Covalent and non-covalent coupling of a Au102 nanocluster with a fluorophore: energy transfer, quenching and intracellular pH sensing

Interactions between an atomically precise gold nanocluster Au102(p-MBA)44 (p-MBA = para mercaptobenzoic acid) and a fluorescent organic dye molecule (KU, azadioxatriangulenium) are studied. In solution, the constituents form spontaneously a weakly bound complex leading to quenching of fluorescence of the KU dye via energy transfer. The KU can be separated from the complex by lowering pH, leading to recovery of fluorescence, which forms a basis for an optical reversible pH sensor. However, the sensor is not a stable entity, which could be delivered inside cells. For this purpose, a covalently bound hybrid is synthesized by linking the KU dye to the ligand layer of the cluster via an ester b…

Simultaneous non-invasive gas analysis in artificial photosynthesis reactions using rotational Raman spectroscopy

Optimising reactions in artificial photosynthesis research requires screening of many reaction and operation parameters, which is often resource-intense and time-consuming. In this paper, we demonstrate the use of a rotational Raman-based spectrometer for non-invasive quantification of several gases (H2, O2, N2, CO, CO2) with short analysis times (15 s), enabling high throughput screening. Furthermore, with this device, reaction progress can be monitored in situ, by real-time simultaneous quantification of multiple gases. We have applied this instrument and developed a method to study the O2 dependency of a prototypic light-driven hydrogen evolution reaction, showcasing the value of this ap…

Relaxation Dynamics of Cr(acac)3 Probed by Ultrafast Infrared Spectroscopy

Ultrafast infrared spectroscopy is used to probe the dynamics of Cr(acac)3 upon ligand field (400 nm) and charge transfer state (345 nm) excitation. At both pump wavelengths, the ground state absorption bands are strongly bleached at zero delay, and new broad transient absorption bands appear red shifted from the bleached bands. Recovery of ground state bleach is dominated by a fast time constant (15 ps), while a small percentage recovers within 760−900 ps. Despite the extensive studies on Cr(acac)3 photophysics, the fast recovery of the ground state as a major channel is reported here for the first time. As a general result, the present communication emphasizes the great value of ultrafast…

Patterning and tuning of electrical and optical properties of graphene by laser induced two-photon oxidation

Graphene, being an ultrathin, durable, flexible, transparent material with superior conductivity and unusual optical properties, promises many novel applications in electronics, photonics and optoelectronics. For applications in electronics, patterning and modification of electrical properties is very desirable since pristine graphene has no band gap. Here we demonstrate a simple all-optical patterning method for graphene, based on laser induced two-photon oxidation. By tuning the intensity of irradiation and the number of pulses the level of oxidation can be controlled to high precision and, therefore, a band gap can be introduced and electrical and optical properties can be continuously t…

Photodynamics of a Molecular Water-Soluble Nanocluster Identified as Au130(pMBA)50

Photodynamics of a highly monodisperse sample of a water-soluble gold nanocluster tentatively identified as Au130(pMBA)50 (pMBA = p-mercaptobenzoic acid) was studied by mid-IR transient absorption spectroscopy with visible excitation. The observed long-lived excited states (>1 ns) indicate a molecular behavior of the cluster. By combining the transient absorption data with DFT calculation results the observed relaxation dynamics could be fully explained by identifying several relaxation processes involving singlet and triplet manifolds. The results indicate that the cluster may have interesting transient magnetic properties due to a long-lived triplet population.

Time-Resolved Coherent Anti-Stokes Raman Scattering of Graphene: Dephasing Dynamics of Optical Phonon.

We report dynamics of the G-mode in graphene probed with time-resolved coherent anti-Stokes Raman scattering measurements. By applying BOXCARS excitation geometry with three different excitation wavelengths, various nonlinear processes can be selectively detected due to energy and momentum conservation and temporal sequence of the pulses. The Raman signal due to resonant coherent excitation of the G-mode shows exponential decay with lifetime of ∼325 ± 50 fs. This decay time is shorter than expected based on the line width of the G-mode in the Raman spectrum. We propose that the unexpectedly short dephasing time is a result of dynamic variation of nonadiabatic coupling of the photoexcited el…

Molecule-like photodynamics of Au102(pMBA)44 nanocluster.

