Near-field double-spot photolithography with subwavelength spacing

We theoretically report a method of the near-field double-spot subwavelength-photolithography by attaching an optical anisotropic metamaterial (OAM) and polymer composite film to a solid immersion lens (SIL). The OAM made up of metallic nanowires embedded in a dielectric matrix can realize all-angle negative refraction for TM waves in the visible regime. When the SIL near-field photolithography system with a nanoscale OAM-polymer composite film is illuminated by a linearly-polarized beam, the longitudinal component of electric field in the focal region of the objective is largely enhanced by surface plasmons and the transverse component is suppressed. Consequently, a spot in the conventional near-field photolithography system with a bare SIL is split into two spots with subwavelength spacing. If the present focusing system with an OAM-polymer film is used to near-field photolithography, a subwavelength-spacing (wavelength/5) and deep photoetching pattern can be achieved and, compared with the conventional single-spot photolithography, the photoetching speed can be doubled.     

Expedient synthesis of α,α-dimethyl-β-hydroxy carbonyl scaffolds via Evans' aldol reaction with a tertiary enolate

An efficient synthetic methodology for 3-hydroxy-2,2-dimethyloctynoic acid (DHOYA) and several variants, which are increasingly common fragments encountered in bioactive marine cyanobacterial metabolites, was developed. These fragments were obtained in three steps via a tertiary aldol reaction utilizing an Evans’ chiral auxiliary to afford the desired stereochemistry at the β-hydroxy carbon. Thus far, this methodology has been successfully applied in determination of the absolute stereochemistry of eight cyanobacterial natural products, including the VGSC activator palymramide A.     

VUV-UV-visible luminescence of Nd3+, Er3+ and Tm3+ in LiLuF4 single crystal host

An overlook of absorption and luminescence characteristics of Nd³⁺, Er³⁺ and Tm³⁺ centers in LiLuF₄ single crystal is provided. Single crystal doped with the mentioned RE ions were prepared by micro-pulling-down technique in the form of few cm long rods with the diameter of about 2 mm. Excitation and emission spectra and fast decay kinetics in VUV spectral region were measured at SUPERLUMI station at synchrotron DESY, Hamburg and characterization was further completed in UV-visible region at conventional spectrophotometers. Observed absorption and emission peaks are ascribed to the 5d–4f and 4f–4f optical transitions in the doped rare earth ions. Concentration dependence of the decay kinetics is discussed.     

Photo-induced polarity alteration and photodegradation behavior of O-acryloyl acetophenone oxime and phenyl vinyl ketone copolymers

Photochemical reactions of copolymers of O-acryloyl acetophenone oxime (AAPO) and phenyl vinyl ketone (PVK) in the solid phase were investigated. The decrease of molecular weight of these copolymers in the photolysis was limited compared to that of PVK homopolymer. Results of IR and elemental analyses showed that pendant acyloxyimino (AOI) groups were phototransformed into the pendant amino groups. This behavior suggests that PVK units in this copolymer worked as a sensitizer for the photolysis of AOI groups. The energy transfer from PVK units to AOI groups was confirmed to proceed via an excited triplet state by the quenching study of phosphorescence of a PVK homopolymer by a model compound, O-cyclohexanecarbonyl acetophenone oxime. Dissolution alteration of AAPO copolymers before and after irradiation was also investigated. © 1996 John Wiley & Sons, Inc.     

Radical-based transformation of vicinal diols to olefins via thioxocarbamate derivatives: a simple approach to 2′,3′-didehydro-2′,3′-dideoxynucleosides

The bis-O-thioxocarbamate derivatives obtained from the reaction of vicinal diols with phenyl isothiocyanate are shown to be reduced with tris(trimethylsilyl)silane in the presence of azobisisobutyronitrile to afford the corresponding olefins in good yields. In this way, 2′,3′-didehydro-2′,3′-dideoxy analogs of adenosine, guanosine, inosine, cytidine and uridine were prepared by the radical-based deoxygenation of the corresponding ribonucleosides via the bis-O-thioxocarbamate derivatives.     

