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1.
The time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) positive and negative ion spectra of poly(2‐vinylpyridine) (P2VP) and poly(4‐vinylpyridine) (P4VP) were analyzed using density functional theory calculations. Most of the ions from these structural isomers shared the same accurate mass, but had different relative abundance. This could be attributed to the fact that from a thermodynamics perspective, the disparity in the molecular structures can affect the ion stability if we assume that they shared the same mechanistic pathway of formation with similar reaction kinetics. The molecular structures of these ions were assigned, and their stability was evaluated based on calculations using the Kohn‐Sham density functional theory with Becke's 3‐parameter Lee‐Yang‐Parr exchange‐correlation functional and a correlation‐consistent, polarized, valence, double‐zeta basis set for cations and the same basis set with a triple‐zeta for anions. The computational results agreed with the experimental observations that the nitrogen‐containing cations such as C5H4N+ (m/z = 78), C8H7N (m/z = 117), C8H8N+ (m/z = 118), C9H8N+ (m/z = 130), C13H11N2+ (m/z = 195), C14H13N2+ (m/z = 209), C15H15N2+ (m/z = 223), and C21H22N3+ (m/z = 316) ions were more favorably formed in P2VP than in P4VP due to higher ion stability because the calculated total energies of these cations were more negative when the nitrogen was situated at the ortho position. Nevertheless, our assumption was invalid in the formation of positive ions such as C6H7N+˙ (m/z = 93) and C8H10N+ (m/z = 120). Their formation did not necessarily depend on the ion stability. Instead, the transition state chemistry and the matrix effect both played a role. In the negative ion spectra, we found that nitrogen‐containing anions such as C5H4N? (m/z = 78), C6H6N? (m/z = 92), C7H6N? (m/z = 104), C8H6N? (m/z = 116), C9H10N? (m/z = 132), C13H11N2? (m/z = 195), and C14H13N2? (m/z = 209) ions were more favorably formed in P4VP, which is in line with our computational results without exception. We speculate that whether anions would form from P2VP and P4VP is more dependent on the stability of the ions.  相似文献   

2.
Focused ion beam implantation of 30‐keV Ga+ ions in single‐crystalline Si and Ge was investigated by SIMS, using Cs+ primary ions for sputtering. Nine different implantation fluences ranging from 1 × 1013 to 1 × 1017 Ga+‐ions/cm2 were used, with implanted areas of 40 × 40 µm2. The Ga concentration distributions of these implants were determined by SIMS depth profiling. Such 30‐keV Ga implantations were also simulated by a dynamic Monte‐Carlo code that takes into account the gradual change of the near‐surface composition due to the Ga incorporation. In both approaches, an essentially linear increase of the Ga peak concentrations with fluence is found up to ~1 × 1016cm?2; for higher fluences, the Ga content approaches a saturation level which is reached at about (1–2) × 1017cm?2. The measured and simulated peak concentrations of the Ga distributions are in good agreement. The most probable ranges obtained from the experiments correspond closely with the respective values from the simulations. The surface morphology caused by Ga+ implantation was investigated by atomic force microscopy (AFM). The AFM data indicate that for low fluences (<3 × 1015cm?2) the surface within the implanted areas is growing outward (i.e. is swelling). For increasingly higher fluences, sputter‐induced erosion of the surface becomes dominant and distinct craters are formed for fluences above ~1 × 1016cm?2. At the boundary of the implanted region a wall‐like structure is found to form upon Ga implantation; its height is growing with increasing fluence, reaching a value of ~15 nm at 1 × 1017 Ga+‐ions/cm2. Copyright © 2008 John Wiley & Sons, Ltd.  相似文献   

3.
Polycarbonate/polystyrene composites films were irradiated by 55 MeV Carbon ion beam with fluence ranging from 1 × 1011 to 1 × 1013 ions/cm2. The polymer composites films were prepared by solution mixing method. The effects of ion beam on structural, optical and surface morphology of PC/PS composites films were investigated by X-ray diffraction (XRD), UV-visible spectroscopy (UV-vis), Fourier Transform Infrared Spectroscopy (FT-IR) and Optical Microscope. The XRD pattern shows the average crystallite size, percentage of crystallinity and inter-chain separation, which decreases with increase in ion fluences. UV-vis spectra show that the energy band gap and transmittance decreases while number of carbon atoms increases with fluences. The FT-IR spectra evidenced very small change in cross linking and chain scissoring at high ion fluences, while the optical microscopy shows a color change with ion fluence.  相似文献   

