Raman scattering and efficient UV photoluminescence from well-aligned ZnO nanowires epitaxially grown on GaN buffer layer

Optical phonon confinement and efficient UV emission of ZnO nanowires were investigated in use of resonant Raman scattering (RRS) and photoluminescence (PL). The high-quality ZnO nanowires with diameters of 80-100 nm and lengths of several micrometers were epitaxially grown through a simple low-pressure vapor-phase deposition method at temperature 550 degrees C on the precoated GaN(0001) buffer layer. The increasing intensity ratio of n-order longitudinal optical (LO) phonon (A(1)(nLO)/E(1)(nLO)) with increasing scattering order in RRS reveals the phonon quantum confinement as shrinking the diameter of ZnO nanowires. The exciton-related recombination near the band-edge transition dominate the UV emissions at room temperature as well as at low temperature that exhibits almost no other nonstoichiometric defects in the ZnO nanowires.     

Structural characterization and luminescence behavior of a silver(I) 1D polymeric chain constructed via a Bridge with unusual 4,5-diazospirobifluorene and perchlorate

A new polymeric silver complex, [Ag(2)(L(2))(ClO(4))(2)] (L = 4,5-diazospirobifluorene), has been synthesized and shown to exhibit interesting luminescence properties in a single crystal. Structural analysis reveals a one-dimensional chain, which contains a [Ag(2)(L(2))](2+) dimer bridged with ClO(4)(-). The Ag...Ag distances are 2.776(1) and 4.575(1) A incorporated by two L ligands and by a ClO(4)(-) bridge, respectively.     

On-column preconcentration and separation of DNA fragments using polymer solutions in the presence of electroosmotic flow

We demonstrated DNA preconcentration and separation in the presence of electroosmotic flow (EOF) using poly(ethylene oxide) (PEO) solutions. After injecting large volumes of DNA samples into a capillary filled with free tris(hydroxymethyl)aminomethane (Tris)-borate (TB) buffers, PEO solutions entered the capillary by EOF and acted as sieving matrices. In contrast to conventional methods (in the absence of EOF), controlling the EOF was also useful for resolution optimization. We have found that PEO adsorption on the capillary wall was more pronounced when low ionic strength buffers were used. Thus, the EOF decreased with increasing injection length, which led to longer migration times and changes in resolution and stacking efficiency. All resolution values were higher than 1.5 when 1.0 microg/mL DNA samples were injected at 240 V/cm for 60 s (0.67 microL). In addition, as low as 0.015 microg/mL DNA samples (an about 66-fold increase in sensitivity) were detected when the injection was performed at 250 V/cm for 60 s.     

Linear artificial molecular muscles

Two switchable, palindromically constituted bistable [3]rotaxanes have been designed and synthesized with a pair of mechanically mobile rings encircling a single dumbbell. These designs are reminiscent of a "molecular muscle" for the purposes of amplifying and harnessing molecular mechanical motions. The location of the two cyclobis(paraquat-p-phenylene) (CBPQT(4+)) rings can be controlled to be on either tetrathiafulvalene (TTF) or naphthalene (NP) stations, either chemically ((1)H NMR spectroscopy) or electrochemically (cyclic voltammetry), such that switching of inter-ring distances from 4.2 to 1.4 nm mimics the contraction and extension of skeletal muscle, albeit on a shorter length scale. Fast scan-rate cyclic voltammetry at low temperatures reveals stepwise oxidations and movements of one-half of the [3]rotaxane and then of the other, a process that appears to be concerted at room temperature. The active form of the bistable [3]rotaxane bears disulfide tethers attached covalently to both of the CBPQT(4+) ring components for the purpose of its self-assembly onto a gold surface. An array of flexible microcantilever beams, each coated on one side with a monolayer of 6 billion of the active bistable [3]rotaxane molecules, undergoes controllable and reversible bending up and down when it is exposed to the synchronous addition of aqueous chemical oxidants and reductants. The beam bending is correlated with flexing of the surface-bound molecular muscles, whereas a monolayer of the dumbbell alone is inactive under the same conditions. This observation supports the hypothesis that the cumulative nanoscale movements within surface-bound "molecular muscles" can be harnessed to perform larger-scale mechanical work.     

