Photochemistry of neutral isonitrile gold(I) complexes: modulation of photoreactivity by aurophilicity and pi-acceptance ability

This work demonstrates for the first time that aurophilicity and ligand pi-acceptance ability sensitize the photoreactivity of Au(I) complexes. Photolysis of LAu(I)Cl (L = RNC or CO) complexes leads to free L, Au(III), and Au(0) photoproducts. Solutions of (p-tosyl)CH(2)NCAuCl in dichloromethane undergo significant oligomerization leading to dimers and trimers with formation constants of 1.61 x 10(3) and 6.61 x 10(3) M(-1), respectively, representing the highest values reported to date for complexes that exhibit aurophilic association in solution. The photoproduct quantum yield (Phi) varies with the LAu(I)Cl concentration in solution. For (p-tosyl)CH(2)NCAuCl, metallic gold forms with Phi = 0.0065 and 0.032 in 4.0 x 10(-5) and 4.0 x 10(-3) M dichloromethane solutions, respectively. Meanwhile, irradiation of t-BuNCAuCl primarily produces t-BuNCAuCl(3) with Phi = 0.0045 and 0.013 for 5.0 x 10(-5) and 5.0 x 10(-3) M dichloromethane solutions, respectively. For Au(CO)Cl, metallic gold forms with Phi = 0.013 and 0.065 upon irradiation of 8.0 x 10(-5) and 8.0 x 10(-3) M dichloromethane solutions, respectively. Hence, *[LAuX](n) oligomeric species are more photoreactive than monomeric species. The results also demonstrate intuitive control of Phi via modulation of the pi-acceptance ability of L, as both follow CO > (p-tosyl)CH(2)NC > (alkyl)NC in LAuCl, a trend that is also commensurate with the relative long-term photosensitivity of the corresponding solids and solutions. A new method for preparing stable small gold nanoparticles is described based on the fundamental findings above. Thus, photolysis of different concentrations of LAuX in solutions containing a primary amine-terminated dendrimer leads to clear solutions exhibiting tunable visible plasmon absorptions of gold nanoparticles; these solutions maintain their colors and stability indefinitely. TEM measurements for representative samples prepared by photolysis of (p-tosyl)CH(2)NCAuCl solutions give rise to spherical nanoparticles as small as 5 nm.     

(Pyridine)pentaamminechromium(III). Synthesis, Characterization, and Photochemistry

The Cr(NH(3))(5)(py)(3+) ion has been obtained by metathesis of Cr(NH(3))(5)(Me(2)SO)(3+) in pyridine, isolated as the perchlorate salt, and characterized by absorption (lambda(max) at 467, 352, and 260 nm) and emission spectra (lambda(max) at 668 nm, tau = 2.0 &mgr;s at 20 degrees C in water) and by the py aquation rate (k = 5 x 10(-)(4) s(-)(1) at 80 degrees C). Ligand-field (LF) band irradiation in acid aqueous solution (10(-)(2) M HClO(4)) induces photoaquation of py (Phi = 0.26) and NH(3) (Phi = 0.16). HPLC indicates that the latter reaction gives rise to both cis- and trans-Cr(NH(3))(4)(py)(H(2)O)(3+), with the predominance of the cis isomer. This is the first Cr(NH(3))(5)X(z+)() species where Phi(x) > Phi(NH)3: the result is compared with the predictions of various photolysis models and is taken as chemical evidence for pi-acceptance by the py ligand. The photostereochemistry is also discussed. The phosphorescence is totally quenched by Cr(C(2)O(4))(3)(3)(-) (k(q) = 2.7 x 10(9) M(-)(1) s(-)(1)), while the photoreactions are only in part. On 470-nm excitation, the Phi(py)/Phi(NH)()3 ratio is approximately 1 and approximately 2 for the unquenchable and the quenchable contributions, respectively. Such a difference, suggesting at least two reactive precursors, can be interpreted in terms of the photochemistry proceeding from either the lowest doublet and quartet excited states or, alternatively, from the (4)E and (4)B(2) states. Irradiation of the very distinct absorption of coordinated pyridine results in both doublet-state emission and loss of py and NH(3). Comparison of this photobehavior with the LF results gives an efficiency of 0.7 for conversion of the py-localized pipi states into the Cr-localized LF states, confirmed by the wavelength dependence of the relative emission yields. Some py release (Phi = 0.03) is concluded to originate in the pipi states.     

