kreativitas,dan cita rasa estetis siswa dalam berkesenian, mengembangkan etika, kesadaran sosial dan kesadaran kultural siswa dalam kehidupan bermasyarakat, serta rasa cinta terhadap kebudayaan Indonesia. Salah satu materi Seni Budaya yang dpelajari untuk tingkat Sekolah Menengah Atas adalah tentang seni rupa dua dimensi. Namun siswa di kelas X IIS 1 SMA Negeri 1 Labuhan Deli mengalami kesulitan sehingga hasil belajar seni rupa dua dimensi menjadi rendah. Oleh karena itu dilakukan penelitian ini yang bertujuan untuk meningkatkan hasil belajar siswa menggunakan model Role Playing . Penelitian ini merupakan penelitian tindakan kelas (PTK) yang dilaksanakan dalam dua siklus. Teknik pengumpulan data yang digunakan adalah tes hasil belajar. Analisis data yang digunakan adalah rumus daya serap individu dan persentase daya serap klasikal. Hasil penelitian membuktikan bahwa terjadi peningkatkan hasil belajar siswa menggunakan model role playing pada materi seni rupa dua dimensi di SMAN 1 Labuhan Deli. Penelitian ini menyarankan agar guru menggunakan model pembelajaran yang mendukung hasil belajar siswa, salah satunya yaitu model role playing yang mempunyai berbagai kelebihan dan keunikan. Kata Kunci: seni rupa, role playing . Author: Nurambia : Sekolah Menengah Atas Negeri 1 Labuhan Deli References: A’la, M. (2011). Quantum Teaching . Yogyakarta: Diva Press. Anderson, H., & Britton, T. (2000). Stochastics Epidemic Models and their Statistical Analysis . New York: Springer-Verlag. Angkowo, R., & Kosasih, A. (2007). Optimalisasi Media Pembelajaran . Jakarta: Grasindo. Arikunto, Suharsimi. (2010). Prosedur Penelitian Suatu Pendekatan . Jakarta: Rineka Cipta. Dewi, T. A. (2017). Efektivitas Model Role Playing dalam Meningkatkan Kompetensi Mahasiswa Pada Mata Kuliah Manajemen Keuangan. JURNAL PROMOSI: Jurnal Pendidikan Ekonomi UM Metro , 5 (1), 95–104. http://dx.doi.org/10.24127/ja.v5i1.850 . Fauzi, H. D. (2015). Buku Guru Seni Budaya . Bandung: Yrama Widiya. Istarani. (2012). Model Pembelajaran Inovatif . Medan: Media Persada. Joyce, & Weil. (1992). Models of Teaching . USA: Allyn and Bacon. Tetty Khairiyah, D. (2013). Pengaruh Model Role Playing pada Pembelajaran Seni Rupa Terhadap Hasil Belajar Menggambar Siswa Kelas IV SDN 01 Baso. Serupa The Journal of Art Education , 2 (1), ___ . Komaruddin. (2000). Model Pembelajaran Aktif . Bandung: Remaja Rosdakarya. Mulyasa, E. (2005). Menjadi Guru Profesional . Bandung: Remaja Rosdakarya. Ngalimun. (2014). Strategi dan Model Pembelajaran . Yogyakarta: Aswaja Pressindo. Rahmat. (2008). Model Pembelajaran Aktif . Jakarta: Balai Pustaka. Reigeluth, C. M. . (1983). Instructional Design Theories and Models: An Overview of Their Curent Status . London: Lawren Erlbaum Associates Publisher. Richey, R. C. (1986). The Theoretical and Conceptual Bases of Instructional Design . London: Kogan Page Ltd. Rohani, A. (2004). Pengelolaan Pengajaran . Jakarta: Rineka Cipta. Sagala, S. (2011). Konsep dan Makna Pembelajaran . Bandung: Alfabeta. Sanjaya, W. H. (2008). Strategi Pembelajaran Berorientasi Standar Proses Pendidikan . Jakarta: Kencana. Sapriya. (2002). Studi Sosial: Konsep dan Model Pembelajaran . Bandung: Buana Nusantara. Sari, J., Tarigan, N., Erdansyah, F., & Sumarsono. (2020). Pengaruh Penguasaan Prinsip Dan Unsur Seni Rupa Terhadap Hasil Belajar Menggambar Flora Di Smp Swasta Al-Ulum Medan. Gorga : Jurnal Seri Rupa , 9 (1), 133–137. https://doi.org/10.24114/gr.v9i1.18308 . Shoimin, A. (2014). 68 Model Pembelajaran Inovatif dalam Kurikulum 2013 . Yogyakarta: Ar-Ruzz Media. Slameto. (2003). Belajar dan Faktor-Faktor yang Mempengaruhinya . Jakarta: Rineka Cipta. Suprijono, A. (2010). Cooperatif Learning Teori dan Aplikasi . Yogyakarta: Pustaka Belajar. Uno, H. B. (2003). Model Pembelajaran Menciptakan Proses Belajar Mengajar yang Kreatif dan Efektif . Jakarta: Bumi Aksara. Uno, H. B. (2009). Perencanaan Pembelajaran . Jakarta: Bumi Aksara. Wahyuni, S., Mering, A., & Isti, W. (2016). Penerapan Metode Role Playing pada Pembelajaran Seni Tari untuk Meningkatkan Kreativitas Siswa di SMP. Jurnal Pendidikan dan Pembelajaran Khatulistiwa , 5 (11), ____ . Yoyok, R. M. (2008). Seni Budaya 3 . Bogor: Yudhistira Ghalia Indonesia.

