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Organic semiconductor materials for fabricating organic light emitting diodes (OLEDs) have attracted significant attention in the field of novel optical and optoelectronic devices. Particulation of OLEDs’ emitting materials in small-scale has been limited only to tris(8-hydroxyquinoline) aluminum (Alq3) that emits green-light. In this study, we attempted to fabricate, for the first time, red-light emitting nanoparticles of phosphorescent organic semiconductor of bis(1-phenylisoquinoline) (acetylacetonate) iridium (Ir(piq)2(acac)). Rectangular particles with length and thickness of ∼2 μm and ∼50 nm were fabricated with guidance of cetyltrimethylammonium bromide (CTAB) and micro-plates with length and thickness of ∼5 μm and ∼100 nm were fabricated by sodium dodecyl sulfate (SDS). By contrast, single-stranded DNA (ssDNA) induced nano-rods with dimension of ∼400 nm in length and 100 nm in thickness. Hence, the choice of guiding agents resulted in distinctive crystal characteristic so that the nanorods by ssDNAs showed UV absorption with a red-shift in metal-ligand charge transfer (MLCT) by 54 nm whereas the particles by surfactants did 35 nm compared to the dissolved precursor. Higher was the ssDNA-guided nanorods in relative phosphorescence of the intensity at 610 nm over that at 695 nm than the surfactant-guided particles.

Plasmonic nanocrystals, which exhibit extraordinary optical properties, are challenging to grow in selective positions with a cost-effective and high-throughput process. We demonstrate that plasmonic isotropic gold nanospheres (AuNSs) can be selectively synthesized on wafer-scale rigid and flexible substrates at room temperature by laser irradiation. First, we prepare gold nanocolumn (AuNC) thin films on sapphire and polydimethylsiloxane substrates with glancing angle deposition (GAD). Then, a KrF excimer laser is exposed at selected positions with a 24 ns pulse duration. Finally, highly isotropic AuNSs as plasmonic nanocrystals are synthesized at the targeted positions. We suggest that the formation of such isotropic AuNSs is caused by reshaping from the top of the AuNCs; this is verified by the temperature distribution in the AuNCs during laser irradiation through finite element method simulations. We further investigate the formation of AuNSs by varying the laser energy density and the kind of substrate. By using a simple mask process, we demonstrate patterning of the letters “KIST” via selectively grown AuNSs on a flexible substrate. The simple laser irradiation process on GAD-grown metal NC thin films is expected to be a promising method for scalable synthesis of plasmonic isotropic NSs at targeted positions with a rapid process and at room temperature.

DNA strands have been recently found to play a role in crystallizing organic semiconductors as a substitute for conventional surfactants. Such DNA-guided organic semiconductor particles possessed the recognition ability to complementary target DNAs, resulting in “enhanced luminescence” due to the lesser degree of non-radiative dissipation. Apart from this, in this study we developed selective recognition of mercury ions by utilizing DNA probes having ion-specific thymine-rich motifs. Strikingly, the specific ion–DNA interaction triggered rather distinctive “depressed luminescence” emitting from the particles. The mercury ions were found to be present both at the surface and the inner regions, which were discovered to relate to the drastic morphological distortion of the particles as evidenced by elemental, electron microscopy, and confocal fluorescence microscopy analyses. This novel phenomenon discovered would expand the technological values of organic semiconductors conjugated with oligonucleotides toward a wider range of target-specific applications.

Shape-persistent replica synthesis of Au/Ag bimetallic nanoplates is invented. Using a tailored silica cage as a template for the synthesis, a successful shape-replication of Au/Ag bimetallic nanoplate is achieved at the cage core having geometry of initial Ag nanoplate. This work can open up the simple fabrication of multicomponent metallic particles, with nanogeometry being defined early at the initial stage.

Graphitized nanodiamonds were conveniently prepared by the laser irradiation of colloidal solution using various solvents. The nanodiamonds were converted into a fully graphitized onion-like structure, which became a cage-like mesoporous structure by the degradation of graphitic layers. Alcohols, acetone, and acetonitrile are more efficient solvents for the graphitization compared to water and hydrocarbons. Therefore the number and morphology of the graphitic layers can be simply controlled by the solvent and laser-irradiation duration. We suggest a graphitization model, in which the photocatalytic oxidation of the solvent accelerates the graphitization of nanodiamonds. The graphitized nanodiamonds were easily doped with the nitrogen and sulfur atoms in a controlled manner. In particular, the spherical graphitic layers were preferentially doped with the pyrrolic nitrogen that enhances remarkably electrocatalytic activity for the oxygen reduction reaction.

