ABSTRACT
In this study, a new phenomenon describing the Janus effect on ice growth by hyperbranched polyglycerols, which can align the surrounding water molecules, has been identified. Even with an identical polyglycerol, we not only induced to inhibit ice growth and recrystallization, but also to promote the growth rate of ice that is more than twice that of pure water. By investigating the polymer architecture and population, we found that the stark difference in the generation of quasi-structured H2O molecules at the ice/water interface played a crucial role in the outcome of these opposite effects. Inhibition activity was induced when polymers at nearly fixed loci formed steady hydrogen bonding with the ice surface. However, the formation-and-dissociation dynamics of the interfacial hydrogen bonds, originating from and maintained by migrating polymers, resulted in an enhanced quasi-liquid layer that facilitated ice growth. Such ice growth activity is a unique property unseen in natural antifreeze proteins or their mimetic materials.
Subject(s)
Ice , Polymers , Hydrogen Bonding , Water/chemistryABSTRACT
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.
Subject(s)
DNA Probes , Mercury/analysis , Oligonucleotides/chemistry , Semiconductors , Thymine/chemistry , DNAABSTRACT
Incorporation of duplex DNA with higher molecular weights has attracted attention for a new opportunity towards a better organic light-emitting diode (OLED) capability. However, biological recognition by OLED materials is yet to be addressed. In this study, specific oligomeric DNA-DNA recognition is successfully achieved by tri (8-hydroxyquinoline) aluminium (Alq3), an organic semiconductor. Alq3 rods crystallized with guidance from single-strand DNA molecules show, strikingly, a unique distribution of the DNA molecules with a shape of an 'inverted' hourglass. The crystal's luminescent intensity is enhanced by 1.6-fold upon recognition of the perfect-matched target DNA sequence, but not in the case of a single-base mismatched one. The DNA-DNA recognition forming double-helix structure is identified to occur only in the rod's outer periphery. This study opens up new opportunities of Alq3, one of the most widely used OLED materials, enabling biological recognition.
Subject(s)
DNA/chemistry , Lighting , Semiconductors , Aluminum Compounds , Electric Conductivity , Electron Transport , Equipment Design , Organic Chemicals/chemistryABSTRACT
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.
ABSTRACT
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.
ABSTRACT
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.
ABSTRACT
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 x < 0.1, 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.
ABSTRACT
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 â CO + 2H(+) + 2e(-), which produced a unique laser-induced reaction: C + H2O â 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.
ABSTRACT
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.
ABSTRACT
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.
ABSTRACT
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.