4.
A Si crystal layer on SiO2/Si was implanted using 0.4-MeV Kr+, Ag+, and Au+ at ion fluences of 0.5 × 1015 to 5.0 × 1015 cm−2. Subsequent annealing was performed at temperatures of 450° and 800° for 1 hour. The structural modification in a Si crystal influences ion beam channelling phenomena; therefore, implanted and annealed samples were investigated by Rutherford backscattering spectrometry under channelling (RBS-C) conditions using an incident beam of 2-MeV He+ from a 3-MV Tandetron in random or in aligned directions. The depth profiles of the implanted atoms and the dislocated Si atom depth profiles in the Si layer were extracted directly from the RBS measurement. The damage accumulation and changes in the crystallographic structure before and after annealing were studied by X-ray diffraction (XRD) analysis. Lattice parameters in modified silicon layers determined by XRD were discussed in connection to RBS-C findings showing the crystalline structure modification depending on ion implantation and annealing parameters.  相似文献   

5.
We report the influence of 100 keV H+ ion beam irradiation on the surface morphology, crystalline structure, and transport properties of as‐deposited Al‐doped ZnO (Al:ZnO) thin films. The films were deposited on silicon (Si) substrate by using DC sputtering technique. The ion irradiation was carried out at various fluences ranging from 1.0 × 1012 to 3.0 × 1014 ions/cm2. The virgin and ion‐irradiated films were characterized by X‐ray diffraction, Raman spectroscopy, atomic force microscopy, and Hall probe measurements. Using X‐ray diffraction spectra, 5 points Williamson‐Hall plots were drawn to deduce the crystallite site and strain in Al:ZnO films. The analysis of the measurements shows that the films are almost radiation resistant in the structural deformation under chosen irradiation conditions. With beam irradiation, the transport properties of the films are also preserved (do not vary orders of magnitude). However, the surface roughness and the crystallite size, which are crucial parameters of the ZnO film as a gas sensor, are at variation with the ion fluence. As ion fluence increases, the root‐mean‐square surface roughness oscillates and the surface undergoes for smoothening with irradiation at chosen highest fluence. The crystallite size decreases initially, increases for intermediate fluences, and drops almost to the value of the pristine film at highest fluence. In the paper, these interesting experimental results are discussed in correlations with ion‐matter interactions especially energy losses by the ion beam in the material.  相似文献   

6.
N‐Boc/Fmoc/Z‐N′‐formyl‐gem‐diaminoalkyl derivatives, intermediates particularly useful in the synthesis of partially modified retro‐inverso peptides, have been characterized by both positive and negative ion electrospray ionization (ESI) ion‐trap multi‐stage mass spectrometry (MSn). The MS2 collision induced dissociation (CID) spectra of the sodium adduct of the formamides derived from the corresponding N‐Fmoc/Z‐amino acids, dipeptide and tripeptide acids show the [M + Na‐NH2CHO]+ ion, arising from the loss of formamide, as the base peak. Differently, the MS2 CID spectra of [M + Na]+ ion of all the N‐Boc derivatives yield the abundant [M + Na‐C4H8]+ and [M + Na‐Boc + H]+ ions because of the loss of isobutylene and CO2 from the Boc protecting function. Useful information on the type of amino acids and their sequence in the N‐protected dipeptidyl and tripeptidyl‐N′‐formamides is provided by MS2 and subsequent MSn experiments on the respective precursor ions. The negative ion ESI mass spectra of these oligomers show, in addition to [M‐H]?, [M + HCOO]? and [M + Cl]? ions, the presence of in‐source CID fragment ions deriving from the involvement of the N‐protecting group. Furthermore, MSn spectra of [M + Cl]? ion of N‐protected dipeptide and tripeptide derivatives show characteristic fragmentations that are useful for determining the nature of the C‐terminal gem‐diamino residue. The present paper represents an initial attempt to study the ESI‐MS behavior of these important intermediates and lays the groundwork for structural‐based studies on more complex partially modified retro‐inverso peptides. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   

