NEXAFS光谱分析聚合物修饰的单壁碳纳米管

利用C1s、O1s、N1s近边X射线吸收精细结构(Near Edge X-Ray Absorption Fine Structure,NEXAFS)光谱对聚合物修饰的碳纳米管进行了分析,研究了氧化及偶联聚合物对碳纳米管结构的影响。氧化碳纳米管及十八胺修饰的、聚合物/十八胺双修饰的碳纳米管的NEXAFS光谱均出现了碳/氧K边π*(C=O)和σ*(C-O)共振峰;而十八胺修饰的、聚合物/十八胺双修饰的碳纳米管则出现了氮K边π*(N-C=O)和σ*(N1s)共振峰。分析表明,NEXAFS光谱可有效表征聚合物修饰的碳纳米管。     

pH dependence of the electronic structure of glycine

The carbon, nitrogen, and oxygen K-edge spectra were measured for aqueous solutions of glycine by total electron yield near-edge X-ray absorption fine structure (TEY NEXAFS) spectroscopy. The bulk solution pH was systematically varied while maintaining a constant amino acid concentration. Spectra were assigned through comparisons with both previous studies and ab initio computed spectra of isolated glycine molecules and hydrated glycine clusters. Nitrogen K-edge solution spectra recorded at low and moderate pH are nearly identical to those of solid glycine, whereas basic solution spectra strongly resemble those of the gas phase. The carbon 1s --> pi*(C=O) transition exhibits a 0.2 eV red shift at high pH due to the deprotonation of the amine terminus. This deprotonation also effects a 1.4 eV red shift in the nitrogen K-edge at high pH. Two sharp preedge features at 401.3 and 402.5 eV are also observed at high pH. These resonances, previously observed in the vapor-phase ISEELS spectrum of glycine, have been reassigned as transitions to sigma* bound states. The observation of these peaks indicates that the amine moiety is in an acceptor-only hydrogen bond configuration at high pH. At low pH, the oxygen 1s --> pi*(C=O) transition exhibits a 0.25-eV red shift due to the protonation of the carboxylic acid terminus. These spectral differences indicate that the variations in electronic structure observed in the NEXAFS spectra are determined by the internal charge state and hydration environment of the molecule in solution.     

Self-assembled carbon nanotubes on gold: polarization-modulated infrared reflection-absorption spectroscopy, high-resolution X-ray photoemission spectroscopy, and near-edge X-ray absorption fine structure spectroscopy study

Recently we reported noncovalent functionalization of nanotubes in an aqueous medium with ionic liquid-based surfactants, 1-dodecyl-3-methylimidazolium bromide (1) and 1-(12-mercaptododecyl)-3-methylimidazolium bromide (2), resulting in positively charged single-wall carbon nanotube (SWNT)-1,2 composites. Thiolation of SWNTs with 2 provides their self-assembly on gold as well as templating gold nanoparticles on SWNT sidewalls via a covalent -S-Au bond. In this investigation, we studied the electronic structure, intermolecular interactions, and packing within noncovalently thiolated SWNTs and also nanotube alignment in the bulk of SWNT-2 dried droplets and self-assembled submonolayers (SAMs) on gold by high-resolution X-ray photoemission spectroscopy (HRXPS), C K-edge X-ray absorption fine structure (NEXAFS) spectroscopy, and polarization-modulated infrared reflection-absorption spectroscopy (PM-IRRAS). HRXPS data confirmed the noncovalent nature of interactions within the nanocomposite of thiolated nanotubes. In PM-IRRAS spectra of SWNT SAMs on gold, the IR-active vibrational SWNT modes have been observed and identified. According to PM-IRRAS data, the hydrocarbon chains of 2 are oriented with less tilt angle to the bare gold normal in a SAM deposited from an SWNT-2 dispersion than those of 1 deposited from an SWNT-1 dispersion on the mercaptoethanesulfonic acid-primed gold. For both the dried SWNT-2 bulk and the SWNT-2 SAM on gold, the C K-edge NEXAFS spectra revealed the presence of CH-pi interactions between hydrocarbon chains of 2 and the pi electronic nanotube structure due to the highly resolved vibronic fine structure of carbon 1s --> R*/sigma*C-H series of states in the alkyl chain of 2. For the SWNT-2 bulk, the observed splitting and upshift of the SWNT pi* orbitals in the NEXAFS spectrum indicated the presence of pi-pi interactions. In the NEXAFS spectrum of the SWNT-2 SAM on gold, the upshifted values of the photon energy for R*/sigma*C-H transitions indicated close contact of 2 with nanotubes and with a gold surface. The angle-dependent NEXAFS for the SWNT-2 bulk showed that most of the molecules of 2 are aligned along the nanotubes, which are self-organized with orientation parallel to the substrate plane, whereas the NEXAFS for the SWNT-2 SAM revealed a more normal orientation of functionality 2 on gold compared with that in the SWNT-2 bulk.     