Concurrently with the rapid development in digital society, the demand for communication skills was clear in childhood. Early childhood education needs to pay attention to children's speech skills development. This study aims to determine the effect of cognitive style and attachment on the ability to speak in early childhood speech development. The method used is a 2 x 2 factorial comparison design which is divided into two groups namely independent and dependent fields involving 138 samples. Re- search findings about differences in the ability to speak early childhood who have independent field cognitive style and children who have field dependent cognitive style in groups of children with high attachment obtained (A2B1), obtained Q count = 9.39 and Q table (0.05; 4: 10) = 4 , 33. 4). Differences in the ability to speak early childhood who have an independent field cognitive style and children who have a field dependent cognitive style in groups of children with low attachment obtained (A2B2), ob- tained Q count = 4.39 and Q table (0.05; 4: 10) = 4 , 33. It show that early children who have independent field cognitive style have higher speech skills scores than early children who have field dependent cog- nitive style while early children who are independent field cognitive style with low attachment have lower speech skills scores than early childhood the field dependent cognitive style with low attachment. Keywords: Cognitive style and Attachment, Early Childhood, Speech Skills Reference Aulya Purnama, R., & Wahyuni, S. (2018). Kelekatan (Attachment) pada Ibu dan Ayah Dengan Kompetensi Sosial pada Remaja. Jurnal Psikologi, 13(1), 30. https://doi.org/10.24014/jp.v13i1.2762 Berk, L. E. (2007). Child Development Boston. Pearson (seventh Ed). Boston: Pearson.Borich, G. D., & Tombari., M. L. (1996). Educational Psychology: A Contemporary Approach. New York: Harper Collins College Publishers. Boroujerdi, F. G., Kimiaee, S. A., Yazdi, S. A. A., & Safa, M. (2019). Attachment style and history of childhood abuse in suicide attempters. Psychiatry Research, 271, 1–7. https://doi.org/10.1016/j.psychres.2018.11.006 Braune, R., & Wickens, C. D. (1986). Time-sharing revisited: Test of a componential model for the assessment of individual differences. Ergonomics, 29(11), 1399–1414. https://doi.org/10.1080/00140138608967254 Brodin, J., & Renblad, K. (2019). Improvement of preschool children’s speech and language skills. Early Child Development and Care, 0(0), 1–9. https://doi.org/10.1080/03004430.2018.1564917 Davis, D. (2011). Child Development, Third Edition: A Practitioner’s Guide (Clinical Practice with Children, Adolescents, and Families) (Third Edit). New York London: The Guilford Press. Desmita. (2010). Psikologi Perkembangan Peserta Didik. Bandung: Rosdakarya. Ding, Y. hua, Xu, X., Wang, Z. yan, Li, H. rong, & Wang, W. ping. (2014). The relation of infant attachment to attachment and cognitive and behavioural outcomes in early childhood. Early Human Development, 90(9), 459–464. https://doi.org/10.1016/j.earlhumdev.2014.06.004 Evans, R., & Jones, D. (2007). Perspectives on oracy-towards a theory of practice. Early Child Development and Care, 177(6–7), 557–567. https://doi.org/10.1080/03004430701424938 Feeney, J. A. (2001). Becoming Parents: Exploring The Bonds Between Mothers, Fathers, And Their Infants Paperback. UK: Cambridge University Press. Gandasetiawan, R. Z. (2009). Mengoptimalkan IQ dan EQ Anak Melalui Metode Sensomotorik. Jakarta: PT BPK Gunung Mulia. Goodman, M. L., Gibson, D., Vo, T. T., Wang, A., Gitari, S., & Raimer, B. (2018). Early childhood attachment and suicidal ideation among young Kenyan men. Advances in Life Course Research, 35(February), 126–134. https://doi.org/10.1016/j.alcr.2018.02.001 Holmes, J. (2014). John Bowlby and Attachment Theory (2nd Editio). https://doi.org/https://doi.org/10.4324/9781315879772 Kerlinger, F. N. (1990). Asas-asas Penelitian Behavioral (3th ed.). Yogyakarta: Gajah Mada University Press. Larasati, N. I., & Desiningrum, dinie R. (2017). Hubungan Antara Kelekatan Aman Dengan Ibu Dan Regulasi Emosi Siswa Kelas X Sma Negeri 3 Salatiga. Empati, 6(3), 127–133. Lwin, M., Khoo, A., Lyen, K., & Sim, C. (2002). How to Multiply Your Child’s Intelligence: A Practical Guide for Parents of Seven-Year-Olds and Below. Singapore: Pearson Education Asia Pte., Ltd. Machado, J. M. (2012). Early Childhood Experiences in Language Arts: Early Literacy (10 edition). Belmont, USA: Wadsworth Publishing. Madyawati, L. (2016). Strategi Pengembangan Bahasa Pada Anak. Jakarta: Kencana. Mahabbati, A. (2013). Layanan Pendidikan untuk Anak Berkebutuhan Khusus dan Pendidikan Inklusif. Retrieved from http://staffnew.uny.ac.id/upload/132318126/pengabdian/ppmlayanan-pendidikan-untuk- anak-berkebutuhan-khusus. McLeod, S., Harrison, L. J., & Wang, C. (2019). A longitudinal population study of literacy and numeracy outcomes for children identified with speech, language, and communication needs in early childhood. Early Childhood Research Quarterly, 47, 507–517. https://doi.org/10.1016/j.ecresq.2018.07.004 Nasution, S. (2011). Berbagai Pendekatan Dalam Proses Belajar Dan Mengajar. Jakarta: Bumi Aksara. Nussipzhanova, B., Berdibayeva, S., Garber, A., Tuyakova, U., Mursaliyeva, A., & Baizhumanova, B. (2017). Cognitive development of pre-school children with language and speech disorders. The European Journal of Social and Behavioural Sciences, 21(1), 2570– 2583. https://doi.org/10.15405/ejsbs.227 Ormrod, J. E. (2009). Psikologi Pendidikan Membantu Siswa Tumbuh dan Berkembang (6th editio). Jakarta: Erlangga. Otto, B. (2015). Perkembangan Bahasa Pada Anak Usia DIni (third Edit). Jakarta: Prenadamedia. Papalia, D. (2008). Human Development. Jakarta: Kencana. Platokhina, N. A., Samarina, I. V., & Abashina, N. N. (2016). Preventive Measures against Speech Disorders in Early Childhood. Procedia - Social and Behavioral Sciences, 233(May), 247–251. https://doi.org/10.1016/j.sbspro.2016.10.212 Pudjaningsih, W. (2013). Pembelajaran Melalui Bermain Dalam Rangka Pengembangan Kemampuan Berbahasa Anak di TK Islam Al-Azhar Kota Jambi. Pena : Jurnal Pendidikan Bahasa Dan Sastra, 53(9), 1689–1699. Santrock, J. W. (2011). Life Span Development. New York: Mc Graw Hill.Shi, C. (2011). A Study of the Relationship between Cognitive Styles and Learning Strategies. Higher Education Studies, 1(1), 20–26. https://doi.org/10.5539/hes.v1n1p20Sternberg, R. J., & Williams, W. M. (2009). Educational Psychology (2nd Editio). Boston: Pearson.Sumantri, M. S., Supriyati, Y., & Nugroho, H. (2015). Pengaruh Kelekatan dan Self Esteem terhadap Kecerdasan Spiritual. Pps UNJ.Taylor, C. (2010). A Practical Guide to Caring for Children and Teenagers with Attachment Difficulties. London and Philadelphia: Jessica Kingsley Publishers. Uno, H. B. (2016). Orientasi Baru Dalam Psikologi Pembelajaran. Jakarta: Bumi Aksara. Waring, R., Liow, S. R., Eadie, P., & Dodd, B. (2019). Speech development in preschool children : evaluating the contribution of phonological short-term and phonological working memory. 1–21. https://doi.org/10.1017/S0305000919000035

The efficient generation of ballistic hot electrons in nanosilicon dots under an electric field is based on the intrinsic carrier transport therein. Due to suppressed phonon scattering losses followed by enhanced tunneling rate, electrons become hot at the early stage of injection [1]. Generated ballistic hot electrons can be utilized either inside or outside the nanosilicon dot layer. The topics on this effect are discussed here toward possible photonic applications. The nanosilicon device is a kind of MIS diode consisting of a thin film surface electrode, a nanosilicon layer (~1 μm thick), a crystalline silicon wafer substrate, and a back contact. The nanosilicon layer includes parallel chains of quantum-sized nanosilicon dots (~3 nm in mean diameter) interconnected with tunnel oxides. When a positive voltage is applied to the surface electrode, electrons injected from the substrate into the nanosilicon layer are drifted toward the outer surface, and then some of them reach the surface electrode as ballistic hot electrons. One possible application of this effect is the avalanche photoconduction by sequential impact ionization in nanosilicon dots. Actually, the photo-carriers multiplication effect was observed in thin oxidized nanosilicon diodes under the reverse bias condition [2]. For a monochromatic near-uv light incidence at low temperatures (e.g., 77 K), the photoconduction quantum efficiency was increased up to 2500% at an external electric field of 9×105 V/cm. The experimental data on the temperature, electric field, and sample thickness dependencies of the photocurrent suggest that the field-induced avalanche multiplication of photo-excited carriers occurs inside the nanosilicon dot layer. From theoretical analyses of carrier dynamics [3], it has been clarified that the impact ionization rate is significantly enhanced in nanosilicon dots compared with in bulk silicon owing to the efficient transition between quantized discrete energy states and the enhanced Coulomb interaction in nanosilicon dots. The threshold electron energy of impact ionization is decreased in realistic nanosilicon dots with disordered surface structures [4]. These facts provide useful information for the development of efficient photo-sensors and photovoltaic cells. Ballistic hot electrons generated in the nanosilicon layer uniformly ejects to outside by tunneling through the thin surface electrode [5]. The most characteristic feature of this emission phenomenon is the high kinetic energy of electrons and its controllability. At applied voltages of 15-20 V, for instance, the mean energy of output electrons varies from 5 to 7 eV. No conventional cold cathodes can emit such energetic electrons. Being a supplier of electrons with an extremely high physical and electrochemical activity, this emitter is available for the operation in every media: vacuum, atmospheric gases, and solutions. In vacuum, this device is applicable to the exposure source for parallel EB lithography [6]. By integrating the emitter array with active-matrix CMOS driver circuit and combining with focusing electron optics system, alternative advanced nanofabrication technology would be developed. Another promising application in vacuum is a probing source for an extremely high-sensitivity image pick-up. The usefulness of the nanosilicon ballistic emitter in atmospheric gases has been demonstrated in air and in Xe gases as a negative ion source and a vacuum-ultraviolet (VUV) light generator, respectively. The former relates to the dissociative hot electron attachment on O2 molecules. In the latter, the output electron energy match well with the internal excitation of Xe gas molecules followed by VUV emission without any impact ionizations. This emitter acts even in solutions as an active electrode which supplies highly reducing electrons. Based on the experimental confirmation of the usefulness in aqueous solutions for H2 generation and pH control, it has been demonstrated that the operation of the emitter in metal-salt solutions is available for depositing thin metal (Cu, Ni, Co, Zn, and so on) films without using any counter electrodes. In contrast to the exchange of thermalized electrons, the ballistic electro-reduction scheme is effective in SiCl4 and GeCl4 solutions. When driven in these solutions, thin Si and Ge films are deposited uniformly on the emitting surface [7]. As in the case in metal-salt solutions, injected energetic electrons can directly reduce Si4+ and Ge4+ ions at the interface leading to the nuclei formation and the subsequent film growth with neither contaminations nor byproducts. Because of a large electrochemical window, it is difficult to get uniform thin Si and Ge films by electroplating. The deposition rate in this unilateral electro-reduction process is comparable to that in the conventional dry process. The structural analyses indicate that the deposited thin Si and Ge films are of amorphous. Visible photoluminescence was observed in ultra-thin Si films. In addition, it is possible to deposit thin SiGe films by the operation in mixture (SiCl4+GeCl4) solutions. Since the ballistic electro-reduction is an alternative clean approach, this is attractive for the low-temperature fabrication of thin-film and multilayered photoelectronic devices. This work was partially supported by the JSPS through a Grant-in-Aid for Scientific Research and the FIRST Program and by the NEDO through the R&D Project. References 1. N. Mori, H. Minari, S. Uno, H. Mizuta, and N. Koshida, Appl. Phys. Lett. 98, 062104 (2011). 2. Y. Hirano, K. Okamoto, S. Yamazaki, and N. Koshida, Appl. Phys. Lett. 95, 063109 (2009). 3. N. Mori, H. Minari, S. Uno, H. Mizuta, and N. Koshida, Jpn. Appl. Phys. 51, 04DJ01 (2012). 4. N. Mori, M. Tomita, H. Inari, T. Watanabe, and N. Koshida, .Jpn. Appl. Phys. 52, 04CJ04 (2013). 5. N. Koshida, X. Sheng, and T. Komoda, Appl. Surf. Sci. 146, 371 (1999). 6. N. Ikegami, N. Koshida, A. Kojima, H. Ohyi, T. Yoshida, and M. Esashi, J. Vac. Sci. & Tech. B 31, 06F703 (2013). 7. T. Ohta, B. Gelloz, and N. Koshida, Appl. Phys. Lett. 102, 022107 (2013).