Self-assembly of a mixed-ligand metal-coordination polymeric network of cadmium(II) croconate with 4,4'-bipyridine

A new cadmium croconate (C5O5(2-)) complex, [Cd2(C5O5)2(4,4'-bpy)(H2O)]infinity (4,4-bpy=4,4'-bipyridine) with an extended network has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction studies. The title compound crystallizes in the monoclinic system, space group P2(1)/n, with empirical formula C20H12Cd2N2O12, a=15.9623(3) A, b=7.5837(1) A, c=18.1181(3) A, beta=99.95(2) degrees, and Z=4. Structural determination reveals that the title compound has a bilayered network, containing two crystallographically independent Cd(II) ions in different coordination environments. Cd(1) lies in a distorted pentagonal bipyramidal environment, consisting of three croconate ions and one 4,4'-bpy nitrogen donor, while Cd(2) lies in a distorted octahedral environment, consisting of two croconate anions, one 4,4'-bpy nitrogen donor, and one water molecule. Of the two crystallographic independent croconate ligands, one presents a bis-bidentate adjacent mu3-coordination mode and the other a new bidentate/three-adjacent mu5-coordination mode. A two-dimensional hybrid layer is formed by two rectangular boxes as the building units through the connectivity between Cd(II) and croconate and 4,4'-bpy ligands.     

The role of physical environment on molecular electromechanical switching

The influences of different physical environments on the thermodynamics associated with one key step in the switching mechanism for a pair of bistable catenanes and a pair of bistable rotaxanes have been investigated systematically. The two bistable catenanes are comprised of a cyclobis(paraquat-p-phenylene) (CBPQT4+) ring, or its diazapyrenium-containing analogue, that are interlocked with a macrocyclic polyether component that incorporates the strong tetrathiafulvalene (TTF) donor unit and the weaker 1,5-dioxynaphthalene (DNP) donor unit. The two bistable rotaxanes are comprised of a CBPQT4+ ring, interlocked with a dumbbell component in which one incorporates TTF and DNP units, whereas the other incorporates a monopyrrolotetrathiafulvalene (MPTTF) donor and a DNP unit. Two consecutive cycles of a variable scan rate cyclic voltammogram (10-1500 mV s(-1)) performed on all of the bistable switches (approximately 1 mM) in MeCN electrolyte solutions (0.1 M tetrabutylammonium hexafluorophosphate) across a range of temperatures (258-303 K) were recorded in a temperature-controlled electrochemical cell. The second cycle showed different intensities of the two features that were observed in the first cycle when the cyclic voltammetry was recorded at fast scan rates and low temperatures. The first oxidation peak increases in intensity, concomitant with a decrease in the intensity of the second oxidation peak. This variation changed systematically with scan rate and temperature and has been assigned to the molecular mechanical movements within the catenanes and rotaxanes of the CBPQT4+ ring from the DNP to the TTF unit. The intensities of each peak were assigned to the populations of each co-conformation, and the scan-rate variation of each population was analyzed to obtain kinetic and thermodynamic data for the movement of the CBPQT4+ ring. The Gibbs free energy of activation at 298 K for the thermally activated movement was calculated to be 16.2 kcal mol(-1) for the rotaxane, and 16.7 and 19.2 kcal mol(-1) for the bipyridinium- and diazapyrenium-based bistable catenanes, respectively. These values differ from those obtained for the shuttling and circumrotational motions of degenerate rotaxanes and catenanes, respectively, indicating that the detailed chemical structure influences the rates of movement. In all cases, when the same bistable compounds were characterized in an electrolyte gel, the molecular mechanical motion slowed down significantly, concomitant with an increase in the activation barriers by more than 2 kcal mol(-1). Irrespective of the environment--solution, self-assembled monolayer or solid-state polymer gel--and of the molecular structure--rotaxane or catenane--a single and generic switching mechanism is observed for all bistable molecules.     