A new zinc(II) fluorophore 2-(9-anthrylmethylamino)ethyl-appended 1,4,7,10-tetraazacyclododecane

A new 2-(9-anthrylmethylamino)ethyl-appended cyclen, L(3) (1-(2-(9-anthrylmethylamino)ethyl)-1,4,7,10-tetraazacyclododecane) (cyclen = 1,4,7,10-tetraazacyclododecane), was synthesized and characterized for a new Zn(2+) chelation-enhanced fluorophore, in comparison with previously reported 9-anthrylmethylcyclen L(1) (1-(9-anthrylmethyl)-1,4,7,10-tetraazacyclododecane) and dansylamide cyclen L(2). L(3) showed protonation constants log K(a)(i)() of 10.57 +/- 0.02, 9.10 +/- 0.02, 7.15 +/- 0.02, <2, and <2. The log K(a3) value of 7.15 was assigned to the pendant 2-(9-anthrylmethylamino)ethyl on the basis of the pH-dependent (1)H NMR and fluorescence spectroscopic measurements. The potentiometric pH titration study indicated extremely stable 1:1 Zn(2+)-L(3) complexation with a stability constant log K(s)(ZnL(3)) (where K(s)(ZnL(3)) = [ZnL(3)]/[Zn(2+)][L(3)] (M(-)(1))) of 17.6 at 25 degrees C with I = 0.1 (NaNO(3)), which is translated into the much smaller apparent dissociation constant K(d) (=[Zn(2+)](free)[L(3)](free)/[ZnL(3)]) of 2 x 10(-)(11) M with respect to 5 x 10(-)(8) M for L(1) at pH 7.4. The quantum yield (Phi = 0.14) in the fluorescent emission of L(3) increased to Phi = 0.44 upon complexation with zinc(II) ion at pH 7.4 (excitation at 368 nm). The fluorescence of 5 microM L(3) at pH 7.4 linearly increased with a 0.1-5 microM concentration of zinc(II). By comparison, the fluorescent emission of the free ligand L(1) decreased upon binding to Zn(2+) (from Phi = 0.27 to Phi = 0.19) at pH 7.4 (excitation at 368 nm). The Zn(2+) complexation with L(3) occurred more rapidly (the second-order rate constant k(2) is 4.6 x 10(2) M(-)(1) s(-)(1)) at pH 7.4 than that with L(1) (k(2) = 5.6 x 10 M(-)(1) s(-)(1)) and L(2) (k(2) = 1.4 x 10(2) M(-)(1) s(-)(1)). With an additionally inserted ethylamine in the pendant group, the macrocyclic ligand L(3) is a more effective and practical zinc(II) fluorophore than L(1).     

Surface area measurement of functionalized single-walled carbon nanotubes

Single-walled carbon nanotubes have been functionalized and the specific surface areas of the functionalized nanotubes measured. Contrary to expectations, functionalization leads to a decrease in specific surface area compared to that of the unfunctionalized nanotubes. Treatment with a concentrated 1:1 nitric/sulfuric acid mixture followed by high-temperature baking at 1000 degrees C was found to increase the specific surface area of the nanotubes. For the unfunctionalized SWNTs, this treatment increases the specific surface area (SSA) by 20%. In the case of SWNTs functionalized by n-butyl groups the increase in the SSA was nearly 2-fold with the value increasing from 410 (drying at 110 degrees C) to 770 m2/gm (acid and bake treatment followed by drying at 110 degrees C). For the ozonized SWNTs, the SSA increases more than 3-fold from 381 (drying at 110 degrees C) to 1068 m2/gm (acid and bake treatment followed by drying at 110 degrees C). SEM images indicate that the nanotubes rebundle in the solid state with an average bundle size of 10-30 nm. AFM studies show that the ozonized tubes have been cut to short bundles after ozonolysis. Hydrogen uptake studies carried out on the baked ozonized tubes led to a 3 wt % hydrogen uptake at 77 K and 30 bar.     