Expanded porphyrins have been received great interest due to the extended p-conjugation, multi-metal coordination, and multiple oxidation states, which consequently make them to be useful for optoelectronic applications, especially in the near-infrared (NIR) region. In contrast to the standard porphyrin with rigid planarity, expanded porphyrins are generally rather flexible and show the uncommon electronic and/or electromagnetic behaviors. However, the large flexibility of the molecules allows them to take various structures with many conformers and tautomers, which sometimes makes the metal coordination difficult and unpredictable. Thus, it has been awaited to synthesize the rigid-shaped expanded porphyrins possessing a large cavity that can accept bis-metals in the core without difficulty. Considering how enormous the achievement of porphyrin chemistry with a single metal is, the development of NIR dye chemistry with bis-metal expanded porphyrin ligands should be promising. We have been working on N-confused porphyrinoids and exploring the unique features in view of their structures and electronic states.1 Replacing the regular pyrrole with N-confused pyrrole ring in the pyrrolic macrocycle, which we call “confusion approach”, is now recognized an effective strategy for controlling the electronic state and molecular shape (Figure 1).2 Recently, we have succeeded in synthesizing the singly, doubly, and triply N-confused [26]hexaphyrins and revealed the effects of confusion on the structures, optical properties, and metal coordination.3-7In this presentation, recent progress of the coordination chemistry of doubly N-confused hexaphyrins is overviewed. References 1) Toganoh, M.; Furuta, H. Chem. Commun. 2012, 48, 937. 2) Srinivasan, A.; Furuta, H. Acc. Chem. Res. 2005, 38, 10. 3) Gokulnath, S.; Nishimura, K.; Toganoh, M.; Mori, S.; Furuta, H. Angew. Chem. Int. Ed. 2013 , 52, 6940. 4) Gokulnath, S.; Toganoh, M.: Yamaguchi, K.; Mori, S.; Uno, H.; Furuta, H. Dalton Trans. 2012, 41, 6283. 5) Gokulnath, S.; Yamaguchi, K.; Toganoh, M.; Mori, S.; Uno, H.; Furuta, H. Angew. Chem. Int. Ed. 2011, 50, 2302. 6) Ikawa, Y.; Takeda, M.; Suzuki, M.; Osuka, A.; Furuta, H. Chem. Commun. 2010, 46, 5689. 7) Xie, Y.-S.; Yamaguchi, K.; Toganoh, M.; Uno, H.; Suzuki, M.; Mori, S.; Saito, S.; Osuka, A.; Furuta, H. Angew. Chem. Int. Ed. 2009, 48, 5496.

Tujuan dari penelitian ini adalah untuk menganalisis tingkat kemampuan bertanya dan berkomunikasi siswa di kelas XI IPA SMA IT Al-Ittihad Pekanbaru Tahun Ajaran 2017/2018. Penelitian ini merupakan penelitian deskriptif kuantitatif. Sampel dalam penelitian ini adalah semua siswa kelas XI IPA yang berjumlah 30 siswa yang diambil melalui teknik total sampling. Teknik pengumpulan data menggunakan kuesioner yang terdiri dari 30 pernyataan kemampuan bertanya dan 30 pernyataan kemampuan berkomunikasi serta menggunakan lembar observasi kualitas pertanyaan. Data dianalisis menggunakan statistik deskriptif. Berdasarkan analisis persentase kemampuan bertanya siswa secara keseluruhan didapatkan skor rata-rata sebesar 3.62 dengan kriteria baik. Hasil analisis kemampuan berkomunikasi siswa secara keseluruhan didapatkan skor rata-rata sebesar 3.82 dengan kriteria baik. Hasil observasi kualitas pertanyaan siswa diperoleh sebanyak 13.33% dari siswa yang ada dengan pertanyaan sebanyak 100% termasuk kedalam tingkat C1-C3 (LOTS), sehingga tidak ada pertanyaan yang termasuk kedalam tingkat C4-C6 (HOTS). Dengan demikian dapat disimpulkan bahwa kemampuan bertanya dan berkomunikasi siswa termasuk kriteria baik pada pembelajaran biologi di SMA IT Al-Ittihad Pekanbaru. References Arif, M. (2016). Peningkatan Kemampuan Bertanya Melalui Metode Debat Aktif Siswa Kelas VIII D SMP N 2 Banguntapan Bantul. E-Jurnal Program Teknologi Pendidikan, Vol. 5 No. 5 Tahun 2016 ( hal. 62-74). Dinata, M. (2018). PENGARUH MODEL PEMBELAJARAN KOOPERATIF TIPE TIME TOKEN BERBANTUAN ANIMASI TERHADAP HASIL BELAJAR SISWA PADA MATERI SISTEM PENCERNAAN MAKANAN DI KELAS VIII SMP BUKIT RAYA PEKANBARU TA 2017/2018. Bio-Lectura, 5(1), 1-10. Jumiati, J. (2014). PENGARUH PEMBELAJARAN BERBASIS PORTOFOLIO TERHADAP PENGUASAAN KONSEP MORFOLOGI TUMBUHAN PADA MAHASISWA SEMESTER III TAHUN 2012/2013. Bio-Lectura, 1(2), 1-13. Jumiati, J., & Taufitri, S. (2018). KENDALA MAHASISWA PENDIDIKAN BIOLOGI FKIP UNIVERSITAS LANCANG KUNING DALAM PELAKSANAAN MATA KULIAH MICROTEACHING TA 2016/2017. Bio-Lectura, 5(1), 79-90. Lestari, R. (2017). Profil Keterampilan Bertanya Siswa Pada Pembelajaran Biologi SMAN 1 Bandar Lampung Tahun Pelajaran 2016/2017. Skripsi Jurusan Pendidikan MIPA FKIP UNILA. Bandar Lampung: Diterbitkan. http://digilib.unila.ac.id. [31 Oktober 2017] Naim, N. (2016). Dasar-Dasar Komunikasi Pendidikan. Ar-Ruzz Media: Jogjakarta Ramadhan, F, Mahanal, S, dan Zubaidah, S. (2016). Kemampuan Bertanya Siswa Kelas X SMA Swasta Kota Batu Pada Pelajaran Biologi. Jurnal Bioedukasi, Vol. 8 No. 1 Tahun 2017 (hal. 11-17). Saputra, H. (2013). Studi Tentang Kemampuan Berkomunikasi Guru Dalam Meningkatkan Motivasi Belajar Siswa Pada Kegiatan Belajar Mengajar di SDN 017 Kota Samarinda. Ejournal Ilmu Komunikasi , 1(1), 290-300. Sari, Y,A. (2012). Penyusunan Lks Derivat Epidermis (Stomata Dan Trikomata) Pada Daun Beberapa Tumbuhan Di Lingkungan Sekolah Sebagai Media Pembelajaran Materi Jaringan Tumbuhan Siswa Kelas XI SMA Negeri 1 Sleman. Skripsi Jurusan Pendidikan Biologi FMIPA UNY. Yogyakarta: Diterbitkan. http://eprints.uny.ac.id. [01 November 2017] Sugiyono. (2015). Statistika Untuk Penelitian. Alfabeta: Bandung Uno, H, B. (2010). Orientasi Baru dalam Psikologi Pembelajaran. Bumi Aksara: Jakarta Widodo, A. (2006). Profil Pertanyaan Guru dan Siswa dalam Pembelajaran Sains. Jurnal Pendidikan dan Pembelajaran. 4(2), 139-148.