Core level study of alanine and threonine

Core level X-ray photoemission spectra (XPS) and near edge X-ray absorption fine structure (NEXAFS) spectra of alanine and threonine in the gas phase have been measured at the carbon, nitrogen, and oxygen K edges and interpreted in the light of theoretical calculations. For the computations, a set of approximations is made which allows sufficiently accurate calculations of several conformers to be performed in reasonable computing time. The accuracy has been checked by comparing results obtained for proline to our previous, higher level calculations. The photoemission spectra at the carbon and oxygen edges are assigned and compared. The nitrogen 1s photoemission peaks show anomalous broadening which we relate to the populations and types of conformers. The carbon K-edge NEXAFS spectra of alanine and threonine are compared with our previous data on glycine and resonances assigned accordingly. The nitrogen K-edge NEXAFS spectra of alanine and threonine do not show measurable effects due to the population of conformers, in contrast to the photoemission results. At the oxygen K edge, the spectra of these amino acids are similar with two prominent peaks assigned to transitions of O 1s electrons from the oxo and hydroxyl groups to vacant pi* and sigma* orbitals and additional intensity for threonine due to the second OH group. Conformer effects are observable in photoemission but appear to be more difficult to resolve in photoabsorption. We explain this by energetic shifts of opposite sign for the core hole states and unoccupied orbitals, which causes partial cancelation in NEXAFS but not in photoemission.     

Etching of carbon nanotubes by ozone--a surface area study

The oxidative etching of single walled carbon nanotubes (SWNTs) is useful for opening the end caps and the sidewalls of the nanotubes to provide access to the interior. We have studied the effect of successive treatment of SWNTs by 95% pure O(3)(g), which is a powerful and convenient oxidizing agent. The surface area of the SWNTs was measured following exposure to O(3)(g) at 300 K and also following heating to 1073 K in a vacuum to decompose the oxidized groups on the nanotubes, a procedure called etching. This O(3)-induced etching process was observed by scanning electron microscopy and by transmission electron microscopy, and the kinetics of the process was studied gravimetrically. It was found that O(3) attack occurs preferentially on the outermost geometric surface of the conglomerate sample of the nanotubes as a result of the high efficiency of O(3) to react in a few collisions with the nanotube surface. Ozone-induced etching causes the loss of pores in the 20 A diameter range as observed by nitrogen adsorption at equilibrium by density functional theory analysis.     

Permanent Trapping of CO(2) in Single-Walled Carbon Nanotubes Synthesized by the HiPco Process

Infrared spectroscopy is used to study trapped and physisorbed CO2 in single-walled carbon nanotube bundles (SWNTs) synthesized by the HiPco process. CO2 is entrapped within the SWNTs by acid oxidation of the unpurified sample followed by vacuum heating to 700 K. The trapped CO2 has a single nu3 mode at 2327 cm-1, is stable during temperature cycling from 77 to 700 K, and remains after venting to room air. CO2 physisorption studies show a nu3 mode at 2330 cm-1 for the as-received HiPco samples, 2340 cm-1 for the acid-oxidized sample, and 2327 and 2340 cm-1 for the oxidized sample after vacuum heating. The sites responsible for the infrared peaks of the physisorbed and trapped species are discussed.     