Direct electrochemistry of uric acid at chemically assembled carboxylated single-walled carbon nanotubes netlike electrode

Carboxylated single-walled carbon nanotubes (SWCNT) chemically assembled on gold substrate was employed as netlike electrode to investigate the charge-transfer process and electrode process kinetics using uric acid as an example. The electrochemical behavior of uric acid in carboxylated SWCNT system was investigated using cyclic voltammetry, chronoamperometry, and single potential time-based techniques. The properties of raw SWCNT electrode were also studied for comparison purpose. Uric acid has better electrochemical behavior whereas ascorbic acid has no effective reaction on the carboxylated SWCNT electrode. Cyclic voltammograms indicate that the assembled carboxylated SWCNT increases more active sites on electrode surface and slows down the electron transfer between the gold electrode and uric acid in solution. The charge-transfer coefficient (alpha) for uric acid and the rate constant (k) for the catalytic reaction were calculated as 0.52 and 0.43 s(-1), respectively. The diffusion coefficient of 0.5 mM uric acid was 7.5 x 10(-6) cm2 x s(-1). The results indicate that electrode process in the carboxylated SWCNT electrode system is governed by the surface adsorption-controlled electrochemical process.     

Electrogenerated chemiluminescence of a spirobifluorene-linked bisanthracene: a possible simultaneous, two-electron transfer

We report the electrogenerated chemiluminescence (ECL) of 2,2'-bis(10-phenylanthracen-9-yl)-9,9'-spirobifluorene (spiro-FPA), a dichromophoric molecule composed of two phenylanthracenes linked by a spirobifluorene moiety (PA-X-PA). The results are compared to those for 9,10-diphenylanthracene (DPA), a related molecule with a single chromophore. Cyclic voltammetry (CV) of spiro-FPA shows two reversible, closely spaced, one-electron transfers on both reduction and oxidation, occurring at E(o)(1,red) = -2.02, E(o)(2,red) = -2.07 V vs SCE and E(o)(1,ox) = 1.14, E(o)(2,ox) = 1.20 V vs SCE. The potentials for each pair are close enough to appear as a single peak in CV, indicating that the spirobifluorene moiety interrupts conjugation between the redox centers. The potentials observed are similar to those of DPA, which shows E(o)(red) = -2.06 V vs SCE and E(o)(ox) = 1.15 V vs SCE. The absorbance spectrum of spiro-FPA shows lambda(max,abs) = 377 nm, with 377 = 25,700 M(-1) s(-1), while DPA exhibited lambda(max,abs) = 374 nm, with 374 = 13,800 M(-1) s(-1), demonstrating that spiro-FPA has twice the available chromophores as DPA. Photoluminescence (PL) data for spiro-FPA shows lambda(max,PL) = 434 nm, with Phi(PL) = 0.74, while DPA fluoresces at 420 nm with Phi(PL) = 0.91; thus, there is greater solvent or structural relaxation in the spiro-FPA excited state, which may account for the greater internal conversion. Unlike DPA, the ECL spectrum of spiro-FPA exhibits long-wavelength emission not observed in the PL. We attribute this emission to excimers formed during annihilation ECL. Steric hindrance prevents DPA from forming excimers, even in ECL, but spiro-FPA annihilation can occur between pairs of di-ions (PA(*-)-X-PA(*-) and PA(*+)-X-PA(*+)), which are electrostatically more strongly attracted to one another than the mono-ions. This greater electrostatic attraction may be sufficient to overcome the steric hindrance to excimer formation. Lowering the electrolyte concentration decreases the electrostatic shielding of the ions from one another; thus, the increase in longer wavelength ECL accompanying a decrease in electrolyte concentration supports the role of the di-ions in excimer formation. Additionally, simulations show, consistent with experiment, a more rapid decrease in excimer concentration than in excited monomer concentration as a function of time after each potential pulse. This is probably due to the greater number of scavenging reactions available for di-ions. The simulations are confirmed experimentally when lower potential pulsing frequencies yield lower relative excimer emission. Since an excited state created by one-electron transfer between two di-ions should be rapidly quenched via electron transfer by the other PA moiety, the existence of excimers suggests the possibility of simultaneous, two-electron transfer to generate the excimer.     