BackgroundHead and neck squamous cell carcinomas (HNSCC) are classified in human papillomavirus (HPV)-positive and HPV-negative tumors. In general, HPV-negative HNSCC are genetically characterized by many chromosomal gains and losses.1 Previously, we and others identified a HPV-negative subgroup with few or absent copy number alterations (CNA-silent), and a more favorable prognosis.2 3 Tumors with low copy number changes have generally been associated with high immune infiltration scores,4 but for CNA-silent versus CNA-high HPV-negative HNSCC such data are lacking.In this study we aim to unravel by functional assays immunological differences between HPV-negative and HPV-positive HNSCC, as well as between CNA-silent and CNA-high HPV-negative HNSCC. We analyzed the immune cell subsets attracted by HNSCC cell lines and by tumor-conditioned supernatants.MethodsEight HNSCC cell lines (3 HPV-positive, 3 HPV-negative CNA-high, 2 HPV-negative CNA-silent) and 24-hour supernatants of thirteen HNSCC biopsies were used to characterize their ability to attract immune cells in a transwell migration system. A chemokine mixture was used as a positive control, while medium alone was used to determine spontaneous migration. Peripheral blood mononuclear cells (PBMCs) of various healthy donors were plated in the upper compartment and after six hours the transwell migration was quantified by flow cytometry.ResultsMost HNSCC cell lines induced migration of monocytes, B cells and CD4+ T-cells up to maximal 12%, whereas CD8+ T-cells and conventional dendritic cells (cDCs) were not attracted, irrespective of the donor. Notably, one HPV-negative CNA-silent cell line induced significantly more migration compared to the negative control and other cell lines. Tumor-conditioned supernatants promoted immune cell migration with no apparent differences between tumor sites or HPV-status. Remarkably, up to 31% of monocytes migrated to these supernatants, 9x more than the chemokine control. Also cDC migration was induced, whereas lymphocytes were not attracted.ConclusionsHNSCC cell lines induced monocyte, B-lymphocyte and CD4+ T-lymphocyte migration, whereas tumor-conditioned supernatants attracted monocytes and cDCs only. No difference in immune cell attraction between HPV-positive and -negative HNSCC was observed. Interestingly, one HPV-negative CNA-silent cell line induced robust immune cell migration. Currently we perform a comprehensive chemokine analysis to explain the observed migration. The noted lack of CD8+ T-cell attraction may explain why current treatments with PD-1 inhibitors are effective in only a minority of HNSCC patients. Our data could provide a means to identify patients who might most likely respond to immune checkpoint blockade and to find clues to improve CD8+ T-cell attraction.ReferencesLeemans CR, Snijders PJF, Brakenhoff RH. The molecular landscape of head and neck cancer. Nat Rev Cancer 2018;18:269–82.Smeets SJ, Brakenhoff RH, Ylstra B, van Wieringen WN, van de Wiel MA, Leemans CR, et al. Genetic classification of oral and oropharyngeal carcinomas identifies subgroups with a different prognosis. Cell Oncol 2009;31:291–300.Cancer Genome Atlas N. Comprehensive genomic characterization of head and neck squamous cell carcinomas. Nature 2015;517:576–82.Davoli T, Uno H, Wooten EC, Elledge SJ. Tumor aneuploidy correlates with markers of immune evasion and with reduced response to immunotherapy. Science 2017;355.Ethics ApprovalWritten informed consent was obtained from all patients from whom fresh tumor biopsies were used for research, as part of the HNcol protocol at the Department of Otolaryngology|Head and Neck Surgery of Amsterdam UMC (VUmc) as approved by the Institutional Review Board (2008.071|A2016.035). Buffy coats, with written consent from the donors, were purchased from the Dutch blood bank (Sanquin) and used to isolate PBMC.

Corrole is known as a contracted tetrapyrrolic macrocycle bearing an α,α'-linked bipyrrole moiety. Using a unique trianionic N4 donor environment at the inner core, various high-valent metal species have been examined for potential catalytic applications. To seek new reactivity of metallocorroles, we have previously designed and synthesized a specific carbacorrole ligand, namely N-confused/N-linked corrole analogs.[1] The former analog contains an inverted pyrrole moiety connected at the α and β’-linking positions, and the latter has a peculiar linkage between the pyrrole α-position and the pyrrolic nitrogen site. The distinct [NNNC] coordination environment of these carbacorroles stabilizes unique organometallic species such as a copper(III).[2] In this work, we synthesized novel cobalt complexes with a benzo-fused corrole analog (i.e., benzonorrole). The electronic structure of the resulting complex is highly dependent on the number of axial pyridine ligands. The bis-pyridine adduct complex can be regarded as a diamagnetic Co(III) species. Removal of an axial pyridine ring from the corresponding complex yielded the oxygenated product at the inner carbon site immediately. Unlike the bis-pyridine adduct, the mono-pyridine cobalt complex is a singlet Co(II) ligand radical at the ground state as inferred from various spectroscopic means and DFT calculations. Due to the intrinsic redox-noninnnocent character, the cobalt(II) radical complex exhibits facile reduction nature. On this basis, we finally applied for catalytic hydrogen evolution reaction with these cobalt complexes. [1] Fujino, K.; Hirata, Y.; Kawabe, Y.; Morimoto, T.; Srinivasan, A.; Toganoh, M.; Miseki, Y.; Kudo, A.; Furuta, H. Angew. Chem. Int. Ed. 2011, 50, 6855-6859; Toganoh, M.; Kawabe, Y.; Uno, H.; Furuta, H. Angew. Chem. Int. Ed. 2012, 51, 8753-8756. [2] Maurya, Y.; Noda, K.; Yamasumi, K.; Mori, S.; Uchiyama, T.; Kamitani, K.; Hirai, T.; Ninomiya, K.; Nishibori, M.; Hori, Y.; Shiota, Y.; Yoshizawa, K.; Ishida, M.; Furuta, H. J. Am. Chem. Soc. 2018, 140, 6883-6892.

Background: Patients who complete definitive therapy for primary, stage I-III breast cancer may develop recurrent disease. However, little is known about the outcomes patients experience after recurrence when treated outside of a clinical trial because population-based datasets usually do not capture recurrence status. We describe the overall survival of patients after developing recurrent breast cancer, identify factors independently associated with improved survival, and compare survival for patients with recurrent versus de novo stage IV metastatic disease. Methods: The cancer registries from two Kaiser Permanente (KP) sites participating in the Cancer Research Network, KP Colorado and KP Northwest, provided data on adult women diagnosed 2000-2011 with primary breast cancer and followed through death, disenrollment or study end (12/31/2012). Among patients with stage I-III disease who completed definitive therapy, recurrence was captured via manual chart abstraction. Survival time was calculated from the date of recurrence or the date of de novo stage IV disease. Multivariable modeling identified factors independently associated with restricted mean survival time (RMST) through 7 years, controlling for age, race, income, co-morbidity, year of recurrence, time from primary diagnosis to recurrence, type of recurrence (local vs. regional/distant), use of chemotherapy or radiation at recurrence, and characteristics of the primary cancer that pre-dated recurrence (i.e., primary stage, grade, hormone-receptor status, and use of chemotherapy or radiation therapy for the primary diagnosis). We compared overall survival after developing recurrent versus de novo stage IV disease after matching for age, race, income, co-morbidity and year. Results: From 7,216 breast cancer diagnoses we identified 506 cases of recurrent disease and 219 cases of de novo stage IV disease (7% and 3%, respectively). Most recurrences were regional or distant (81%). From the time of recurrence, median survival was 21 months and 2-year survival was 47%. Factors significantly associated with inferior RMST included regional/distant vs. local recurrence (-35.6 months; P4 years vs. Conclusions: Recurrent breast cancer is at least two-fold more common than de novo stage IV disease. Among patients who develop recurrence, characteristics of the primary cancer and its treatment are associated with survival after recurrence. Survival differences between patients with recurrent and de novo stage IV disease suggest that prognostic estimates and treatment paradigms should be tailored. Citation Format: Hassett MJ, Cronin AM, Carroll NM, Uno H, Hornbrook MC, Ritzwoller D. The incidence of and survival after breast cancer recurrence. [abstract]. In: Proceedings of the Thirty-Eighth Annual CTRC-AACR San Antonio Breast Cancer Symposium: 2015 Dec 8-12; San Antonio, TX. Philadelphia (PA): AACR; Cancer Res 2016;76(4 Suppl):Abstract nr P1-07-07.