7.
In context to the ion induced surface nanostructuring of metals and their burrowing in the substrates, we report the influence of Xe and Kr ion‐irradiation on Pt:Si and Ag:Si thin films of ~5‐nm thickness. For the irradiation of thin films, several ion energies (275 and 350 keV of Kr; 450 and 700 keV of Xe) were chosen to maintain a constant ratio of the nuclear energy loss to the electronic energy loss (Sn/Se) in Pt and Ag films (five in present studies). The ion‐fluence was varied from 1.0 × 1015 to 1.0 × 1017 ions/cm2. The irradiated films were characterized using Rutherford backscattering spectroscopy (RBS), atomic force microscopy (AFM) and scanning electron microscopy (SEM). The AFM and SEM images show ion beam induced systematic surface nano‐structuring of thin films. The surface nano‐structures evolve with the ion fluence. The RBS spectra show fluence dependent burrowing of Pt and Ag in Si upon the irradiation of both ion beams. At highest fluence, the depth of metal burrowing in Si for all irradiation conditions remains almost constant confirming the synergistic effect of energy losses by the ion beams. The RBS analysis also shows quite large sputtering of thin films bombarded with ion beams. The sputtering yield varied from 54% to 62% by irradiating the thin films with Xe and Kr ions of chosen energies at highest ion fluence. In the paper, we present the experimental results and discuss the ion induced surface nano‐structuring of Pt and Ag and their burrowing in Si. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   

8.
In the title compound, {[Co2(C14H8O4)2(C10H8N2)2(H2O)2]·2C14H10O4}n, each CoII ion is six‐coordinate in a slightly distorted octahedral geometry. Both CoII ions are located on twofold axes. One is surrounded by two O atoms from two biphenyl‐2,2′‐dicarboxylate (dpa) dianions, two N atoms from two 4,4′‐bipyridine (bpy) ligands and two water molecules, while the second is surrounded by four O atoms from two dpa dianions and two N atoms from two bpy ligands. The coordinated dpa dianion functions as a κ3‐bridge between the two CoII ions. One carboxylate group of a dpa dianion bridges two adjacent CoII ions, and one O atom of the other carboxylate group also chelates to a CoII ion. The CoII ions are bridged by dpa dianions and bpy ligands to form a chiral sheet. There are several strong intermolecular hydrogen bonds between the H2dpa solvent molecule and the chiral sheet, which result in a sandwich structure.  相似文献   

9.
《Electroanalysis》2005,17(14):1269-1278
Oxidation/reduction of polypyrrole films coupled with ion exchange on the polymer/solution interface can be utilized for amperometric sensing of electroinactive ions. Anion or cation exchanging films (polypyrrole doped by chloride or poly(4‐styrenesulfonate) ions, respectively) can be used to determine common anions (as Cl?, NO , SO etc) or cations (K+, Na+, Li+, Ca2+, Mg2+) under conditions of alternating current (AC) amperometry in the range 10?4–1 M. A sensitivity can be tuned by choosing appropriate electrode potential, corresponding to polypyrrole oxidation (anion‐exchanging films) or reduction (cation‐exchangers). Electrochemical impedance spectroscopy and AC‐voltammetry studies have shown that applied frequency and potential could also affect the observed dependence of the signal (admittance or AC‐current) on ion concentration. For high frequency the sensitivity is higher but selectivity lower, due to influence of solution conductivity on the response. For low frequencies the sensitivity is lower; however, a selectivity increase was observed due to diverse mobility of ions in the polymer film. Selectivity of AC‐amperometric responses was studied both in separate and mixed solutions.  相似文献   

