Negatively charged pi-(C60-)2 dimer with biradical state at room temperature

A negatively charged pi-(C60-)2 dimer bonded by two single bonds was found in the ionic multicomponent complex {(MDABCO+).CoIITMPP}2.(C60-)2.(C6H4Cl2)2.5.(C6H5CN)1.5 (1). In contrast to the previously described diamagnetic sigma-(C60-)2 dimer, the negatively charged pi-dimer has a biradical state at room temperature: (C60*-)2 (S = 1). The behavior of spins in this dimer can be described by a model with a singlet ground state (S = 0) and a close lying excited triplet (S = 1) state with the energy gap of 2|JAF| = 70 +/- 2 cm-1. On the whole, complex 1 shows a strong antiferromagnetic interaction of spins with a Weiss constant of -34 K.     

The advantage of using carbon nanotubes compared with edge plane pyrolytic graphite as an electrode material for oxidase-based biosensors

Carbon nanotubes (CNTs) are promising materials for use in amperometric biosensors. The defect sites at their ends, and on their sidewalls, are considered to be edge plane-like defects and show high electrocatalytic activity toward several biological molecules. However, electrocatalytic activity toward H(2)O(2) has not been compared among bamboo-structured CNTs (BCNTs), which have many defect sites; hollow-structured CNTs (HCNTs), which have few defect sites; edge plane pyrolytic graphite (EPG); and traditional glassy carbon (GC). The advantages of using CNTs in electrodes for biosensors are still equivocal. To confirm the utility of CNTs, we analyzed the electrochemical performance of these four carbon electrodes. The slope of the calibration curve for H(2)O(2) at potentials of both +0.6 V and -0.1 V obtained with a BCNT paste electrode (BCNTPE) was more than 10 times greater than the slopes obtained with an HCNT paste electrode and a GC electrode, reflecting the BCNT's larger number of defect sites. Although the slope with the EPG electrode (EPGE) was about 40 times greater than that with BCNTPE at +0.6 V, the slopes with these two carbon electrodes were nearly equivalent at -0.1 V. EPGE demonstrated excessive electrochemical activity, detecting currents on the basis of consumption of oxygen and oxidation of ascorbic acid, even at -0.1 V. In contrast, BCNTPE could dominantly detect a cathodic current for H(2)O(2) at -0.1 V, even when interfering molecules were added. BCNTPE possesses appropriate electrochemical activity and is an effective electrode materials for developing interference-free oxidase-based biosensors operated by the application of an appropriate potential.     

Assisting the diagnosis of thyroid diseases with Bayesian-type and SOM-type neural networks making use of routine test data

Patients with hyperthyroidism sometimes take much time to receive the final diagnosis. To improve patient QOL, simple screening for hyperthyroidism by thyroid non-specialists at the physical check-up is highly expected. Therefore, we applied both Bayesian-type and SOM-type neural networks since we assured the approach useful in analysing thyroid function diagnosis in the previous work. Routine test (14 parameters) data from 66 subjects with a known diagnosis (18 patients with hyperthyroidism and 48 healthy volunteers) were adopted as learning data, and then 142 individuals who also received the same routine tests at the Tohoku University Hospital were screened to predict patients with hyperthyroidism. Both neural networks using 14 parameters predicted several patients as having hyperthyroidism with high probability, including all three hyperthyroid patients diagnosed later by the physician. Further detailed analysis of the routine test parameters that were important for classification found that screening with a set of three parameters (alkaline phosphatase, serum creatinine and total cholesterol) or plus aspartate aminotransferase allowed for quite accurate screening. These results showed that the same neural networks as previous work allows simple screening of patients for hyperthyroidism on the basis of routine test data, and that physicians not specializing in the thyroid can rapidly identify individuals suspected of having hyperthyroidism, to permit a rapid referral for examination and treatment by thyroid specialists.     