Near edge X-ray absorption fine structure spectroscopy of bacterial hydroxamate siderophores in aqueous solutions

X-ray absorption spectroscopy (XAS) is widely used to explore the coordination environments and structures of metal complexes in aqueous solutions and disordered phases. Although soft-XAS studies on gaseous phases, solid phases and their interfaces have shown that XAS is a versatile tool in studying the functional group composition of organic molecules, the application of XAS to studying aqueous solutions is seriously limited because of experimental difficulties. In this report, using a modified synchrotron endstation geometry, we show how soft-XAS was used to study the changes in electronic states of reactive functional groups in a bacterial macromolecule, desferrioxamine B (desB, a hydroxamate siderophore) and its structural analogue (acetohydroxamic acid (aHa)). We collected C, N, and O near edge X-ray absorption fine structure (NEXAFS) spectra of these molecules in aqueous solutions and complemented their spectral interpretation with calculated X-ray spectra of "hydrated" aHa. The experimental spectra of desB are similar to those for aHa at the C, N, and O K-edges. In addition, the electronic transitions of amide and hydroxamate functional groups in the macromolecule can be distinguished from the N spectra. Small energy differences in the pi*(C=O)NO and the transitions at the C- and N-edges of aHa and desB indicate that the substituent attached to N in desB ((CH2)n) determines the electron density in the (C=O)NO core. As the solution pH increased, the pi*(C=O)NO transition of the hydroxamate group of these two molecules exhibit energy shifts at the C-, N-, and O-edges, which are consistent with increased electron delocalization in the (C=O)NO core of aHa (and desB), predicted from the calculations. The spectra of the aHa(H2O)3- anion also provide evidence for partial N-deprotonation at pH values usually attributed to an O-acid. These results indicate that soft-XAS is well suited for studying the electronic states of different functional groups in aqueous organic macromolecules.     

Orbital-resolved partial charge transfer from the methoxy groups of substituted pyrenes in complexes with tetracyanoquinodimethane--a NEXAFS study

It is demonstrated that the near-edge X-ray absorption fine structure (NEXAFS) provides a powerful local probe of functional groups in novel charge transfer (CT) compounds and their electronic properties. Microcrystals of tetra-/hexamethoxypyrene as donors with the strong acceptor tetracyano-p-quinodimethane (TMP/HMP-TCNQ) were grown by vapor diffusion. The oxygen and nitrogen K-edge spectra are spectroscopic fingerprints of the functional groups in the donor and acceptor moieties, respectively. The orbital selectivity of the NEXAFS pre-edge resonances allows us to precisely elucidate the participation of specific orbitals in the charge transfer process. Upon complex formation, the intensities of several resonances change substantially and a new resonance occurs in the oxygen K-edge spectrum. This gives evidence of a corresponding change of hybridization of specific orbitals in the functional groups of the donor (those derived from the frontier orbitals 2e and 6a(1) of the isolated methoxy group) and acceptor (orbitals b(3g), a(u), b(1g), and b(2u), all located at the cyano group) with π*-orbitals of the ring systems. Along with this intensity effect, the resonance positions associated with the oxygen K-edge (donor) and nitrogen K-edge (acceptor) shift to higher and lower photon energies in the complex, respectively. A calculation based on density functional theory qualitatively explains the experimental results. NEXAFS measurements shine light on the action of the functional groups and elucidate charge transfer on a submolecular level.     

Local hydration environments of amino acids and dipeptides studied by X-ray spectroscopy of liquid microjets

The nitrogen K-edge spectra of aqueous proline and diglycine solutions have been measured by total electron yield near-edge X-ray absorption fine structure (NEXAFS) spectroscopy at neutral and high pH. All observed spectral features have been assigned by comparison to the recently reported spectrum of aqueous glycine and calculated spectra of isolated amino acids and hydrated amino acid clusters. The sharp preedge resonances at 401.3 and 402.6 eV observed in the spectrum of anionic glycine indicate that the nitrogen terminus is in an "acceptor-only" configuration, wherein neither amine proton is involved in hydrogen bonding to the solvent, at high pH. The analogous 1s --> sigma(NH) preedge transitions are absent in the NEXAFS spectrum of anionic proline, implying that the acceptor-only conformation observed in anionic glycine arises from steric shielding induced by free rotation of the amine terminus about the glycine CN bond. Anionic diglycine solutions exhibit a broadened 1s --> pi(CN) resonance at 401.2 eV and a broad shoulder resonance at 403 eV, also suggesting the presence of an acceptor-only species. Although this assignment is not as unambiguous as for glycine, it implies that the nitrogen terminus of most proteins is capable of existing in an acceptor-only conformation at high pH. The NEXAFS spectrum of zwitterionic lysine solution was also measured, exhibiting features similar to those of both anionic and zwitterionic glycine, and leading us to conclude that the alpha amine group is present in an acceptor-only configuration, while the end of the butylammonium side chain is fully solvated.     