Visible-light photochromism of triarylamine- or ferrocene-bound diethynylethenes that switches electronic communication between redox sites and luminescence

Redox-active ferrocene- and triarylamine-terminated diethynylethene derivatives have been synthesized and their photochromic properties and switching behavior based on through-bond electronic communication between the two redox sites, as well as their emissions, have been examined. Both bis(ferrocenylethynyl)ethene 1 and bis(triarylaminoethynyl)ethene 2 show visible-light photochromism induced by donor-acceptor charge-transfer (CT) transitions from the ferrocene or triarylamine to the diethynylethene moieties. The reversibility and quantum yields of the photochromism of 2 (Phi(E-->Z)=6.1 x 10(-2), Phi(Z-->E)=1.4 x 10(-2)) are far higher than those of 1 (Phi(E-->Z)=8.6 x 10(-6), Phi(Z-->E)=2.5 x 10(-6)). The higher efficiency in 2 may be attributed to the absence of the heavy atom effect and of a low-lying (3)LF state, which are characteristic of ferrocenyl compounds. This proposition is further supported by the fact that bis(ferrocenylbuta-1,3-diynyl)ethene 3, which, unlike 1, is free from steric interference between the two ferrocenyl groups in the Z form, does not show a significant improvement in its photoisomerization quantum yields (Phi(E-->Z)=6.2x10(-5), Phi(Z-->E)=3.4 x 10(-5)). The visible-light photochromism of 1 and 2 is accompanied by a switch in the strength of the electronic communication between the two redox sites in their mixed-valence states (DeltaE(0)' values are 70 and 48 mV for (E)-1 and (Z)-1, and 74 and 63 mV for (E)-2 and (Z)-2). In the case of 2, further evaluations were carried out through intervalence charge-transfer (IVCT) band analyses and DFT calculations. We have also demonstrated that steric repulsion between the methyl ester moieties in the Z form is implicated in the reduction in the through-bond electronic communication. Compound 2 exhibits photoluminescence, which is more efficient in the E form than in the Z form, whereas 1 and 3 show no photoluminescence.     

Encapsulation of carbon chain molecules in single-walled carbon nanotubes

The vacuum space inside carbon nanotubes offers interesting possibilities for the inclusion, transportation, and functionalization of foreign molecules. Using first-principles density functional calculations, we show that linear carbon-based chain molecules, namely, polyynes (C(m)H(2), m = 4, 6, 10) and the dehydrogenated forms C(10)H and C(10), as well as hexane (C(6)H(14)), can be spontaneously encapsulated in open-ended single-walled carbon nanotubes (SWNTs) with edges that have dangling bonds or that are terminated with hydrogen atoms, as if they were drawn into a vacuum cleaner. The energy gains when C(10)H(2), C(10)H, C(10), C(6)H(2), C(4)H(2), and C(6)H(14) are encapsulated inside a (10,0) zigzag-shaped SWNT are 1.48, 2.04, 2.18, 1.05, 0.55, and 1.48 eV, respectively. When these molecules come inside a much wider (10,10) armchair SWNT along the tube axis, they experience neither an energy gain nor an energy barrier. They experience an energy gain when they approach the tube walls inside. Three hexane molecules can be encapsulated parallel to each other (i.e., nested) inside a (10,10) SWNT, and their energy gain is 1.98 eV. Three hexane molecules can exhibit a rotary motion. One reason for the stability of carbon chain molecules inside SWNTs is the large area of weak wave function overlap. Another reason concerns molecular dependence, that is, the quadrupole-quadrupole interaction in the case of the polyynes and electron charge transfer from the SWNT in the case of the dehydrogenated forms. The very flat potential surface inside an SWNT suggests that friction is quite low, and the space inside SWNTs serves as an ideal environment for the molecular transport of carbon chain molecules. The present theoretical results are certainly consistent with recent experimental results. Moreover, the encapsulation of C(10) makes an SWNT a (purely carbon-made) p-type acceptor. Another interesting possibility associated with the present system is the direction-controlled transport of C(10)H inside an SWNT under an external field. Because C(10)H has an electric dipole moment, it is expected to move under a gradient electric field. Finally, we derive the entropies of linear chain molecules inside and outside an open-ended SWNT to discuss the stability of including linear chain molecules inside an SWNT at finite temperatures.     