Excited state properties and quadratic optical nonlinearities in charged organic chromophores: theoretical analysis

As it has been found experimentally [K. Clays and B. Coe, Chem. Mater. 15, 642 (2003); B. J. Coe et al., 126, 10418 (2004)], elongation of the conjugation path length and N-arylation in stilbazolium chromophores both lead to substantial enhancement of the molecular optical nonlinearities. In the present contribution the authors perform a quantum chemical analysis of the excited state properties and quadratic nonlinear optical responses of a series of this type of dyes. Nonlinear optical responses are estimated by both finite-field and two-state model approaches that demonstrate an excellent qualitative mutual agreement. Time-dependent density functional theory calculations on the isolated cations predict redshift in the energy of the intramolecular charge transfer transition that is overestimated for cations with the longer conjugation path length. At the same time, in comparison with the Stark spectroscopy measurements the differences between the excited and ground state dipole moments are grossly underestimated for all compounds. The inclusion of solvent effect by polarizable continuum model affords a better agreement with experiment for these quantities. The authors' calculations demonstrate the crucial dependence of the electronic excitation properties on the way of the investigated compound geometry optimization. The origin of such dependence is discussed.     

Mechanism of ion permeation in a model channel: Free energy surface and dynamics of K+ ion transport in an anion-doped carbon nanotube

The mechanism of the ion permeation is investigated for an anion-doped carbon nanotube, as a model of the K+ channel, by analyzing the free energy surface and the dynamics of the ion permeation through the model channel. It is found that the main rate-determining step is how an ion enters the channel. The entrance of the ion is mostly blocked by a water molecule located at this entrance. Only about 10% of K+ ions which reach the mouth of the channel can really enter the channel. The rejection rate sensitively depends on the location of this water molecule, which is easily controlled by the charge of the carbon nanotube; for example, the maximum permeation is obtained when the anion charge is at a certain value, -5.4e in the present model. At this charge, the facile translocation of the ion inside the channel is also induced due to the number of fluctuations of the ions inside the channel. Therefore, the so-called "Newton's balls", a toy model, combined with a simple ion diffusion model for explaining the fast ion permeation should be modified. The present analysis thus suggests that there exists an optimum combination of the length and the charge of the carbon nanotube for the most efficient ion permeation.     

Experimental determination of the absorption cross-section and molar extinction coefficient of CdSe and CdTe nanowires

Absorption cross-sections and corresponding molar extinction coefficients of solution-based CdSe and CdTe nanowires (NWs) are determined. Chemically grown semiconductor NWs are made via a recently developed solution-liquid-solid (SLS) synthesis, employing low melting Au/Bi bimetallic nanoparticle "catalysts" to induce one-dimensional (1D) growth. Resulting wires are highly crystalline and have diameters between 5 and 12 nm as well as lengths exceeding 10 microm. Narrow diameters, below twice the corresponding bulk exciton Bohr radius of each material, place CdSe and CdTe NWs within their respective intermediate to weak confinement regimes. Supporting this are solution linear absorption spectra of NW ensembles showing blue shifts relative to the bulk band gap as well as structure at higher energies. In the case of CdSe, the wires exhibit band edge emission as well as strong absorption/emission polarization anisotropies at the ensemble and single-wire levels. Analogous photocurrent polarization anisotropies have been measured in recently developed CdSe NW photodetectors. To further support fundamental NW optical/electrical studies as well as to promote their use in device applications, experimental absorption cross-sections are determined using correlated transmission electron microscopy, UV/visible extinction spectroscopy, and inductively coupled plasma atomic emission spectroscopy. Measured CdSe NW cross-sections for 1 microm long wires (diameters, 6-42 nm) range from 6.93 x 10(-13) to 3.91 x 10(-11) cm2 at the band edge (692-715 nm, 1.73-1.79 eV) and between 3.38 x 10(-12) and 5.50 x 10(-11) cm2 at 488 nm (2.54 eV). Similar values are obtained for 1 microm long CdTe NWs (diameters, 7.5-11.5 nm) ranging from 4.32 x 10(-13) to 5.10 x 10(-12) cm2 at the band edge (689-752 nm, 1.65-1.80 eV) and between 1.80 x 10(-12) and 1.99 x 10(-11) cm2 at 2.54 eV. These numbers compare well with previous theoretical estimates of CdSe/CdTe NW cross-sections far to the blue of the band edge, having order of magnitude values of 1.0 x 10(-11) cm2 at 488 nm. In all cases, experimental NW absorption cross-sections are 4-5 orders of magnitude larger than those for corresponding colloidal CdSe and CdTe quantum dots. Even when volume differences are accounted for, band edge NW cross-sections are larger by up to a factor of 8. When considered along with their intrinsic polarization sensitivity, obtained NW cross-sections illustrate fundamental and potentially exploitable differences between 0D and 1D materials.     