Geometric and electronic structure of the heme-peroxo-copper complex [(F8TPP)FeIII-(O22-)-CuII(TMPA)](ClO4)

The geometric and electronic structure of the untethered heme-peroxo-copper model complex [(F(8)TPP)Fe(III)-(O(2)(2)(-))-Cu(II)(TMPA)](ClO(4)) (1) has been investigated using Cu and Fe K-edge EXAFS spectroscopy and density functional theory calculations in order to describe its geometric and electronic structure. The Fe and Cu K-edge EXAFS data were fit with a Cu...Fe distance of approximately 3.72 A. Spin-unrestricted DFT calculations for the S(T) = 2 spin state were performed on [(P)Fe(III)-(O(2)(2)(-))-Cu(II)(TMPA)](+) as a model of 1. The peroxo unit is bound end-on to the copper, and side-on to the high-spin iron, for an overall mu-eta(1):eta(2) coordination mode. The calculated Cu...Fe distance is approximately 0.3 A longer than that observed experimentally. Reoptimization of [(P)Fe(III)-(O(2)(2)(-))-Cu(II)(TMPA)](+) with a 3.7 A Cu...Fe constrained distance results in a similar energy and structure that retains the overall mu-eta(1):eta(2)-peroxo coordination mode. The primary bonding interaction between the copper and the peroxide involves electron donation into the half-occupied Cu d(z)2 orbital from the peroxide pi(sigma) orbital. In the case of the Fe(III)-peroxide eta(2) bond, the two major components arise from the donor interactions of the peroxide pi*(sigma) and pi*(v) orbitals with the Fe d(xz) and d(xy) orbitals, which give rise to sigma and delta bonds, respectively. The pi*(sigma) interaction with both the half-occupied d(z)2 orbital on the copper (eta(1)) and the d(xz) orbital on the iron (eta(2)), provides an effective superexchange pathway for strong antiferromagnetic coupling between the metal centers.     

Surface sensitive study to determine the reactivity of soot with the focus on the European emission standards IV and VI

Diesel soot (Euro IV and Euro VI) was investigated with spectroscopic methods such as near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and X-ray photoemission spectroscopy (XPS). C and O K-edge NEXAFS show that structural disorder on the surface is accompanied by a higher amount of oxygen functional groups. O K-edge NEXAFS and O1s XPS results are discussed with the aim to elucidate the nature of the oxygen surface species. The analysis of the data presented here allows the postulation of a hypothetical structure for soot samples emitted by diesel engines.     

Structure analyses of dodecylated single-walled carbon nanotubes

Alkylation of nanotube salts prepared using either lithium, sodium, or potassium in liquid ammonia yields sidewall-functionalized nanotubes that are soluble in organic solvents. Atomic force microscopy and transmission electron microscopy studies of dodecylated SWNTs prepared from HiPco nanotubes and 1-iodododecane show that extensive debundling results from intercalation of the alkali metal into the SWNT ropes. TGA-FTIR analyses of samples prepared from the different metals revealed radically different thermal behavior during detachment of the dodecyl groups. The SWNTs prepared using lithium can be converted into the pristine SWNTs at 180-330 degrees C, whereas the dodecylated SWNTs prepared using sodium require a much higher temperature (380-530 degrees C) for dealkylation. SWNTs prepared using potassium behave differently, leading to detachment of the alkyl groups over the temperature range 180-500 degrees C. These differences can be observed by analysis of the solid-state 13C NMR spectra of the dodecylated SWNTs that have been prepared using the different alkali metals and may indicate differences in the relative amounts of 1,2- and 1,4-addition of the alkyl groups.     