We developed a new high-yield synthesis method of free-standing germanium nanocrystals (Ge NCs) by means of the gas-phase photolysis of tetramethyl germanium in a closed reactor using a Nd:YAG puls...

We developed a new high-yield synthesis method of free-standing germanium nanocrystals (Ge NCs) by means of the gas-phase photolysis of tetramethyl germanium in a closed reactor using an Nd-YAG pulsed laser. Size control (5-100 nm) can be simply achieved using a quenching gas. The Ge1-xSix NCs were synthesized by the photolysis of a tetramethyl silicon gas mixture and their composition was controlled by the partial pressure of precursors. The as-grown NCs are sheathed with thin (1-2 nm) carbon layers, and well dispersed to form a stable colloidal solution. Both Ge NC and Ge-RGO hybrids exhibit excellent cycling performance and high capacity of the lithium ion battery (800 and 1100 mAh/g after 50 cycles, respectively) as promising anode materials for the development of high-performance lithium batteries. This novel synthesis method of Ge NCs is expected to contribute to expand their applications in high-performance energy con- version systems.

Various germanium-based nanostructures have recently demonstrated outstanding lithium ion storage ability and are being considered as the most promising candidates to substitute current carbonaceous anodes of lithium ion batteries. However, there is limited understanding of their structure and phase evolution during discharge/charge cycles. Furthermore, the theoretical model of lithium insertion still remains a challenging issue. Herein, we performed comparative studies on the cycle-dependent lithiation/delithiation processes of germanium (Ge), germanium sulfide (GeS), and germanium oxide (GeO2) nanocrystals (NCs). We synthesized the NCs using a convenient gas phase laser photolysis reaction and attained an excellent reversible capacity: 1100-1220 mAh/g after 100 cycles. Remarkably, metastable tetragonal (ST12) phase Ge NCs were constantly produced upon lithiation and became the dominant phase after a few cycles, completely replacing the original phase. The crystalline ST12 phase persisted through 100 cycles. First-principles calculations on polymorphic lithium-intercalated structures proposed that the ST12 phase Ge12Lix structures at x ≥ 4 become more thermodynamically stable than the cubic phase Ge8Lix structures with the same stoichiometry. The production and persistence of the ST12 phase can be attributed to a stronger binding interaction of the lithium atoms compared to the cubic phase, which enhanced the cycling performance.

Nanodiamonds (ND) were found to generate hydrogen (H2) and carbon monoxide (CO) from water at a remarkable rate under pulsed laser (532 nm) irradiation. The transformation of diamond structure into graphitic layers takes place to form an onion-like carbon structure. The CO generation suggests the oxidative degradation reaction of graphitic layers, C + H2O → CO + 2H(+) + 2e(-), which produced a unique laser-induced reaction: C + H2O → CO + H2. Au, Pt, Pd, Ag, and Cu nanoparticles on the ND enhance both gas evolution rates (~2 times for Au) and graphitization and, specifically, Au was found to be the most efficient amongst other nanoparticles. The enhancement effect was ascribed to effective charge separation between the metal nanoparticles and ND. The Au-ND hybrid on the reduced graphene oxide produced consistently a greater photocurrent than the ND upon visible light irradiation.

Scaling-down of phase change materials to a nanowire (NW) geometry is critical to a fast switching speed of nonvolatile memory devices. Herein, we report novel composition-phase-tuned GeSbTe NWs, synthesized by a chemical vapor transport method, which guarantees promising applications in the field of nanoscale electric devices. As the Sb content increased, they showed a distinctive rhombohedral-cubic-rhombohedral phase evolution. Remarkable superlattice structures were identified for the Ge(8)Sb(2)Te(11), Ge(3)Sb(2)Te(6), Ge(3)Sb(8)Te(6), and Ge(2)Sb(7)Te(4) NWs. The coexisting cubic-rhombohedral phase Ge(3)Sb(2)Te(6) NWs exhibited an exclusively uniform superlattice structure consisting of 2.2 nm period slabs. The rhombohedral phase Ge(3)Sb(8)Te(6) and Ge(2)Sb(7)Te(4) NWs adopted an innovative structure; 3Sb(2) layers intercalated the Ge(3)Sb(2)Te(6) and Ge(2)Sb(1)Te(4) domains, respectively, producing 3.4 and 2.7 nm period slabs. The current-voltage measurement of the individual NW revealed that the vacancy layers of Ge(8)Sb(2)Te(11) and Ge(3)Sb(2)Te(6) decreased the electrical conductivity.