10.
Cu nanoparticles with average particles size around 10 nm were incorporated on the surface of a mesoporous carbon nitride support. The XRD and N2 adsorption isotherms show that it maintains a hexagonal mesoporous structure with a high surface area (600.03 m2 g?1). The embedded Cu nanoparticles exhibit extremely high catalytic performance in two different kinds of organic reactions. The Huisgen 1,3‐dipolar cycloaddition and N‐arylation of N‐heterocycles were all accomplished.  相似文献   

11.
Helical structures are interesting due to their inherent chirality. Helicenium ions are triarylmethylium structures twisted into configurationally stable helicenes through the introduction of two heteroatom bridges between the three aryl substituents. Of the configurationally stable [4]helicenium ions, derivatives with sulfur, oxygen and nitrogen bridges have already been synthesised. However, one [4]helicenium ion has proven elusive, until now. We present herein the first synthesis of the 1,13‐dimethoxychromeno[2,3,4‐kl]acridinium (DMCA+) [4]helicenium ion. A series of six differently N‐substituted DMCA+ ions as their hexafluorophosphate salts are reported. Their cation stability was evaluated and it was found that DMCA+ is ideally suited as a phase‐transfer catalyst with a pKR+ of 13.0. The selectivity of nucleophilic addition to the central carbon atom of DMCA+ has been demonstrated with diastereotopic ratios of up to 1:10. The single‐crystal structures of several of the DMCA+ salts were determined, and structural differences between N‐aryl‐ and N‐alkyl‐substituted cations were observed. The results of a comparative study of the photophysics of the [4]helicenium ions are presented. DMCA+ is found to be a potent red‐emitting dye with a fluorescence quantum yield of 20 % in apolar solvents and a fluorescence lifetime of 12 ns. [4]Helicenium ions, including DMCA+, all suffer from solvent‐induced quenching, which reduces the fluorescence quantum yields significantly (?fl<5 %) in polar solvents. A difference in photophysical properties is observed between N‐aryl‐ and N‐alkyl‐substituted DMCA+, which has tentatively been attributed to a difference in molecular conformation.  相似文献   

12.
The N2 negative ion chemical ionization (NICI) mass spectra of aniline, aminonaphthalenes, aminobiphenyls and aminoanthracenes show an unexpected addition appearing at [M + 11]. This addition is also observed in the N2 positive chemical ionization (PCI) mass spectra. An ion at [M – 15]? is found in the NICI spectra of aminoaromatics such as aniline, 1- and 2-aminonaphthalene and 1- and 2-aminoanthracene. Ion formation was studied using labeled reagents, variation of ion source pressure and temperature and examination of ion chromatograms. These experiments indicate that the [M + 11], [M – 15] and [M + 11] ions result from the ionization of analytes altered by surface-assisted reactions. Experiments with 15N2, [15N] aniline, [2,3,4,5,6-2H5] aniline and [13C6] aniline show that the [M + 11] ion corresponds to [M + N – 3H]. The added nitrogen originates from the N2 buffer gas and the addition occurs with loss of one ring and two amino group hydrogens. Fragmentation patterns in the N2 PCI mass spectrum of aniline suggest that the neutral product of the surface-assisted reaction is 1,4-dicyanobuta-1,3-diene. Experiments with diamino-substituted aromatics show analogous reactions resulting in the formation of [M – 4H] ions for aromatics with ortho-amino groups. Experiments with methylsubstituted aminoaromatics indicate that unsubstituted sites ortho to the amino group facilitate nitrogen addition, and that methyl groups provide additional sites for nitrogen addition.  相似文献   

13.
Thin films of Al doped ZnO (Al:ZnO) were deposited on two substrates (Si and glass) at room temperature and 300°C using DC magnetron sputtering. These films were bombarded with 50 keV H+ beam at several fluences. The pristine and ion beam irradiated films were analysed by X‐ray diffraction, Raman spectroscopy, scanning electron microscopy, and UV‐Vis spectroscopy. The X‐ray diffraction analysis, Hall measurements, Raman and UV‐Vis spectroscopy confirm that the structural and transport properties of Al:ZnO films do not change substantially with beam irradiation at chosen fluences. However, in comparison to film deposited at room temperature, the Al:ZnO thin film deposited at 300°C shows increased transmittance (from 70% to approximately 90%) with ion beam irradiation at highest fluence. The studies of surface morphology by scanning electron microscopy reveal that the ion irradiation yields smoothening of the films, which also increases with ion fluences. The films deposited at elevated temperature are smoother than those deposited at room temperature. In the paper, we discuss the interaction of 50 keV H+ ions with Al:ZnO films in terms of radiation stability in devices.  相似文献   