Quantum-sized nanocrystalline Si (nc-Si) dots behave as a drift layer which efficiently generates ballistic hot electrons. This is due to little phonon scattering losses in nc-Si at the early stage of injection and subsequent multiple-tunneling cascade through nc-Si dots chain interconnected with thin oxides [1]. At a sufficient electric field, generated ballistic hot electrons are ejected through the surface electrode. In solutions, the nc-Si emitter operates as an active electrode supplying highly reducing electrons. This is applicable to deposition of thin films of metals [2], Si [3], and Ge [4]. Details of this thin film deposition scheme based on the ballistic reduction effects is discussed here including the availability for the deposition of thin Ge and SiGe films. The nc-Si emitter is a kind of MIS diode consisting of a thin film surface electrode, a nanosilicon layer (~1 μm thick), a crystalline silicon wafer substrate, and a back contact. The nc-Si layer includes parallel chains of quantum-sized nanosilicon dots (~3 nm in mean diameter) interconnected with tunnel oxides. When a positive voltage is applied to the surface electrode, electrons injected from the substrate into the nc-Si layer are accelerated toward the outer surface, and then some of them are emitted from the surface electrode as ballistic hot electrons [5]. This planar cold cathode emits energetic and directional electrons. The kinetic energy of electrons can be controlled by the applied voltage. At applied voltages of 15-20 V, for instance, the mean energy of output electrons varies from 5 to 7 eV. Besides in vacuum, the nc-Si emitter operates in atmospheric-pressure gases and even in solutions. Since electrons with an extremely high and electrochemical activity are supplied at relatively low applied voltage, positive ion species are directly reduced. Following the experimental confirmation of the usefulness in aqueous solutions as means for H2 generation and pH control, it has been demonstrated that the ballistic hot electron injection into metal-salt solutions leads to the deposition of thin metal (Cu, Ni, Co, Zn, and so on) films without using any counter electrodes. After the device is mounted in a N2 gas filled glove box, a small amount (5~10 μl) of SiCl4, GeCl4, or their mixture (1:1 in volume) was dripped onto the emission surface, and then the emitter was driven at V b=10-15 V. After the emitter operation for several min without using any counter electrodes, thin films were uniformly deposited on the emitting area in the same way as the previous dipping method. The structure and composition of the deposited films were investigated by transmission electron microscope (TEM), scanning electron microscope (SEM), atomic force microscope (AFM), energy dispersive X-ray (EDX) spectra, X-ray photoelectron spectroscopy (XPS), and secondary ion mass spectroscopy (SIMS). In accordance with TEM analyses, the deposited films are amorphous. The observed EDX spectra indicate that the respective deposited films are composed of Si, Ge, and SiGe. The contamination signals of Cl were below the detection limit of XPS measurements. The result of SIMS of thin SiGe films, the compositional ratio of Si to Ge was about 0.9:0.1. This can be controlled by changing the mixture ratio of SiCl4+GeCl4 solution. In contrast to the electro-plating based on exchange of thermalized electrons, the ballistic electro-reduction proceeds with neither Cl2 evolution nor byproducts generation at the counter electrode. Despite a significantly large electrochemical window between the reduction (Si/Si4+) and oxidation (Cl2/Cl-) potentials, injected electrons have energies sufficient enough for unilateral reduction. Being a low-temperature and clean process, this ballistic electro-reduction mode is attractive as an alternative approach for fabrication of group-IV thin-films, multilayered nanostructures, and devices. This work was partially supported by the JSPS through a Grant-in-Aid for Scientific Research and the FIRST Program and by the NEDO through the R&D Project. References 1. N. Mori, H. Minari, S. Uno, H. Mizuta, and N. Koshida, Appl. Phys. Lett. 98, 062104 (2011). 2. T. Ohta, B. Gelloz, and N. Koshida, Electrochem. Solid-State Letters 13, D73 (2010). 3. T. Ohta, B. Gelloz, and N. Koshida, Appl. Phys. Lett. 102, 022107 (2013). 4. N. Koshida, A. Kojima, T. Ohta, R. Mentek, B. Gelloz, N. Mori, J. Shirakashi, ECS Solid State Lett. 3(5), P57 (2014). 5. N. Koshida, X. Sheng, and T. Komoda, Appl. Surf. Sci. 146, 371 (1999).

This paper describes hardware architecture of mobile robot, design and implementation of Android and Windows applications. It is use Bluetooth communication between mobile phone and mobile robot. The mobile robot is control by applications. Applications send message to the mobile robot to turn left, right or move forward or backward and to stop. The mobile robot is composed of Bluetooth module, Arduino Uno, H-Bridge, two DC motors, jumper wires and Breadboard.

Author(s): Lyons, Jennifer L; Uno, Hajime; Ancuta, Petronela; Kamat, Anupa; Moore, David J; Singer, Elyse J; Morgello, Susan; Gabuzda, Dana | Abstract: ObjectiveMild forms of HIV-associated neurocognitive disorders (HAND) remain prevalent in the era of combination antiretroviral therapy (cART). Although elevated lipopolysaccharide (LPS) and immune activation are implicated in HAND pathogenesis, relationships of LPS and inflammatory markers to mild forms of HAND or impairment in specific cognitive domains are unknown. To examine these relationships, we compared plasma soluble CD14 (sCD14), CCL2, and LPS levels with neurocognitive test scores in a cART era cohort.MethodsWe analyzed plasma from HIV+ subjects (n = 97) with nadir CD4 counts l300 and high frequency of hepatitis C virus coinfection and illicit drug use for relationships between sCD14, CCL2, and LPS levels and neurocognitive test scores.ResultsPlasma sCD14 levels were higher in subjects with test scores indicating global impairment (P = 0.007), particularly in attention and learning domains (P = 0.015 and P = 0.03, respectively), regardless of HAND diagnosis. Plasma sCD14 levels correlated inversely with global, attention, and learning T scores (P = 0.036, 0.047, and 0.007, respectively) and yielded higher area under receiver operating characteristic values for predicting impaired scores than single-marker models based on plasma or cerebrospinal fluid viral load or CD4 count (area under receiver operating characteristic values = 0.71, 0.81, and 0.71, respectively) and in 4-marker models based on plasma sCD14 and 3 conventional markers compared with the 3-marker models.ConclusionsPlasma sCD14 is a biomarker associated with impaired neurocognitive testing in attention and learning domains in HIV-infected individuals with advanced disease, suggesting involvement of cortical and limbic pathways by inflammatory processes in the cART era. Plasma sCD14 is a potential biomarker to monitor HAND progression and therapeutic responses.

Polyoxometalate (POM) derivatives have been reported to show various specific electronic properties. For example, (NH4)6V10O28 and H7SiW9V3O40 show negative differential resistance (NDR) when measured by scanning tunneling spectroscopic (STS) technique in air.1,2 We have reported that a composite of H3PMo12O40 with single-walled carbon nanotubes (SWNT) showed complex phenomena depending on the size of the POM nanoparticles. When the size of the POM was smaller than ~6 nm with a semiconducting SWNT, the composite showed rectification with positive bias suppression. By contrast, if the size of the POM was larger, the suppression was observed at negative bias. However, when the SWNT is metallic, the suppression occurred at the opposite bias.3 There are several POM/porphyrin derivatives or analogues reported, saddle-distorted Mo(V)-dodecaphenylporphyrin with Keggin-type H2SiW12O40,4 cyclo[8]pyrrole with H4SiW12O40,5 tetraphenylporphyrin (TPP) with SW10V2O40.6 The electronic properties of these complexes are interesting to measure in macro-scale and in single molecule-scale, because of the versatile electronic behaviors are expected from multi redox characters of POM cores tuned by the surrounding porphyrin derivatives. The single crystal structure of [H4TPP][SV2W10O40] was successfully determined, in which one POM anion is surrounded by four H4TPP cations. Although this complex is dissociated in solution, the casted sample retains crystalline structures partially as observed by the powder X-ray diffraction study. Devices were made by casting the solution of the complex on Au electrodes with 5 μm gap. The current-voltage curve at ambient conditions showed broad negative differential resistance (NDR) with large hysteresis. The impedance measurements between 10-1 to 106 Hz at 0.0 to 3.0 V DC bias indicated that in low frequency range ( 10Hz) the impedance is almost independent on voltage. The impedance results indicate that non-linear NDR behavior observed in DC measurement is because of a slow process of the carrier movement, probably by ionic conductance. References (1) Ogawa, T.; Handayani, M. In Molecular Architectonics; Ogawa, T., Ed.; Springer Nature: Switzerland, 2017, p 419. (2) Watson, B. A.; Barteau, M. A.; Haggerty, L.; Lenhoff, A. M.; Weber, R. S. Langmuir 1992, 8, 1145. (3) Hong, L.; Tanaka, H.; Ogawa, T. J. Mat. Chem., C 2013, 1, 1137. (4) Yokoyama, A.; Kojima, T.; Ohkubo, K.; Fukuzumi, S. Chem. Commun. 2007, 3997. (5) Okujima, T.; Matsumoto, H.; Mori, S.; Nakae, T.; Takase, M.; Uno, H. Tetrahedron Lett. 2016, 57, 3160. (6) Shi, Z. H.; Zhou, Y. S.; Zhang, L. J.; Mu, C. C.; Ren, H. Z.; ul Hassan, D.; Yang, D.; Asif, H. M. RSC Adv. 2014, 4, 50277. Figure 1