Hydrogen bonding in methanol clusters probed by inner-shell photoabsorption spectroscopy in the carbon and oxygen K-edge regions

Hydrogen bonding in methanol clusters has been investigated by using inner-shell photoabsorption spectroscopy and density functional theory (DFT) calculations in the carbon and oxygen K-edge regions. The partial-ion-yield (PIY) curves of H(CH(3)OH)(n)(+) were measured as the soft x-ray absorption spectra of methanol clusters. The first resonance peak in the PIY curves, which is assigned to the sigma*(O-H) resonance transition, exhibits a 1.20 eV blueshift relative to the total-ion-yield (TIY) curves of molecular methanol in the oxygen K-edge region, while it exhibits a shift of only 0.25 eV in the carbon K-edge region. Decreased intensities of the transitions to higher Rydberg orbitals were observed in the PIY curves of the clusters. The drastic change in the sigma*(O-H) resonance transition is interpreted by the change in the character of the sigma*(O-H) molecular orbital at the H-donating OH site due to the hydrogen-bonding interaction.     

Covalent sidewall functionalization of single wall carbon nanotubes

Alkyllithium reagents may be used to attach alkyl groups to the sidewalls of fluoro nanotubes. Thermal gravimetric analysis combined with UV-vis-Nir spectroscopy has been used to provide a quantitative measure of the degree of functionalization. SWNTs prepared using the HiPco process exhibit a higher degree of alkylation than SWNTs from the laser-oven method, indicating that the smaller diameter fluoro tubes are alkylated more readily. The spectral signature of the pristine SWNTs can be regenerated when the alkylated SWNTs are heated in Ar at 500 degrees C, demonstrating that dealkylation occurs at this temperature. TGA-MS analysis using a sample of n-butylated h-SWNTs showed that 1-butene and n-butane are formed during thermolysis.     

Individual single-walled nanotubes and hydrogels made by oxidative exfoliation of carbon nanotube ropes

Single-walled carbon nanotubes were oxidized by a technique previously developed for the oxidation of graphite to graphite oxide (GO). This process involves treatment with concentrated H(2)SO(4) containing (NH(4))(2)S(2)O(8) and P(2)O(5), followed by H(2)SO(4) and KMnO(4). Oxidation results in complete exfoliation of nanotube ropes to yield individual oxidized tubes that are 40-500 nm long. The C:O:H atomic ratio of vacuum-dried oxidized nanotubes is approximately 2.7:1.0:1.2. XPS and IR spectra show evidence for surface O-H, C=O, and COOH groups. The oxidized nanotubes slowly form viscous hydrogels at unusually low concentration (>or=0.3 wt %), and this behavior is attributed to the formation of a hydrogen-bonded nanotube network. The oxidized tubes bind readily to amine-coated surfaces, on which they adsorb as smooth and dense monolayer films. Thin films of the oxidized nanotubes show ohmic current-voltage behavior, with resistivities in the range of 0.2-0.5 Omega-cm.     

On the unusual 2J(C2-H(f)) coupling dependence on syn/anti CHO conformation in 5-X-furan-2-carboxaldehydes

A remarkable difference for (2)J(C(2)-H(f)) coupling constant in syn and anti conformers of 5-X-furan-2-carboxaldehydes (X = CH(3), Ph, NO(2), Br) and a rationalization of this difference are reported. On the basis of the current knowledge of the Fermi-contact term transmission, a rather unusual dual-coupling pathway in the syn conformer is presented. The additional coupling pathway resembles somewhat that of the J(H-H) in homoallylic couplings, which are transmitted by hyperconjugative interactions involving the pi(C=C) electronic system. The homoallylic coupling pathway can be labeled as sigma*(C-H) <-- pi(C=C) --> sigma*(C-H). In the present case, this additional coupling pathway, using an analogous notation, can be labeled as sigma*(C(2)-C(C)) <-- LP(1)(O(1))...LP(2)(O(C)) --> sigma*(C(C)-H(f)) (sigma*(C(2)-C(C))) where O(1) and O(C) stand for the ring and carbonyl O atoms, respectively. This additional coupling pathway is not activated in the anti conformers since both oxygen lone pairs do not overlap.     