14.
Fullerence C60‐cryptand 22 was prepared and successfully applied as the electric carrier in the PVC electrode membrane of a bifunctional ion‐selective electrode for cations, e.g., Ag+ ions as well as anions, e.g., I? ions. The bifunctional ion‐selective electrode based on C60‐cryptand 22 can be applied as a Silver (Ag+) ion selective electrode with an internal electrode solution of 10?3 M AgNO3 in water (pH = 6.3), or as an Iodide (I?) ion selective electrode with an acidic internal electrode solution of 10?4 M KI(aq) (pH = 2) in which the cryptand 22 is protonated, and the C60‐cryptand 22 is changed to C60‐Cryptand22–H+ and becomes an anionic electro‐carrier to absorb the I? ion. The Ag+ ion selective electrode based on C60‐cryptand 22 gave a linear response with a near‐Nernstian slope (59.5 mV decade?1) within the concentration range 10?1‐10?3 M Ag+(aq). The Ag+ ion electrode exhibited comparatively good selectivity for silver ions, over other transition‐metal ions, alkali and alkaline earth metal ions. The Ag+ ion selective electrode with good stability and reproducibility was successfully used for the titration of Ag+(aq) with Cl? ions. The Iodide (I?) Ion selective electrode based on protonated C60–cryptand22‐H+ also showed a linear response with a nearly Nernstian slope (58.5 mV decade?1) within 10?1 ‐ 10?3 M I? (aq) and exhibited good selectivity for I? ions and had small selectivity coefficients (10?2–10?3) for most of other anions, e.g., F? , OH?, CH3COO?, SO42?, CO32?, CrO42?, Cr2O72? and PO43? ions.  相似文献   

15.
Swift heavy ion (SHI) induced modification at metal/Si interfaces has emerged as an interesting field of research due to its large applications. In this study, we investigate SHI‐induced mixed molybdenum silicide film with ion fluences. The molybdenum thin films were deposited on silicon substrates using e‐beam evaporation at 10?8 torr vacuum. Thin films were irradiated with Au ions of energy 120 MeV to form molybdenum silicide. The samples were characterized by grazing incidence X‐ray diffraction (GIXRD) technique for the identification of phase formation at the interface. Rutherford backscattering spectrometry (RBS) was used to investigate the elemental distribution in the films. The mixing rate calculations were made and the diffusivity values obtained lead to a transient melt phase formation at the interface according to thermal spike model. Irradiation‐induced effects at surface have been observed and roughness variations at the surface were calculated using atomic force microscopy (AFM) technique. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

16.
Electroconductive poly(N‐butylaniline)–lignosulfonate (PBA–LS) composite nanospheres were prepared in a facile way by in situ, unstirred polymerization of N‐butylaniline with lignosulfonate (LS) as a dispersant and dopant. The LS content was used to optimize the size, structure, electroconductivity, solubility, and silver ion adsorptive capacity of the PBA–LS nanospheres. Uniform PBA–LS10 nanospheres with a minimal mean diameter of 375 nm and high stability were obtained when the LS content was 10 wt %. The PBA–LS10 nanospheres possess an increased electroconductivity of 0.109 S cm?1 compared with that of poly(N‐butylaniline) (0.0751 S cm?1). Furthermore, the PBA–LS10 nanospheres have a maximal silver‐ion sorption capacity of 815.0 mg g?1 at an initial silver ion concentration of 50 mmol L ?1 (25 °C for 48 h), an enhancement of 70.4 % compared with PBA. Moreover, a sorption mechanism of silver ions on the PBA–LS10 nanospheres is proposed. TEM and wide‐angle X‐ray diffraction results showed that silver nanoparticles with a diameter size range of 6.8–55 nm was achieved after sorption, indicating that the PBA–LS10 nanospheres had high reductibility for silver ions.  相似文献   