Enantiomerically pure â-amino alcohols have been extensively used as building blocks for the syntheses of pharmaceuticals1 and insecticidal agents,2 as chiral ligands in asymmetric catalysis,3 or as auxiliaries4 and resolving agents5 in asymmetric synthesis. Furthermore, they can be converted to chiral oxazoline ligands, which show tremendous utility in various asymmetric catalytic processes.6 The broad application of amino alcohol derivatives has generated considerable interest in developing efficient synthetic routes to these compounds.7 Such amino alcohols generally are obtained by reduction of the corresponding R-amino acids or esters.8 However, not all of the precursor R-amino acids are readily available, and sometimes low yields are observed in this reduction. To overcome these deficiencies, several alternative asymmetric synthetic methods have been developed.9 In principle, asymmetric catalytic hydrogenation of protected â-hydroxy enamides is a practical way to generate such amino alcohols. Although high enantioselectivities and reactivities have been reported for the asymmetric hydrogenation of dehydroamino acids,10 there have been no reports describing the synthesis of â-amino alcohols via asymmetric catalytic hydrogenation of enamides as illustrated in Scheme 1. Herein, we describe the first highly enantioselective, practical synthesis of â-amino alcohols using BICP-Rh and Me-DuPhos-Rh complexes as the catalysts [BICP, 2,2′-bis(diphenylphosphino)-1,1′-dicyclopentane; DuPhos, 1,2-bis(2,5-dialkylphospholane)benzene]. The key elements of this method involve: (a) facile synthesis of R-hydroxy ketones, (b) new enamide formation procedure from oximes using Fe/ Ac2O in DMF as reagents, and (c) high enantioselectivity in the hydrogenation step. The basic strategy for the synthesis of chiral â-amino alcohols involves asymmetric hydrogenation of R-arylenamides with a MOM-protected â-hydroxy group.11 Rhcatalyzed asymmetric hydrogenation must tolerate the E and Z isomers of these enamides since preparation and isolation of the isomerically pure E and Z isomers are difficult. Another practical issue in this approach is the formation of the â-hydroxy-substituted enamide substrates. We have prepared these MOM-protected â-hydroxy-substituted enamides in gram quantities from readily available 2-haloacetophenone derivatives 3 as outlined in Scheme 2.11 The first step involves synthesis of 2-hydroxyacetophenone derivatives 4 through nucleophilic attack on corresponding 2-haloacetophenone by sodium formate. An in situ hydrolysis reaction then follows. Nucleophiles other than formate such as acetate or hydroxide are not desirable for the synthesis of 2-hydroxyacetophenone derivatives. Protection of the hydroxy group with methoxymethyl chloride (MOMCl) went smoothly, giving MOM-protected keto alcohol 5 in good yield. The key step in the synthesis of enamide 1 is the conversion of the corresponding oxime 6 of the MOMprotected keto alcohol by Fe/Ac2O in DMF. The reported † The Pennsylvania State University. ‡ DuPont Agricultural Products. (1) (a) Roemer, D.; Buescher, H. H.; Hill, R. C.; Pless, J.; Bauer, W.; Cardinaux, F.; Closse, A.; Hauser, D.; Huguenin, R. Nature 1977, 268, 547. (b) TenBrink, R. E. J. Org. Chem. 1987, 52, 418. (c) Fincham, C. I.; Higginbottom, M.; Hill, D. R.; Horwell, D. C.; O’Toole, J. C.; Ratcliffe, G. S.; Rees, D. C.; Roberts, E. J. Med. Chem. 1992, 35, 1472. (d) Auvin-Guette, C.; Rebuffat, S.; Prigent, Y.; Bodo, B. J. Am. Chem. Soc. 1992, 114, 2170. (2) Wu, S.; Takeya, R.; Eto, M.; Tomizawa, C. J. J. Pestic. Sci. 1987, 12, 221. (3) (a) Soai, K.; Niwa, S. Chem. Rev. 1992, 92, 833. (b) Butsugan, Y.; Araki, S.; Watanabe, M. Ferrocenes; VCH: Weinheim, 1995; pp 143-169. (c) Takehara, J.; Hashiguchi, S.; Fujii, A.; Inoue, S.-I.; Ikariya, T.; Noyori, R. Chem. Commun. 1996, 233. (d) Peper, V.; Martens, J. Chem. Ber. 1996, 129, 691. (4) (a) Evans, D. A. in Asymmetric Synthesis; Morrison, J. D., Ed.; Academic Press: Orlando, 1984; Vol. 3, p 1. (b) Heathcock, C. H. In Asymmetric Synthesis; Morrison, J. D., Ed.; Academic Press: Orlando, 1984; Vol. 3, p 111. (c) Blaser, H.-U. Chem. Rev. 1992, 92, 935 and references cited therein. (d) Ghosh, A. K.; Onishi, M. J. Org. Chem. 1996, 61, 2527. (e) Meyers, A. I.; Brengel, G. P. J. Chem. Soc., Chem. Commun. 1997, 1 and references therein. (5) (a) Sawayama, T.; Tsukamoto, M.; Sasagawa, T.; Naruto, S.; Matsumoto, J.; Uno, H. Chem. Pharm. Bull. 1989, 37, 1382. (b) Kawai, M.; Omori, Y.; Yamamura, H.; Butsugan, Y. Tetrahedron: Asymmetry. 1992, 3, 1019. (6) For a few related reviews, see: (a) Pfaltz, A. Acc. Chem. Res. 1993, 26, 339. (b) Ager, D.; Prakash, I.; Schaad, D. R. Aldrichim. Acta 1997, 30, 3. (c) Puts, R. D.; Chao, J.; Spagh, D. Y. Synthesis 1997, 431. (d) Ghosh, A. K.; Mathivanan, P.; Cappiello, J. Tetrahedron: Asymmetry. 1998, 9, 1 and references therein. (7) Ager, D. J.; Prakash, I.; Schaad, D. R. Chem. Rev. 1996, 96, 835 and references therein. (8) (a) Giannis, A.; Sandhoff, K. Angew. Chem., Int. Ed. Engl. 1989, 28, 218. (b) Pridgen, L. N.; Prol, J., Jr.; Alexander, B.; Gillyard, L. J. Org. Chem. 1989, 54, 3231. (c) Gage, J. R.; Evans, D. A. Org. Synth. 1990, 68, 77. (d) Abiko, A.; Masamune, S. Tetrahedron Lett. 1992, 33, 5517. (e) McKennon, M. J.; Meyers, A. I. J. Org. Chem. 1993, 58, 3568. (f) Dickman, D. A.; Meyers, A. I.; Smith, G. A.; Gawley, L. Organic Syntheses; Wiley: New York, 1990; Collect, Vol. VII, p 530. (g) Nicolas, E.; Rusell, K. C.; Hruby, V. J. J. Org. Chem. 1993, 58, 766. (9) (a) Ager, D. J.; East, M. B. Tetrahedron 1993, 49, 5683. (b) Harris, C. E.; Fisher, G. B.; Beardsley, D.; Lee, L. Goralski, C. T.; Nicholson, L. W.; Singaram, B. J. Org. Chem. 1994, 59, 7746 and references therein. (c) Tillyer, R. D.; Boudreau, C.; Tschaen, D.; Dolling, U.-H.; Reider, P. J. Tetrahedron Lett. 1995, 36, 4337. (d) Fisher, G. B.; Goralski, C. T.; Nicholson, L. W.; Hasha, D. L.; Zakett, D.; Singaram, B. J. Org. Chem. 1995, 60, 2026. (e) Chang, H. T.; Sharpless, K. B. Tetrahedron Lett. 1996, 37, 3219. (f) Reddy, K. L.; Sharpless, K. B. J. Am. Chem. Soc. 1998, 120, 1207 and references therein. (10) (a) Ojima, I., Ed. Catalytic Asymmetric Synthesis; VCH: New York, 1993. (b) Sheldon, R. A. Chirotechnology; Marcel Dekker: New York, 1993. (c) Noyori, R. Asymmetric Catalysis In Organic Synthesis; John Wiley & Sons: New York, 1994. (11) The initial demonstration of this strategy was carried out by A. Casalnuovo, K. M. Sun, R. Shapiro, T. Pahutski, M. Angiolelli, and J. Feaster using Me-DuPhos-Rh and Me-BPE-Rh catalyst systems. DuPont Agrichicultural Products, private communication. Scheme 1