Synthesis of [2]rotaxanes by the catalytic reactions of a macrocyclic copper complex

We synthesized [2]rotaxanes by the reactions catalyzed by a macrocyclic Cu(I)-phenanthroline complex. The catalytic site was located inside the ring component so that the rotaxane could be selectively formed. A C-S bond-forming reaction and oxidative dimerization of alkyne was utilized for the efficient synthesis of a new series of [2]rotaxanes. [reaction: see text]     

Isocratic separation of ginsenosides by high-performance liquid chromatography on a diol column at subambient temperatures

An improved high-performance liquid chromatographic method for separation of a number of ginsenosides has been developed. The influence of temperature (from 0 to 25°C) on the retention and separation of the ginsenosides was studied by applying a binary mobile phase (acetonitrile/water, 82:18 v/v) and a diol column (LiChrospher 100 Diol). The column temperature is one of the more important parameters for the retention and separation of the components investigated. Selected thermodynamic parameters, including changes of enthalpy (ΔH°) and entropy (ΔS°), were estimated from linear van’t Hoff plots, and possible retention mechanisms were discussed. Moreover, the best separation conditions were selected based on optimization criteria including maximum retention time (t _{R max}), minimum resolution (R _{s min}), and relative resolution product (r). Temperature regions close to 14°C offered the highest selectivity and almost equal distribution of the ginsenosides peaks across the chromatogram. Under such isocratic conditions, excellent separation of chromatographic standards and selected ginseng samples was achieved in less than 16 min.     

Simultaneous analysis of cationic, anionic, and neutral compounds using monolithic CEC columns

A new capillary electrochromatography (CEC) column for the simultaneous analysis of cationic, neutral, and anionic compounds using CEC-ESI-MS is described. Three different silica monolith columns were prepared by changing the poly(ethylene glycol) (PEG) contents for comparison of the separation property of these columns. Different separation programs were used for the simultaneous separation of different charged compounds under the same conditions. The column prepared with 80 mg of PEG separated typical compounds within 15 min using 1 M formic acid as the electrolyte. The analytes migrated in the order of cationic, neutral, and anionic compounds, which means that the migration order was mainly determined by the electrophoresis. The hydrodynamic flow by pressure from the inlet side was significant for a stable analysis to be achieved. The effect of the composition of the sheath liquid was also examined. All analytes (14 amino acids, thiourea, urea, citric acid, and ATP) were detectable when 1% acetic acid in 50% (v/v) methanol was used as the sheath liquid.     

Observation of strong low-lying E1 strength in the two-neutron halo nucleus 11Li

An exclusive measurement has been made of the Coulomb dissociation of the two-neutron halo nucleus 11Li at 70 MeV/nucleon at RIKEN. Strong low-energy (soft) E1 excitation is observed, peaked at about Ex = 0.6 MeV with B(E1) = 1.42(18) e2fm2 for Erel < or = 3 MeV, which was largely missed in previous measurements. This excitation represents the strongest E1 transition ever observed at such low excitation energies. The spectrum is reproduced well by a three-body model with a strong two-neutron correlation, which is further supported by the E1 non-energy-weighted cluster sum rule.