DFT study of ionic peapod structures from single-walled carbon nanotubes and Lindqvist tungstates

DFT investigations have been carried out on encapsulation of Lindqvist-type W(6)O(19)(2-) anion inside hydrogenated (n,n) armchair single-walled carbon nanotubes (h-CNTs) with n = 8, 9, 10 to understand the confinement effect of the CNTs on the rotation of W(6)O(19)(2-). The energy-decomposition analysis (EDA) of interaction between W(6)O(19)(2-) and CNTs shows that with the increase of confinement effect from n = 8, 9, to 10, the destabilizing ΔE(Pauli) plays a more important role in the relative orientation of W(6)O(19)(2-) inside CNTs. For W(6)O(19)(2-)@(9,9) h-CNT, the most stable orientation appears at the y/z angle 45°/36°. The confinement effect reduces significantly the energy gap of W(6)O(19)(2-)@(n,n) h-CNT (n = 8, 9, 10) compared with free W(6)O(19)(2-). Electron transfer from the W(6)O(19)(2-) to CNT is observed.     

Aligned single-walled carbon nanotubes array electrode:Fabrication,characterization and application

In the presence of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride(EDC)and N-hydroxysuccinimide(NHS), carboxylic group-functionalized single-walled carbon nanotubes(SWNTs)were assembled vertically on the glassy carbon electrode using ethylenediamine as linking agent to fabricate an aligned electrode(SWNTE).The morphological characteristic was studied with atomic force microscope(AFM)and its electrochemical property was investigated using K_3[Fe(CN)_6]as probe. ssDNA had a sensitive voltammetr...     

Ion diffusion and electrochemical capacitance in aligned and packed single-walled carbon nanotubes

Direct measurement of ion diffusion in aligned, densified single-walled carbon nanotube electrodes showed that the diffusion coefficient for transport of ions (KSCN in acetonitrile) parallel to the alignment direction of the nanotubes was close to the theoretical limit of perfectly straight pores, achieving a value 20 times larger than that of activated carbon electrodes (1 × 10(-5) vs 5 × 10(-7) cm(2)/s). In contrast, the diffusion coefficient for ion transport perpendicular to the alignment direction was an order of magnitude smaller (8 × 10(-7) cm(2)/s). As an example of the ramifications of this anisotropic diffusion phenomenon, the difference in performance of the aligned carbon nanotubes as electrochemical-capacitor electrodes was evaluated. At low discharge rates, the performances of the two orientations were identical, but as the discharge rate was increased, a more rapid decline in capacitance was observed for the perpendicular orientation (66 vs 14% decline in capacitance when the discharge current was increased from 0.01 to 1 A/g). Furthermore, the maximum power rating of the perpendicular electrode was lower than that of the parallel electrode (1.85 vs 3 kW/kg during operation at 1 V).     