Electrochemically anodized nano-crystalline Si (nc-Si) behaves as a functional material with a confined structure. In the electron transport through a chain of nc-Si dots, phonon scattering losses are minimized due to discrete energy levels in the conduction band, and then ballistic electrons are generated at the early stage of injection [1]. This induces efficient ballistic hot electron emission from an nc-Si diode. It is possible to use this emitter not only in vacuum, but also in atmospheric-pressure gases and solutions [2]. Extremely lowered thermal conductivity and heat capacity of the nc-Si layer [3], on the other hand, significantly enhances thermo-acoustic effect. In contrast to the conventional piezoelectric transducer, the thermally induced acoustic emission exhibits no resonant peaks in the frequency response. Here we discuss topics in the studies on these subjects. The nc-Si emitter is a kind of MIS diode consisting of a thin film surface electrode, an nc-Si layer (~1 μm thick), a crystalline silicon wafer substrate, and a back contact. The nc-Si layer includes chains of nc-Si dots (~3 nm in mean diameter) interconnected with tunnel oxides. When a positive voltage is applied to the surface electrode, electrons are accelerated in the nc-Si layer toward the outer surface, and then some of them are emitted through the surface electrode as ballistic hot electrons with a small angle dispersion (±10°with respect to the normal). At applied voltages of 12-20 V, the mean energy of output electrons reaches 3-7 eV [2]. One possible application of the nc-Si emitter is the use as an exposure source of multibeam parallel lithography. The emitter array is fabricated on a Si substrate by planar processes. Each emitter with an active area of 10 μm☐ is connected to an active matrix driving circuit through a TSV technique. The evaluation was performed with the 1:1 exposure test system, in which an EB-resist coated target wafer was placed at about 4 mm distance from the emitter surface. The wafer was grounded, and emitter surface was set at -5 kV for accelerating the electron. It has been demonstrated that the selected emitter patterns is delineated well corresponding to the activated emitters [4]. The integrated nc-Si emitter array is compatible with the active-matrix drive for multi-beam massive parallel lithography. Another application is thin film deposition using the reducing activity of ballistic hot electrons. When the emitter is driven in metal-salt solutions such as CuSO4, CuCl2, NiCl2, SiCl4, and GeCl4, injected electrons directly reduce Cu2+, Si4+ and Ge4+ ions, and then thin Cu films [5] and amorphous Si and Ge films [6,7] are grown on the emitting area with neither contaminations nor byproducts. Based on this observation, a printing scheme has been employed, in which a target substrate is separately located in close proximity to the emitter. A gap between the nc-Si emitter and the target substrate is controlled by a piezoelectric actuator depending the ambient (N2 gas) pressure. Emitted electrons hit metal-salt solutions on the substrate leading to the reducing reaction. The first printing experiment was sought for deposition of thin metal film, where an extremely small amount of CuSO4 or CuCl2 solution was coated on a single-crystalline Si wafer and used as a target substrate. It has been observed that thin Cu films are deposited on the irradiated area. The broad-band flat emissivity of the nc-Si thermo-acoustic device is useful for developing low-distortion digital speaker [8] and reproducing complicated ultrasonic communication calls between mice [9]. References 1. N. Mori, H. Minari, S. Uno, H. Mizuta, and N. Koshida, Appl. Phys. Lett. 98, 062104 (2011). 2. N. Koshida, T. Ohta, B. Gelloz, and A. Kojima, Curr. Opin. Solid State Mater. Sci. 15, 183 (2011). 3. N. Koshida, Thermal Properties of Porous Silicon, in “Handbook of Porous Silicon”, ed. L. Canham (Springer, 2015), pp 207-212. 4. N. Koshida et al, Proc. SPIE Symp. on Advanced Lithography, Vol. 9423, 942313 (2015). 5. T. Ohta, B. Gelloz, and N. Koshida, ECS Solid State Lett. 13, D73 (2010) 6. N. Koshida, A. Kojima, T. Ohta, R. Mentek, B. Gelloz, N. Mori, and J. Shirakashi, ECS Solid State Lett. 3(5), P57 (2014). 7. R. Suda, M. Yagi, A. Kojima, R. Mentek, N. Mori, J. Shirakashi, and N. Koshida, Jpn. J. Appl. Phys. 54, 04DH11 (2015). 8. N. Koshida, D. Hippo, M. Mori, H. Yanazawa, H. Shinoda, and T. Shimada, Appl. Phys. Lett. 102, 123504 (2013). 9. A. Asaba, S. Okabe, M. Nagasawa, M. Kato, N. Koshida, K. Mogi, and T. Kikusui, PLoS One Vol. 9(2), e87186 (2014).

Background The World Health Organization Fracture Risk Assessment Tool (FRAX®) algorithm can be used to estimate 10-year probabilities of hip and major osteoporotic fractures. This tool has not yet been validated in Japanese patients with rheumatoid arthritis (RA). Previously, we [1,2] and others have reported a significant association between the Health Assessment Questionnaire Disability Index (HAQ-DI) and clinical fracture risk in patients with RA. This has generated interest in the possible role the HAQ-DI could play in improving fracture risk assessment for patients with RA [3]. Objectives The aim of this study was to evaluate the prognostic accuracy of the Japanese version of FRAX to predict the 10-year probability of hip and major osteoporotic fractures in Japanese patients with RA, and investigate whether the HAQ-DI can further improve the prediction of hip and major osteoporotic fractures. Methods We analyzed the database of the Institute of Rheumatology Rheumatoid Arthritis (IORRA) study, our large prospective observational cohort study in Japanese patients with RA. IORRA study subjects included 3,095 women and 703 men with RA ranging in age from 40 to 90 years. The mean (± standard deviation) age was 60.6±9.6 years. Self-reported major osteoporotic fractures of the hip, vertebrae, humerus, and wrist were verified using patient medical records. The association of FRAX with fractures was evaluated by the Cox model, and C-statistics [4] were used in the risk prediction model to account for censored survival data. The Japanese version of HAQ-DI (J-HAQ-DI) was used in the assessment in conjunction with FRAX, without considering bone mineral density (BMD) values, and C-statistics were used for the 10-year risk calculated by the Cox model. Results A total of 3,798 Japanese patients with RA were followed for an average of 5.8 years. Using FRAX without BMD, the mean 10-year predicted fracture probability for hip and major osteoporotic fractures was 5.3% and 14.5%, respectively. Among the patients, 52 (1.4%) and 216 (5.7%) presented with hip and major osteoporotic fractures (including n=85 vertebral, n=41 humeral, n=38 distal radial, and n=52 hip fractures), respectively. For hip fractures, the C-statistic was 0.735 (95% CI: 0.665, 0.804) for the statistical model prediction based on both J-HAQ-DI and FRAX, and it was 0.688 (95% CI: 0.613, 0.762) for FRAX alone. For major osteoporotic fractures, the C-statistic was 0.678 (95% CI: 0.636, 0.719) for both J-HAQ-DI and FRAX, and 0.664 (95% CI: 0.624, 0.704) for FRAX alone. Conclusions We evaluated the performance of FRAX in Japanese patients with RA using our prospective observational cohort study data. Our results were similar to those in other previously reported longitudinal studies evaluating FRAX. The HAQ-DI appears to improve hip fracture risk assessment when used in conjunction with this conventional risk assessment tool in patients with RA. References Furuya T, et al. J Rheumatol. 2007; 34(2):303-10. Furuya T, et al. Osteoporos Int. 2013; 24(4):1257-65. Broy SB, et al. J Clin Densitom. 2011; 14(3):184-9. Uno H, et al. Stat Med. 2011; 30(10):1105-17. Acknowledgements We thank all members of the Institute of Rheumatology, Tokyo Women9s Medical University for the successful management of the IORRA cohort. This work was supported in part by grants-in-aid for scientific research from the Japan Osteoporosis Foundation to TF. Disclosure of Interest T. Furuya: None declared, E. Inoue: None declared, K. Ochi: None declared, O. Ishida: None declared, A. Taniguchi: None declared, S. Momohara: None declared, H. Yamanaka Grant/research support: Abbott, AbbVie, Asahikasei, Astellas, AstraZeneca, Bristol-Myers Squib, Chugai, Daiichi Sankyo, Eisai, GlaxoSmithKline, Janssen, Mitsubishi Tanabe, MSD, Nippon Kayaku, Pfizer, Santen, Taishotoyama, Takeda, Teijin, Consultant for: Abbott, AbbVie, Astellas, AstraZeneca, Bristol-Myers Squib, Chugai, Daiichi Sankyo, Eisai, Mitsubishi Tanabe, Nippon Kayaku, Pfizer, Takeda, Teijin, Speakers bureau: Abbott, AbbVie, Astellas, Bristol-Myers Squib, Chugai, Eisai, Mitsubishi Tanabe, Pfizer, Takeda, Teijin DOI 10.1136/annrheumdis-2014-eular.1579

Acenes and their derivatives are commonly employed in organic electronics studies. However, they often lack the required solubility for solution deposition, which considerably limits their applicability to cost-effective devices. One of the proposed methodologies to evade this obstacle is the precursor approach, in which a soluble precursor is first deposited by a solution process then converted to a target acene compound within resulting thin films. The focus of this study is to develop solution-processed thin-film organic photovoltaic (OPV) cells by employing α-diketone derivatives of acenes in active-layer deposition by the precursor approach.1 α-Diketone-type precursors are characterized by clean, quantitative conversion to corresponding acene compounds by visible-light irradiation even in the solid state. For example, anthradithiophene (ADT) can be obtained from its α-diketone-type precursor (ADTDK) in thin films, allowing solution-process fabrication of planar-junction OPV cells based on ADT as a p-type semiconductor. The maximum photo-conversion efficiency (PCE) of 1.54% was obtained when PC71BM was used as an n-type semiconductor.2 In another case, dithienylanthracene (DTAnt) was generated in thin films from its precursor DTAntDK, and the combination with PC71BM led to 1.66% PCE in a p–i–n type OPV cell. Results with more p-extended systems will also be presented. Suzuki, M.; Aotake, T; Yamaguchi Y.; Noguchi, N.; Nakano, H.; Nakayama, K.; Yamada, H. J. Photochem. Photobiol. C. 2014, 18, 50–70. Yamada, H.; Yamaguchi, Y.; Katoh, R.; Motoyama, Y.; Aotake, T.; Kuzuhara, D.; Suzuki, M.; Okujima, T.; Uno, H.; Aratani, N.; Nakayama, K. Chem. Commun. 2013, DOI: 10.1039/C3CC46178E.