Aqueous dispersion, surface thiolation, and direct self-assembly of carbon nanotubes on gold

We report the efficient aqueous dispersion of pristine HiPco single-walled carbon nanotubes (SWNTs) with ionic liquid (IL)-based surfactants 1-dodecyl-3-methylimidazolium bromide (1) and 1-(12-mercaptododecyl)-3-methylimidazolium bromide (2), the thiolation of nanotube sidewalls with 2, and the controlled self-assembly of positively charged SWNT-1,2 composites on gold. Optical absorption spectra and resonance Raman (RR) data of obtained aqueous SWNT-1,2 dispersions are consistent with debundled and noncovalently functionalized nanotubes whose electronic properties have not been disturbed. Additionally, the dispersion of pristine nanotube material with surfactants 1 and 2 leads to a high degree of purification from carbonaceous particles. The chiralities of the 14 smallest semiconducting HiPco SWNTs in resonance with Raman excitation at 1064 nm (1.165 eV) were determined in SWNT-2 aqueous dispersion using UV-vis-NIR and RR spectra. X-ray photoelectron spectroscopy (XPS) and surface-enhanced resonance Raman scattering (SERRS) spectroscopy of SWNT-2 submonolayers on gold verified the encapsulation of individualized SWNTs with IL surfactants, the cleavage of S-S disulfide bonds formed in aqueous SWNT-2 suspensions, and the direct chemisorption of the SWNT-2 composite on bare gold via the Au-S bond. Aqueous dispersions of SWNTs with IL-based surfactants add biofunctionality to carbon nanotubes by imparting the positive surface charge necessary for interactions with cell membranes. Our technique, which purifies pristine nanotube material and produces water-soluble, positively charged nanotubes with pendent surface-active thiol groups, may also be translated to other carbon nanotubes and carbon nanostructures. Self-assembled, positively charged submonolayers of SWNTs can be further used for applications in cell biology and sensor technology.     

Axially Chiral Facial Amphiphiles with a Dihydronaphthopentaphene Structure as Molecular Tweezers for SWNTs

Syntheses of chiral 6,15‐dihydronaphtho[2,3‐c]pentaphene derivatives of opposite configurations are reported. Starting from anthracene, the strategy involves two key steps: a Diels–Alder reaction on a prochiral dianthraquinone, and an enantiomeric resolution using (?)‐menthol. The final molecules exhibit very strong optical activity, as shown by their circular dichroism spectra, and are examples of chiral facial amphiphiles. Their adsorption at the surface of single‐walled carbon nanotubes (SWNTs) has also been studied, and has been found to occur preferentially on 0.8–1.0 nm diameter nanotubes among the population of a high‐pressure CO conversion (HiPco) SWNT sample (0.8–1.2 nm). The synthesised facial amphiphiles act as nano‐tweezers for the diameter‐selective solubilisation of SWNTs in water. The expected optical activities of the SWNT samples solubilised by each of the chiral amphiphiles have been studied by circular dichroism spectroscopy, but the results are not yet conclusive.     

Photoactivity and UV absorption spectroscopy of RCo(CO)4 (R = H, CH3) organometallic complexes

The photoactivity of RCo(CO)4 (R = H, CH3) complexes has been investigated and compared by means of state correlation diagrams connecting the low-lying singlet (1)E (d(Co) --> sigma*(Co-R) and d(Co) --> pi*(CO)) and (1)A1 (d(Co) --> pi*(CO)) electronic states accessible through UV irradiation, and the low-lying triplet states ((3)E and (3)A1), to the corresponding states of the primary products R + Co(CO)4 and CO(ax) + RCo(CO)3. The electronic absorption spectra have been calculated by time-dependent wave packet propagations on two-dimensional potential energy surfaces describing both channels of dissociation, namely the homolysis of the R-Co and the CO(ax)-Co bonds. It is shown that the absorption spectrum of HCo(CO)4 is characterized by two peaks; the most intense peaks for each set are located respectively at 42,659 and 45,001 cm(-1). The CH(3)Co(CO)4 absorption spectrum also gives two sets of signals with maximum intensities found at 42,581 and 51,515 cm(-1). These bands for both molecules are assigned to the two metal-to-ligand-charge-transfer (MLCT; d(Co) --> pi*(CO)) states. Three photoactive states have been determined in both molecules, namely the singlet metal-to-sigma-bond-charge-transfer (MSBCT) states (a(1)E and b(1)E), simultaneously dissociative for both the homolysis of CO and the R-Co bond, and the (3)A1 (sigma(Co-R) --> sigma*(Co-R)), dissociative along the R-Co bond.