Pegylated single-walled carbon nanotubes with gelable block copolymers

Functional amphiphilic block copolymer poly（ethylene glycol）-block-poly[（3-（triethoxysilyl）propyl methacrylate）-co -（1-pyrene-methyl） methacrylate],PEG₁₁₃-b-P(TEPM₂₆-co-PyMMA₄),was synthesized via atom transfer radical polymerization（ATRP） initiated by monomethoxy capped poly（ethylene glycol） bromoisobutyratc.This polymer exhibited strong ability to disperse and exfoliate single-walled carbon nanotubes（SWNTs） in different solvents due to the adhesion of pyrene units to surface of SWNTs.In aqueous solution,the PTEPM segments that were located on the nanotube surfaces with the pyrene units could be gelated and,as a result,the silica oxide networks with PEG coronas were formed on the surface of nanotubes,which ensured the composites with a good dispersibility and stability.Furthermore,functional silane coupling agents,3-mercaptopropyltrimethoxysilane and 3-aminopropyltriethoxysilanc,were introduced during dispersion of SWNTs using the block copolymers.They were co-gelated with PTEPM segments,and the-SH and-NH₂ functionalities were introduced into the silica oxide coats respectively.     

Voltammetric determination of tinidazole using a glassy carbon electrode modified with single-wall carbon nanotubes.

An electrochemical method based on a single-wall carbon nanotubes (SWNTs) film-coated glassy carbon electrode (GCE) was described for the determination of tinidazole. In a 0.1 M Britton-Robinson buffer with a pH of 10.0, tinidazole yields a very sensitive and well-defined reduction peak at -0.78 V (vs. SCE) on a SWNTs-modified GCE. Compared with that on a bare GCE, the reduction peak of tinidazole increases significantly on the modified GCE. Thus, all of the experimental parameters were optimized and a sensitive voltammetric method is proposed for tinidazole determination. It is found that the reduction peak current is proportional to the concentration of tinidazole over the range from 5 x 10(-8) to 4 x 10(-5) M, and that the detection limit is 1 x 10(-8) M at 3 min open-circuit accumulation. This new analysis method was demonstrated with tinidazole drugs.     

Simultaneous determination of 2-nitrophenol and 4-nitrophenol based on the multi-wall carbon nanotubes Nafion-modified electrode

In this work, multi-wall carbon nanotubes (MWNT) were conveniently dispersed into Nafion-ethanol solution, and the MWNT-Nafion-modified glassy carbon electrode (GCE) was described for the simultaneous determination of 2-nitrophenol and 4-nitrophenol. At pH 4.0 phosphate buffer, the reduction peak currents of 2-nitrophenol (at -0.8 V) and 4-nitrophenol (at -1.0 V) increase significantly at the MWNT-Nafion-modified GCE, in comparison with that at the Nafion-modified GCE and the bare GCE. The experimental parameters, such as solution pH of phosphate buffer, accumulation potential and time, and the amounts of MWNT-Nafion onto the GCE surface, were optimized. The reduction peak currents are linear with the concentration of 2-nitrophenol from 5 x 10(-8) to 1 x 10(-5) mol L(-1) and with that of 4-nitrophenol from 1 x 10(-7) to 1 x 10(-5) mol L(-1). The detection limits after 3-min accumulation are 1 x 10(-8) mol L(-1) for 2-nitrophenol and for 4 x 10(-8) mol L(-1) for 4-nitrophenol. This modified electrode was applied to direct determination of 2-nitrophenol and 4-nitrophenol in lake water samples.     