A MNDO study of carbon clusters with specifically fitted parameters

Summary A MNDO method with new parameters for carbon clusters is presented. The parameters in the new sets are specifically tuned to fit the properties of small carbon clusters, C₂, C₃, C₅ and C₇–C₁₀, and buckminsterfullerene, C₆₀. The validity of these MNDO parameters is verified by experimental data. The calculated (with new parameters) IR spectra of C₆₀ and the heat of formation, geometry and IR spectra of C₇₀ agree satisfactorily with observed data. Heats of formation of other fullerenes, from C₂₀ to C₈₄, and C₆₀O are evaluated. The resulting heats of formation of the isomers of C₇₆ and C₈₄ are reliable and their relative stability is in excellent agreement with other reports. The predicted IR spectra of several fullerenes, C₂₄(C_6v ), C₂₈(T _d ), C₃₂(D₃), C₃₆(D_6h ), C₅₀(C_5h ) and C₈₀(D_5d ) are provided to aid assignments of experimental spectra.     

DNA analysis on microfabricated electrophoretic devices with bubble cells

Microfluidic devices with bubble cells have been fabricated on poly(methyl methacrylate) (PMMA) plates and have been employed for the analysis of DNA using polyethylene oxide (PEO) solutions. First, the separation channel was fabricated using a wire-imprinting method. Then, wires with greater sizes or a razor blade glued in a polycarbonate plate was used to fabricate bubble cells, with sizes of 190-650 microm. The improvements in resolution and sensitivity have been achieved for large DNA (> 603 base pair, bp) using such devices, which depend on the geometry of the bubble cell. The main contributor for optimal resolution is mainly due to DNA migration at lower electric field strengths inside the bubble cell. On the other hand, slight losses of resolution for small DNA fragments have been found mainly due to diffusion, supported by the loss of resolution when separating two small solutes. With a bubble cell of 75 microm (width) x 500 microm (depth), the sensitivity improvement up to 17-fold has been achieved for the 271 bp fragment in the separation of PhiX-174/HaeIII DNA restriction fragments. We have also found that a microfluidic device with a bubble cell of 360 microm x 360 microm is appropriate for DNA analysis. Such a device has been used for separating DNA ranging from 8 to 2176 bp and polymerase chain reaction (PCR) products amplified after 30 cycles, with rapidity and improvements in the sensitivity as well as resolution.     

Amplification of small analytes in polymer solution by capillary electrophoresis

We report concentration methods for the analysis of small solutes by capillary electrophoresis in conjunction with laser-induced native fluorescence using a Nd:YAG laser. After injecting samples, poly(ethylene oxide) (PEO) in the anode reservoir entered a capillary filled with Tris-borate buffer. When migrating in PEO solution, the analytes slowed down and stacked at the interface between the sample zone and PEO solution. As a result, the limits of detection (LODs) down to 8 pM for 2-naphthalenesulfonic acid and 70 pM for L-tryptophan have been achieved when injecting at 30 cm height for 120 s and 230 s, respectively. Such low LODs are partially due to the effects of NaCl in the samples and PEO on the fluorescence characteristics of the analytes. In addition, the concentrations of NaCl and PEO have great impacts on the migration of the analytes and electroosmotic flow, thereby affecting resolution and speed. Without pretreatment, the determinations of five important markers in urine samples and two acids in a cerebrospinal fluid sample have been performed separately, with the relative standard deviations of the concentrations less than 3.6%. Furthermore, by applying a short plug of low-pH buffer after injection, the analysis of greater volumes of the urine sample has been carried out, resulting in detecting more peaks.