Photophysical properties of a water-soluble cluster Au102(pMBA)44 (pMBA = para-mercaptobenzoic acid) are studied by ultrafast time-resolved mid-IR spectroscopy and density functional theory calculations in order to distinguish between molecular and metallic behavior. In the mid-IR transient absorption studies, visible or near-infrared light is used to electronically excite the sample, and the subsequent relaxation is monitored by studying the transient absorption of a vibrational mode in the ligands. Based on these studies, a complete picture of energy relaxation dynamics is obtained: (1) 0.5-1.5 ps electronic relaxation, (2) 6.8 ps vibrational cooling, (3) intersystem crossing from the low…

Internal Rotation in Propionic Acid:  Near-Infrared-Induced Isomerization in Solid Argon

The conformational system of propionic acid (CH3CH2COOH) is studied in solid argon. It is predicted by the ab initio calculations that this molecule has four stable conformers. These four structures are denoted Tt, Tg+/-, Ct, and Cg+/-, and they differ by the arrangement around the C-O and Calpha-C bonds. The ground-state Tt conformer is the only form present at 8 K after deposition of an argon matrix containing propionic acid. For the CH3CH2COOH and CH3CH2COOD isotopologues, narrow-band excitation of the first hydroxyl stretching overtone of the conformational ground state promotes the Calpha-C and C-O internal rotations producing the Tg+/- and Ct conformers, respectively. A subsequent vib…

Nonlinear photo-oxidation of graphene and carbon nanotubes probed by four wave mixing imaging and spectroscopy (Presentation Recording)

Graphene has high potential for becoming the next generation material for electronics, photonics and optoelectronics. However, spatially controlled modification of graphene is required for applications. Here, we report patterning and controlled tuning of electrical and optical properties of graphene by laser induced non-linear oxidation. We use four wave mixing (FWM) as a key method for imaging graphene and graphene oxide patterns with high sensitivity. FWM produces strong signal in monolayer graphene and the signal is highly sensitive to oxidation providing good contrast between patterned and non-patterned areas. We have also performed photo-oxidation and FWM imaging for air suspended carb…

Raman spectroscopy and crystal-field split rotational states of photoproducts CO and H2 after dissociation of formaldehyde in solid argon.

Raman signal is monitored after 248 nm photodissociation of formaldehyde in solid Ar at temperatures of 9-30 K. Rotational transitions J = 2 ← 0 for para-H(2) fragments and J = 3 ← 1 for ortho-H(2) are observed as sharp peaks at 347.2 cm(-1) and 578.3 cm(-1), respectively, which both are accompanied by a broader shoulder band that shows a split structure. The rovibrational spectrum of CO fragments has transitions at 2136.5 cm(-1), 2138.3 cm(-1), 2139.9 cm(-1), and 2149 cm(-1). To explain the observations, we performed adiabatic rotational potential calculations to simulate the Raman spectrum. The simulations indicate that the splitting of rotational transitions is a site effect, where H(2) …

Making Graphene Luminescent by Direct Laser Writing

Graphene is not intrinsically luminescent, due to a lack of bandgap, and methods for its creation are tricky for device fabrication. In this study, we create luminescent graphene patterns by a simple direct laser writing method. We analyze the graphene using Raman spectroscopy and find that the laser writing leads to generation of line defects after initial formation of point defects. This Raman data enables us to create a model that explains the luminescence by a formation of small domains due to confinement of graphene by line defects, which is conceptually similar to the mechanism of luminescence in graphene quantum dots. peerReviewed

Local photo-oxidation of individual single walled carbon nanotubes probed by femtosecond four wave mixing imaging

Photo-oxidation of individual, air-suspended single walled carbon nanotubes (SWCNTs) is studied by femtosecond laser spectroscopy and imaging. Individual SWCNTs are imaged by four wave mixing (FWM) microscopy under an inert gas (Ar or N2) atmosphere. When imaging is performed in an ambient air atmosphere, the decay of the FWM signal takes place. Electron microscopy shows that SWCNTs are not destroyed and the process is attributed to photoinduced oxidation reactions which proceed via a non-linear excitation mechanism, when irradiation is performed with ∼30 fs pulses in the visible spectral region (500-600 nm). Photo-oxidation can be localized in specific regions of SWCNTs within optical reso…