Vibrational behavior of adsorbed CO2 on single-walled carbon nanotubes

We present theoretical and experimental evidence for CO(2) adsorption on different sites of single walled carbon nanotube (SWNT) bundles. We use local density approximation density functional theory (LDA-DFT) calculations to compute the adsorption energies and vibrational frequencies for CO(2) adsorbed on SWNT bundles. The LDA-DFT calculations give a range of shifts for the asymmetric stretching mode from about -6 to -20 cm(-1) for internally bound CO(2), and a range from -4 to -16 cm(-1) for externally bound CO(2) at low densities. The magnitude of the shift is larger for CO(2) adsorbed parallel to the SWNT surface; various perpendicular configurations yield much smaller theoretical shifts. The asymmetric stretching mode for CO(2) adsorbed in groove sites and interstitial sites exhibits calculated shifts of -22.2 and -23.8 cm(-1), respectively. The calculations show that vibrational mode softening is due to three effects: (1) dynamic image charges in the nanotube; (2) the confining effect of the adsorption potential; (3) dynamic dipole coupling with other adsorbate molecules. Infrared measurements indicate that two families of CO(2) adsorption sites are present. One family, exhibiting a shift of about -20 cm(-1) is assigned to internally bound CO(2) molecules in a parallel configuration. This type of CO(2) is readily displaced by Xe, a test for densely populated adsorbed species, which are expected to be present on the highest adsorption energy sites in the interior of the nanotubes. The second family exhibits a shift of about -7 cm(-1) and the site location and configuration for these species is ambiguous, based on comparison with the theoretical shifts. The population of the internally bound CO(2) may be enhanced by established etching procedures that open the entry ports for adsorption, namely, ozone oxidation followed by annealing in vacuum at 873 K. Xenon displacement experiments indicate that internally bound CO(2) is preferentially displaced relative to the -7 cm(-1) shifted species. The -7 cm(-1) shifted species is assigned to CO(2) adsorbed on the external surface based on results from etching and Xe displacement experiments.     

Individual dissolution of single-walled carbon nanotubes in aqueous solutions of steroid or sugar compounds and their Raman and near-IR spectral properties

The individual solubilization of single-walled carbon nanotubes (SWNTs), achieved by using ten different anionic-, zwitterionic-, and nonionic-steroid biosurfactants and three different sugar biosurfactants, was examined. Aqueous micelles of anionic cholate analogues, such as sodium cholate (SC), sodium deoxycholate (SDC), sodium taurocholate (STC), sodium taurodeoxycholate (STDC), sodium glycocholate (SGC), as well as N,N-bis(3-D-gluconamidopropyl)cholamide (BIGCHAP) and N,N-bis(3-D-gluconamidopropyl)deoxycholamide (deoxy-BIGCHAP), exhibited good abilities to dissolve the SWNTs individually. Aqueous micelles of nonionic biosurfactants, such as sucrose monocholate (SMC), n-octyl-beta-D-glucoside (OG), n-decyl-beta-D-maltoside (DM), and n-decanoyl-N-methylglucamide (MEGA-10), could dissolve the SWNTs, however, the solubilization abilities were weaker than those of the anionic cholate analogues. In sharp contrast, the solubilization abilities of the zwitterionic micelles of 3-[(3-cholamidopropyl)dimethylammonio]propanesulfonic acid (CHAPS) and 3-[(3-cholamidopropyl)dimethylammonio]-2-hydroxypropanesulfonic acid (CHAPSO) were very low, and almost zero for OG. It is evident that the chemical structures, in particular the substituent groups of the surfactants, play an important role in the solubilization of SWNTs. The near-IR photoluminescence behaviors of the SWNTs dissolved in aqueous micelles and in 1 mM biosurfactants were investigated. The chirality indices of the SWNTs dissolved in these solutions depend on the chemical structures of the biosurfactants. The Raman spectra of the SWNTs dissolved in a 1 mM solution of SC suggest the selective extraction of the metallic SWNTs. Finally, a possible solubilization mechanism using steroid surfactants is described. The SWNTs dissolved individually in water-containing biocompounds are useful in many areas of nano- and materials chemistry.     

Nanoscale vibrational analysis of single-walled carbon nanotubes

We use near-field Raman imaging and spectroscopy to study localized vibrational modes along individual, single-walled carbon nanotubes (SWNTs) with a spatial resolution of 10-20 nm. Our approach relies on the enhanced field near a laser-irradiated gold tip which acts as the Raman excitation source. We find that for arc-discharge SWNTs, both the radial breathing mode (RBM) and intermediate frequency mode (IFM) are highly localized. We attribute such localization to local changes in the tube structure (n, m). In comparison, we observe no such localization of the Raman active modes in SWNTs grown by chemical vapor deposition (CVD). The direct comparison between arc-discharge and CVD-grown tubes allows us to rule out any artifacts induced by the supporting substrate.     