Study of reaction of finely-divided silica with barium carbonate by TG and DTA

The reaction between equimolar silica and barium carbonate powders in oxygen, air or carbon dioxide was studied by means of TG and DTA. The particle size of the silica showed appreciable effects on the reactivity of the silica, on the activation energy of the reaction, and on the formation of an intermediate silicate, Ba₂SiO₄. The formation of Ba₂SiO₄ is depressed by a decrease in the silica particle size or by an increase in the partial pressure of carbon dioxide in the ambient atmosphere.

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Zusammenfassung Die Reaktion zwischen äquimolaren Siliciumdioxid und Bariumcarbonatpulvern wurde in Sauerstoff, Luft oder Kohlendioxid mittels TG und DTA studiert. Die Teilchengröße von Siliciumdioxid zeigte eine bedeutende Wirkung auf die Reaktivität desselben und auf die Aktivierungsenergie der Reaktion, sowie die Bildung eines intermediären Silikats der Formel Ba₂SiO₄. Die Bildung des Ba₂SiO₄ wird durch die Abnahme der Teilchengröße des Siliciumdioxid sowie durch die Zunahme des Partialdrucks des Kohlendioxids in der Atmosphäre zurückgedrängt.

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Résumé On a étudié, par TG et ATD, la réaction de mélanges équimolaires pulvérulents de silice et de carbonate de baryum dans l'oxygène, l'air ou l'anhydride carbonique. La taille des particules de silice influence considérablement la réactivité de celle-ci, l'énergie d'activation de la réaction ainsi que la formation d'un silicate intermédiaire, Ba₂SiO₄. La diminution des dimensions des particules de silice ou l'augmentation de la pression partielle de l'anhydride carbonique réduisent la formation de Ba₂SiO₄.

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, , . , , , Ba₂SiO₄. Ba₂SiO₄ .

     

A new class of sulfido/oxo(dithiolene)-molybdenum(IV) complexes derived from sulfido/oxo-bis(tetrasulfido)molybdenum(IV) anions

Mono(dithiolene)sulfidomolybdenum(IV) complexes, [MoS(S4)(bdt)](2-) (2) and [MoS(S4)(bdtCl2)](2-) (3) (1,2-benzenedithiolate = bdt, 3,6-dichloro-1,2-benzenedithiolate = bdtCl2), were prepared by the substitution reaction of a tetrasulfido ligand in known [MoS(S4)2](2-) (1) with the corresponding dithiol. Complexes 2 and 3 were irreversibly oxidized to give bis(mu-sulfido) dimolybdenum(V) species, {[MoS(bdt)]2(mu-S)2}(2-) (4) and {[MoS(bdtCl2)]2(mu-S)2}(2-) (5), in aerobic acetonitrile. Mono(dithiolene)oxomolybdenum(IV) complexes, [MoO(S4)(bdt)](2-) (7) and [MoO(S4)(bdtCl2)](2-) (8), that are oxo derivatives of 2 and 3 were also synthesized from a known [MoO(S4)2](2-) (6) of an oxo derivative of 1 and the corresponding dithiol. Further, the electrophilic addition of dimethyl acetylenedicarboxylate to 7 gave [MoO(bdt)(S2C2(COOMe)2)](2-) (9), and ligand substitution of the tetrasulfido group of 7 with bdt and bdtCl2 yielded [MoO(bdt)2](2-) ( 10) and [MoO(bdt)(bdtCl2)](2-) (11), respectively. New sulfido/oxo molybdenum complexes were characterized by (1)H NMR, IR, ESI-MS, Raman, and UV-vis spectroscopies; cyclic voltammetry; and elemental analysis, and crystal structures of 2, 3, 5, 7, and 8 were determined by X-ray analysis.     

Improved resolution for aerial imaging by retro-reflection with two transparent spheres

Optical Review - This paper proposes a method to improve the modulation transfer function (MTF) of aerial images by combining an aerial imaging optical system by retro-reflection with conjugated...