Rotational coherence imaging and control for CN molecules through time-frequency resolved coherent anti-Stokes Raman scattering

Numerical wave packet simulations are performed for studying coherent anti-Stokes Raman scattering (CARS) for CN radicals. Electronic coherence is created by femtosecond laser pulses between the X²Σ and B²Σ states. Due to the large energy separation of vibrational states, the wave packets are superpositions of rotational states only. This allows for a specially detailed inspection of the second- and third-order coherences by a two-dimensional imaging approach. We present the time-frequency domain images to illustrate the intra- and intermolecular interferences, and discuss the procedure to rationally control and experimentally detect the interferograms in solid Xe environment. peerReviewed

Femtosecond four-wave-mixing spectroscopy of suspended individual semiconducting single-walled carbon nanotubes.

Femtosecond four-wave-mixing (FWM) experiments of individual suspended semiconducting single-walled carbon nanotubes (SWCNTs) are presented. The chiral indices of the tubes were determined by electron diffraction as (28,14) and (24,14) having diameters of 2.90 and 2.61 nm, respectively. The diameter and semiconducting character of the tubes were additionally confirmed by resonance Raman measurements. The FWM signal showed electronic response from the SWCNTs. The results demonstrate that ultrafast dynamics of individual SWCNTs can be studied by FWM spectroscopies.

Chemical composition of two-photon oxidized graphene

Chemical composition of two-photon oxidized single-layer graphene is studied by micrometer X-ray photoelectron spectroscopy (XPS). Oxidized areas with a size of 2 × 2 μm2 are patterned on graphene by tightly focused femtosecond pulsed irradiation under air atmosphere. The degree of oxidation is controlled by varying the irradiation time. The samples are characterized by four wave mixing (FWM) imaging and Raman spectroscopy/imaging. Micrometer-XPS is used to study local chemical composition of oxidized areas. XPS imaging shows good contrast between oxidized and non-oxidized areas. Gradual oxidation is observed from growth of signals attributed mainly to hydroxyl (Csingle bondOH) and epoxide …

Why are hydrogen ions best for MeV ion beam lithography?

The exposure characteristics of poly-(methyl methacrylate) (PMMA) for 2MeV ^1H^+, 3MeV ^4He^2^+ and 6MeV ^1^2C^3^+ have been investigated. The samples were characterised using Atomic Force Microscopy (AFM), optical microscopy and Raman spectroscopy. Development was carried out using a 7:3 propan-2-ol:H"2O mixture to determine clearing and cross-linking fluences. It was found that protons had a considerably wider tolerance to exposure variations and a smaller span of doses within the ion track. Furthermore, the void formation and consequent stress-induced surface roughening were smaller for protons. For all ions, the C?C bond Raman signal increased continuously with dose and fluence, even we…

Dynamics behind the long-lived coherences of I2 in solid Xe.

The absorption spectrum of I2 in solid Xe shows resolved zero-phonon lines and phonon side bands near the origin of the B←X transition (550-625 nm). The long-lived |B⟩⟨X| coherence in this energy range (T2 = 600 fs on average) emerges as vibrationally unrelaxed fluorescence in resonance Raman (RR) spectra. Upon excitation in the structureless continuum at 532 nm, the oscillatory RR progression exhibits electronic dephasing time of T2 = 150 fs. Two RR progressions with markedly different vibrational coherence on the X-state are observed. The main progression of sharp overtones (T221 ps) is assigned to molecules trapped in double-substitution sites. The minor progression, which shows dephasin…

Area‐Selective Atomic Layer Deposition on Functionalized Graphene Prepared by Reversible Laser Oxidation