17.
Pentacyanocyclopentadienide (PCCp?), a stable π‐electronic anion, provided various ion‐pairing assemblies in combination with various cations. PCCp?‐based assemblies exist as single crystals and mesophases owing to interionic interactions with π‐electronic and aliphatic cations with a variety of geometries, substituents, and electronic structures. Single‐crystal X‐ray analysis revealed that PCCp? formed cation‐dependent arrangements with contributions from charge‐by‐charge and charge‐segregated assembly modes for ion pairs with π‐electronic and aliphatic cations, respectively. Furthermore, some aliphatic cations gave dimension‐controlled organized structures with PCCp?, as observed in the mesophases, for which synchrotron XRD analysis suggested the formation of charge‐segregated modes. Noncontact evaluation of conductivity for (C12H25)3MeN+ ? PCCp? films revealed potential hole‐transporting properties, yielding a local‐scale hole mobility of 0.4 cm2 V?1 s?1 at semiconductor–insulator interfaces.  相似文献   

18.
Li‐rich layered oxide Li1.18Ni0.15Co0.15Mn0.52O2 (LNCM) is, for the first time, examined as the positive electrode for hybrid sodium‐ion battery and its Na+ storage properties are comprehensively studied in terms of galvanostatic charge–discharge curves, cyclic voltammetry and rate capability. LNCM in the proposed sodium‐ion battery demonstrates good rate capability whose discharge capacity reaches about 90 mA h g?1 at 10 C rate and excellent cycle stability with specific capacity of about 105 mA h g?1 for 200 cycles at 5 C rate. Moreover, ex situ ICP‐OES suggests interesting mixed‐ions migration processes: In the initial two cycles, only Li+ can intercalate into the LNCM cathode, whereas both Li+ and Na+ work together as the electrochemical cycles increase. Also the structural evolution of LNCM is examined in terms of ex situ XRD pattern at the end of various charge–discharge scans. The strong insight obtained from this study could be beneficial to the design of new layered cathode materials for future rechargeable sodium‐ion batteries.  相似文献   

19.
Anion sensor properties of N‐alkyl‐substituted 1,4′‐diazaflavonium bromides in methanol–water were evaluated by UV–vis spectrometry. Pronounced changes were observed in the absorption spectra of all compounds for only OH?, CO32?, and CN? among F?, Cl?, Br?, I?, OH?, CO32?, NO3?, PO43?, CN?, SO42?, HSO4?, HCO3?, SCN?, NO2?, and P2O72? ions. Two new absorption bands at 385 and 685 nm accompanying the distinct color change for OH?, CO32?, and CN? ions were observed in case of all compounds. The color changes were from pink to blue for CO32? and OH? ions and from pink to purple for CN? ion. Thanks to the distinct color change, the compounds can be used as selective colorimetric anion sensors. Linear changes of absorbance of N‐heptyl‐substituted compound at 385 nm as a function of the ion concentration were used to determine CN? ion in water samples. Detection and quantification limits of the proposed method were 0.94 and 2.82 mg/L, respectively.  相似文献   

20.
Swift heavy ion beam irradiation induces modification in the dielectric properties and surface morphologies of polycarbonate (PC) films. The PC films were irradiated by 55 MeV energy of C5+ beam at various ions fluences ranging from 1 × 1011 to 1 × 1013 ions cm?2. The dielectric properties (i.e., dielectric constant, dielectric loss, and AC conductivity) and surface morphologies of pristine and SHI beam irradiated PC films were investigated by dielectric measurements, atomic force microscopy (AFM), and optical microscopy. The dielectric measurements show that the dielectric constant, dielectric loss, and AC conductivity increase with ion fluences and temperature, however, the dielectric constant and AC conductivity decrease while dielectric loss increases with frequency. AFM shows the increase in average roughness values with ion fluences. The change of color in PC films has been observed from colorless to yellowish and then dark brown with increases of ion fluence by using optical microscopy.  相似文献   

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