Enantiomerically pure â-amino alcohols have been extensively used as building blocks for the syntheses of pharmaceuticals1 and insecticidal agents,2 as chiral ligands in asymmetric catalysis,3 or as auxiliaries4 and resolving agents5 in asymmetric synthesis. Furthermore, they can be converted to chiral oxazoline ligands, which show tremendous utility in various asymmetric catalytic processes.6 The broad application of amino alcohol derivatives has generated considerable interest in developing efficient synthetic routes to these compounds.7 Such amino alcohols generally are obtained by reduction of the corresponding R-amino acids or esters.8 However, not all of the precursor R-amino acids are readily available, and sometimes low yields are observed in this reduction. To overcome these deficiencies, several alternative asymmetric synthetic methods have been developed.9 In principle, asymmetric catalytic hydrogenation of protected â-hydroxy enamides is a practical way to generate such amino alcohols. Although high enantioselectivities and reactivities have been reported for the asymmetric hydrogenation of dehydroamino acids,10 there have been no reports describing the synthesis of â-amino alcohols via asymmetric catalytic hydrogenation of enamides as illustrated in Scheme 1. Herein, we describe the first highly enantioselective, practical synthesis of â-amino alcohols using BICP-Rh and Me-DuPhos-Rh complexes as the catalysts [BICP, 2,2′-bis(diphenylphosphino)-1,1′-dicyclopentane; DuPhos, 1,2-bis(2,5-dialkylphospholane)benzene]. The key elements of this method involve: (a) facile synthesis of R-hydroxy ketones, (b) new enamide formation procedure from oximes using Fe/ Ac2O in DMF as reagents, and (c) high enantioselectivity in the hydrogenation step. The basic strategy for the synthesis of chiral â-amino alcohols involves asymmetric hydrogenation of R-arylenamides with a MOM-protected â-hydroxy group.11 Rhcatalyzed asymmetric hydrogenation must tolerate the E and Z isomers of these enamides since preparation and isolation of the isomerically pure E and Z isomers are difficult. Another practical issue in this approach is the formation of the â-hydroxy-substituted enamide substrates. We have prepared these MOM-protected â-hydroxy-substituted enamides in gram quantities from readily available 2-haloacetophenone derivatives 3 as outlined in Scheme 2.11 The first step involves synthesis of 2-hydroxyacetophenone derivatives 4 through nucleophilic attack on corresponding 2-haloacetophenone by sodium formate. An in situ hydrolysis reaction then follows. Nucleophiles other than formate such as acetate or hydroxide are not desirable for the synthesis of 2-hydroxyacetophenone derivatives. Protection of the hydroxy group with methoxymethyl chloride (MOMCl) went smoothly, giving MOM-protected keto alcohol 5 in good yield. The key step in the synthesis of enamide 1 is the conversion of the corresponding oxime 6 of the MOMprotected keto alcohol by Fe/Ac2O in DMF. The reported † The Pennsylvania State University. ‡ DuPont Agricultural Products. (1) (a) Roemer, D.; Buescher, H. H.; Hill, R. C.; Pless, J.; Bauer, W.; Cardinaux, F.; Closse, A.; Hauser, D.; Huguenin, R. Nature 1977, 268, 547. (b) TenBrink, R. E. J. Org. Chem. 1987, 52, 418. (c) Fincham, C. I.; Higginbottom, M.; Hill, D. R.; Horwell, D. C.; O’Toole, J. C.; Ratcliffe, G. S.; Rees, D. C.; Roberts, E. J. Med. Chem. 1992, 35, 1472. (d) Auvin-Guette, C.; Rebuffat, S.; Prigent, Y.; Bodo, B. J. Am. Chem. Soc. 1992, 114, 2170. (2) Wu, S.; Takeya, R.; Eto, M.; Tomizawa, C. J. J. Pestic. Sci. 1987, 12, 221. (3) (a) Soai, K.; Niwa, S. Chem. Rev. 1992, 92, 833. (b) Butsugan, Y.; Araki, S.; Watanabe, M. Ferrocenes; VCH: Weinheim, 1995; pp 143-169. (c) Takehara, J.; Hashiguchi, S.; Fujii, A.; Inoue, S.-I.; Ikariya, T.; Noyori, R. Chem. Commun. 1996, 233. (d) Peper, V.; Martens, J. Chem. Ber. 1996, 129, 691. (4) (a) Evans, D. A. in Asymmetric Synthesis; Morrison, J. D., Ed.; Academic Press: Orlando, 1984; Vol. 3, p 1. (b) Heathcock, C. H. In Asymmetric Synthesis; Morrison, J. D., Ed.; Academic Press: Orlando, 1984; Vol. 3, p 111. (c) Blaser, H.-U. Chem. Rev. 1992, 92, 935 and references cited therein. (d) Ghosh, A. K.; Onishi, M. J. Org. Chem. 1996, 61, 2527. (e) Meyers, A. I.; Brengel, G. P. J. Chem. Soc., Chem. Commun. 1997, 1 and references therein. (5) (a) Sawayama, T.; Tsukamoto, M.; Sasagawa, T.; Naruto, S.; Matsumoto, J.; Uno, H. Chem. Pharm. Bull. 1989, 37, 1382. (b) Kawai, M.; Omori, Y.; Yamamura, H.; Butsugan, Y. Tetrahedron: Asymmetry. 1992, 3, 1019. (6) For a few related reviews, see: (a) Pfaltz, A. Acc. Chem. Res. 1993, 26, 339. (b) Ager, D.; Prakash, I.; Schaad, D. R. Aldrichim. Acta 1997, 30, 3. (c) Puts, R. D.; Chao, J.; Spagh, D. Y. Synthesis 1997, 431. (d) Ghosh, A. K.; Mathivanan, P.; Cappiello, J. Tetrahedron: Asymmetry. 1998, 9, 1 and references therein. (7) Ager, D. J.; Prakash, I.; Schaad, D. R. Chem. Rev. 1996, 96, 835 and references therein. (8) (a) Giannis, A.; Sandhoff, K. Angew. Chem., Int. Ed. Engl. 1989, 28, 218. (b) Pridgen, L. N.; Prol, J., Jr.; Alexander, B.; Gillyard, L. J. Org. Chem. 1989, 54, 3231. (c) Gage, J. R.; Evans, D. A. Org. Synth. 1990, 68, 77. (d) Abiko, A.; Masamune, S. Tetrahedron Lett. 1992, 33, 5517. (e) McKennon, M. J.; Meyers, A. I. J. Org. Chem. 1993, 58, 3568. (f) Dickman, D. A.; Meyers, A. I.; Smith, G. A.; Gawley, L. Organic Syntheses; Wiley: New York, 1990; Collect, Vol. VII, p 530. (g) Nicolas, E.; Rusell, K. C.; Hruby, V. J. J. Org. Chem. 1993, 58, 766. (9) (a) Ager, D. J.; East, M. B. Tetrahedron 1993, 49, 5683. (b) Harris, C. E.; Fisher, G. B.; Beardsley, D.; Lee, L. Goralski, C. T.; Nicholson, L. W.; Singaram, B. J. Org. Chem. 1994, 59, 7746 and references therein. (c) Tillyer, R. D.; Boudreau, C.; Tschaen, D.; Dolling, U.-H.; Reider, P. J. Tetrahedron Lett. 1995, 36, 4337. (d) Fisher, G. B.; Goralski, C. T.; Nicholson, L. W.; Hasha, D. L.; Zakett, D.; Singaram, B. J. Org. Chem. 1995, 60, 2026. (e) Chang, H. T.; Sharpless, K. B. Tetrahedron Lett. 1996, 37, 3219. (f) Reddy, K. L.; Sharpless, K. B. J. Am. Chem. Soc. 1998, 120, 1207 and references therein. (10) (a) Ojima, I., Ed. Catalytic Asymmetric Synthesis; VCH: New York, 1993. (b) Sheldon, R. A. Chirotechnology; Marcel Dekker: New York, 1993. (c) Noyori, R. Asymmetric Catalysis In Organic Synthesis; John Wiley & Sons: New York, 1994. (11) The initial demonstration of this strategy was carried out by A. Casalnuovo, K. M. Sun, R. Shapiro, T. Pahutski, M. Angiolelli, and J. Feaster using Me-DuPhos-Rh and Me-BPE-Rh catalyst systems. DuPont Agrichicultural Products, private communication. Scheme 1