Publisher Copyright: © 2022 The Authors. Advanced Materials Interfaces published by Wiley-VCH GmbH. Area-selective atomic layer deposition (ALD) is a promising “bottom-up” alternative to current nanopatterning techniques. While it has been successfully implemented in traditional microelectronic processes, selective nucleation of ALD on 2D materials has so far remained an unsolved challenge. In this article, a precise control of the selective deposition of ZnO on graphene at low temperatures (<250 °C) is demonstrated. Maskless femtosecond laser writing is used to locally activate predefined surface areas (down to 300 nm) by functionalizing graphene to achieve excellent ALD selectivity (up to…

Tuning protein adsorption on graphene surfaces via laser-induced oxidation

An approach for controlled protein immobilization on laser-induced two-photon (2P) oxidation patterned graphene oxide (GO) surfaces is described. Selected proteins, horseradish peroxidase (HRP) and biotinylated bovine serum albumin (b-BSA) were successfully immobilized on oxidized graphene surfaces, via non-covalent interactions, by immersion of graphene-coated microchips in the protein solution. The effects of laser pulse energy, irradiation time, protein concentration and duration of incubation on the topography of immobilized proteins and consequent defects upon the lattice of graphene were systemically studied by atomic force microscopy (AFM) and Raman spectroscopy. AFM and fluorescence…

New nitrene functionalizations onto sidewalls of carbon nanotubes and their spectroscopic analysis

Abstract The reactivity of p -toluenesulfonyl, methylsulfonyl and trimethylsilyl nitrene, derived from the corresponding azides, was studied towards single-walled carbon nanotubes (SWCNT) prepared by electric arc or HiPCO (High-pressure CO conversion) methods. The functionalized SWCNTs were analyzed by Raman, IR, and VIS/NIR spectroscopy. The spectroscopic results indicated that covalent modification of the SWCNTs was successful. While the IR measurements gave evidence of successful reaction in all studied cases, the Raman measurements indicated differences in the reactivity of the two tube types and between different nitrenes. VIS/NIR spectrum was measured for reaction with p -toluenesulfo…

Nanoscale probing of the supramolecular assembly in a two‐component gel by near‐field infrared spectroscopy

The design of soft biomaterials requires a deep understanding of molecular self-assembly. We introduce here a nanoscale infrared (IR) spectroscopy study of a two-component supramolecular gel to assess the system´s heterogeneity and supramolecular assembly. In contrast to far-field IR spectroscopy, near-field IR spectroscopy revealed differences in the secondary structures of the gelator molecules and non-covalent interactions at three distinct nano-locations of the gel network. A β-sheet arrangement is dominant in single and parallel fibres with a small proportion of an α-helix present, while the molecular assembly derives from strong hydrogen bonding. However, at the crossing point of two …

Formation of HXeO in a xenon matrix: Indirect evidence of production, trapping, and mobility of XeO (1 1Σ+) in solid Xe

IR spectroscopy, laser induced fluorescence (LIF), and thermoluminescence (TL) measurements have been combined to monitor trapping, thermal mobility, and reactions of oxygen atoms in solid xenon. HXeO and O(3) have been used as IR active species that probe the reactions of oxygen atoms. N(2)O and H(2)O have been used as precursors for oxygen atoms by photolysis at 193 nm. Upon annealing of matrices after photolysis, ozone forms at two different temperatures: at 18-24 K from close O ...O(2) pairs and at approximately 27 K due to global mobility of oxygen atoms. HXeO forms at approximately 30 K reliably at higher temperature than ozone. Both LIF and TL show activation of oxygen atoms around 3…

Nondestructive Size Determination of Thiol-Stabilized Gold Nanoclusters in Solution by Diffusion Ordered NMR Spectroscopy

Diffusion ordered NMR spectroscopy (DOSY) was used as an analytical tool to estimate the size of thiol-stabilized gold nanoclusters in solution, namely, phenylethanethiol (PET) stabilized Au25(PET)18, Au38(PET)24, and Au144(PET)60. This was achieved by determining the diffusion coefficient and hydrodynamic radius from solution samples that were confirmed to be monodispersed by electrospray ionization mass spectrometry. The average cluster diameters obtained by this technique were estimated to be 1.7, 2.2, and 3.1 nm for the Au25(PET)18, Au38(PET)24, and Au144(PET)60 nanoclusters, respectively, which were shown to agree well with the average diameters of the corresponding single crystal or t…