Direct electrochemistry and reagentless biosensing of glucose oxidase immobilized on chitosan wrapped single-walled carbon nanotubes

Single-walled carbon nanotubes (SWCNTs) selectively wrapped by a water-soluble, environmentally friendly, biocompatible polymer chitosan (CHI) were employed for the construction of a bioelectrochemical platform for the direct electron transfer (DET) of glucose oxidase (GOD) and biosensing purposes. Scanning electron microscopy and Raman spectroscopy were used to investigate the properties of the SWCNT-CHI film. The results show that the preferentially wrapped small-diameter SWCNTs are dispersed within the CHI film and exist on the surface of the electrode as small bundles. The DET between GOD and the electrode surface was observed with a formal potential of about ca. -460 mV vs. SCE in phosphate buffer solution. The heterogeneous electron transfer rate constant and the surface coverage of GOD are estimated to be 3.0 s(-1) and 1.3 x 10(-10)mol/cm(2), respectively. The experimental results demonstrate that the immobilized GOD retains its catalytic activity towards the oxidation of glucose. Such a GOD/SWCNT-CHI film-based biosensor not only exhibits a rapid response time, a wide linear rang and a low detection limits at a detection potential of -400 mV but also shows the effective anti-interference capability. Significantly improved analytical capabilities of the GOD/SWCNT-CHI/GC electrode could be ascribed to the unique properties of the individual SWCNTs and to the biocompatibility of CHI.     

Optical behaviors of conjugated-chain compounds containing benzene and furan units

Thirteen conjugated-chain compounds which contain benzene and furan units were prepared, their optical behaviors, including UV-vis absorption coefficient (varepsilon), absorption wavelengths (lambdaa), fluorescence emission wavelengths (lambdae), and quantum yields (Phi) were measured. Meanwhile, their LUMO and HOMO energy were determined by cyclic voltammetry and their second-order polarizations (betaxxx) values were determined by solvatochromic method, respectively. The results showed that this kind of compounds possess a shorter lambdaa (320-365 nm) and performance a higher Phi values, especially for 2aa, 2ab, 2ac and 2bb, their Phi values are all more than 90%. These compounds, except 2db, showed a higher betaxxx values in DMSO, especially for 2dc (75.77x10(-30) m5 C-1) and 2dd (83.32x10(-30) m5 C-1), than that 10-methyl-acridone (6.578x10(-30) m5 C-1) or 10-benzylacridone (6.845x10(-30) m5 C-1) in DMSO did, and second harmonic generation value of 10-methylacridone and 10-benzylacridone in powder are, respectively, 1.381 and 1.861 times of that value of urea. The betaxxx values and Phi values determined for these compounds in this work were lower than these values which were desired in the original work, this phenomena was explained from their molecular structures. This work confirmed that as these compounds performance shorter lambdaa and higher Phi values, they could be good blue-color optical materials for some fields, such as OLED materials, two-photo absorption materials, fluorescent dyes.     

Antenna chemistry with metallic single-walled carbon nanotubes

We show that, when subjected to microwave fields, surfactant-stabilized single-walled carbon nanotubes (SWNTs) develop polarization potentials at their extremities that readily drive electrochemical reactions. In the presence of transition metal salts with high oxidation potential (e.g., FeCl3), SWNTs drive reductive condensation to metallic nanoparticles with essentially diffusion-limited kinetics in a laboratory microwave reactor. Using HAuCl4, metallic particles and sheaths deposit regioselectively at the SWNT tips, yielding novel SWNT-metal composite nanostructures. This process is shown to activate exclusively metallic SWNTs; a degree of diameter selectivity is observed using acceptors with different oxidation potentials. The reaction mechanism is shown to involve Fowler-Nordheim field emission in solution, where electric fields concentrate at the SWNT tips (attaining approximately 10(9) V/m) due to the SWNT high aspect ratio (approximately 1000) and gradient compression in the insulating surfactant monolayer. Nanotube antenna chemistry is remarkably simple and should be useful in SWNT separation and fractionation processes, while the unusual nanostructures produced could impact nanomedicine, energy harvesting, and synthetic applications.