Germanium chalcogenide GeS(x)Se(1-x) nanocrystals (NC) were synthesized using a novel gas-phase laser photolysis reaction. The composition was simply controlled by the partial pressure of precursors in a closed reactor. Remarkably, these ligand-free NC undergo the photo-induced cation exchange reaction to produce a series of Cd, Zn, Pb, and Ag chalcogenide NC in aqueous solution, which is governed by the thermodynamic driving force based on solubility.

511 Background: The purpose of this study was to evaluate rate of pathologic complete response (pCR) in patients with locally advanced rectal cancer treated with neoadjuvant chemoradiotherapy (CRT) with 5-FU/leucovorin (FL) versus Irinotecan/S-1 (IS) and surgery followed by fluoropyrimidine based adjuvant chemotherapy. Methods: Patients with resectable, locally advanced (cT3-4 and/or cN positive) adenocarcinoma of rectum were randomly assigned to receive preoperative radiation (45-50.4 Gy in 25-28 daily fractions) and concomitant chemotherapy with bolus injections of 5-FU 400 mg/m2/day and LV 20 mg/m2/day for 3 consecutive days every 4 weeks for 2 cycles (FL group), or with irinotecan 40 mg/m2 on days 1, 8, 15, 22, 29 and S-1 35mg/m2 twice on the day of irradiation (Monday-Friday) (IS group). Curative surgery was performed for about 4-8 weeks after the completion of chemoradiotherapy. Postoperative chemotherapy regimen is FL. The primary endpoint was pCR rate. Results: 142 eligible patients were randomly assigned. Of 142, 130 patients (91.5%) underwent total mesorectal excision. The pCR was achieved 11 (17.2 %) of 64 patients in the FL group and was 16 (24.2%) of 66 patients in the IS group (p=0.1). When pCR was combined with few residual cells, the rate was significantly higher in IS group compared to FL group (57.6 % vs. 39.1 %, p-value=0.035). Preoperative rate of grade 3-4 toxicity was 1.4% with FL and 7.0 % with IS group (p=0.095). Conclusions: The results have suggested that neoadjuvant CRT using IS is feasible and effective for patients with locally advanced rectal cancer. Longer follow-up is needed to assess survival. Clinical trial information: NCT01269216.

Germanium sulfide (GeS and GeS2) nanoparticles were synthesized by novel gas-phase laser photolysis and subsequent thermal annealing. They showed excellent cycling performance for lithium ion batteries, with a maximum capacity of 1010 mA h g(-1) after 100 cycles. Metastable tetragonal phase Ge nanoparticles were suggested as active materials for a reversible lithium insertion-extraction process.

We synthesized polytypic tin sulfide, SnS, Sn2S3, and SnS2 nanocrystals, by means of novel gas-phase laser photolysis of tetramethyl tin and hydrogen sulfide. A facile composition tuning through the pressure of precursors (addition of dimethyl selenium) yields a series of orthorhombic phase SnX and hexagonal phase SnX2, where X = SxSe1−x with 0 ≤ x ≤ 1. Various polytypic hybrids such as SnS–Sn2S3–SnS2, SnS–SnS2, Sn2S3–SnS2, and SnSe–SnSe2 were synthesized. This resulted in the ability to tune the band gap over a wide range (1.0–2.3 eV). Their photon energy conversion properties were investigated by fabricating photodetector devices using the nanocrystal-reduced graphene oxide nanocomposites. The enhanced photoconversion efficiency was observed from the polytypic hybrid nanostructures. This original synthesis method for tin chalcogenide nanocrystals is expected to help expand applications in high-performance energy conversion systems.

Germanium-tin (Ge(1-x)Sn(x)) alloy nanocrystals were synthesized using a gas-phase laser photolysis reaction of tetramethyl germanium and tetramethyl tin. A composition tuning was achieved using the partial pressure of precursors in a closed reactor. For x0.1, cubic phase alloy nanocrystals were exclusively produced without separation of the tetragonal phase Sn metal. In the range of x = 0.1-0.4, unique Ge(1-x)Sn(x)-Sn alloy-metal hetero-junction nanocrystals were synthesized, where the Sn metal domain becomes dominant with x. Thin graphitic carbon layers usually sheathed the nanocrystals. We investigated the composition-dependent electrochemical properties of these nanocrystals as anode materials of lithium ion batteries. Incorporation of Sn (x = 0.05) significantly increased the capacities (1010 mA h g(-1) after 50 cycles) and rate capabilities, which promises excellent electrode materials for the development of high-performance lithium batteries.