Preface to the Special Issue “ISSPIC XVIII: International Symposium on Small Particles and Inorganic Clusters 2016”

Covalent and non-covalent coupling of a Au102 nanocluster with a fluorophore : energy transfer, quenching and intracellular pH sensing

Interactions between an atomically precise gold nanocluster Au102(p-MBA)44 (p-MBA = para mercaptobenzoic acid) and a fluorescent organic dye molecule (KU, azadioxatriangulenium) are studied. In solution, the constituents form spontaneously a weakly bound complex leading to quenching of fluorescence of the KU dye via energy transfer. The KU can be separated from the complex by lowering pH, leading to recovery of fluorescence, which forms a basis for an optical reversible pH sensor. However, the sensor is not a stable entity, which could be delivered inside cells. For this purpose, a covalently bound hybrid is synthesized by linking the KU dye to the ligand layer of the cluster via an ester b…

Water-soluble carbon nanotubes through sugar azide functionalization

In this work we report a covalent functionalization of pristine single-walled carbon nanotubes (SWCNTs) directly with three sugar azides, 2,3,4,6-tetra-O-acetyl-β-d-glucopyranosyl, 2,3,4,6-tetra-O-acetyl-β-d-galactopyranosyl or 2,3,4,6-tetra-O-acetyl-β-d-mannopyranosyl azide. Microwave-assisted functionalization was carried out for SWCNTs prepared with the HiPCO method. The as-prepared, new type of sugar-functionalized SWCNTs were analyzed by Raman and IR spectroscopy. Deacetylation of the functionalized tubes by sodium methoxide yielded nitrogen-linked, sugar-functionalized carbon nanotubes (CNTs) that formed stable dispersions in water. Reactivity of the sugar azides towards SWCNTs was es…

Raman spectroscopy and high-overtone driven isomerization of glyoxylic acid in solid argon

High-overtone induced chemistry of glyoxylic acid isolated in a low-temperature argon matrix was investigated using Raman spectroscopy. The Raman spectra of two most stable conformers of glyoxylic acid are presented. Upon excitation in high overtone vibrational bands by 532 nm irradiation of the lowest energy conformer most abundant in neat deposited sample, the isomerization of glyoxylic acid was observed. The process most plausible proceeds via absorption into the fifth vibrational overtone state of the OH group or its combination with the torsional vibrational transition. The assignment of the fundamental vibrational spectra was assisted by quantum chemical harmonic and anharmonic vibrat…

Effect of low amount of nanosilica on dielectric properties of polypropylene

This paper presents the results of the dielectric properties measurements conducted on Silica-Polypropylene (PP) nanocomposites. According to prior investigations by the authors silica nanoparticles have improved the performance of the dielectric material considering capacitor applications. Especially breakdown strengths with ac and dc voltages and resistance against surface degradation have increased. The relative permittivity and dielectric losses have also been comparable to reference PP. In this paper the results of the dielectric measurements conducted on composites with 1-2 wt-% silica are compared with reference PP. Silica dispersion in PP was confirmed with transmission electron mic…

Modification of the supramolecular structure of [(thione)IY] (Y = Cl, Br) systems by cooperation of strong halogen bonds and hydrogen bonds

Four interhalogen complexes of heterocyclic thione ligands N-methylbenzothiazole-2-thione (mbtt) and 2(3)H-benzothiazole-thione (btt) with strong and tunable S⋯I halogen bonds were synthesized and characterized by X-ray single crystal diffraction. The study of the strength and nature of the interactions was supported by computational analysis using the Quantum Theory of Atoms in Molecules (QTAIM). Halogen bond and hydrogen bond directed self-assemblies of thione compounds were efficiently modified by the changes in the halogen bond donor and acceptor structures. In structures [(mbtt)ICl] (1) and [(mbtt)IBr] (2) the interplay of halogen bonds and hydrogen bonds between the thione hydrogens a…

Electronic spectroscopy of I2-Xe complexes in solid Krypton

In the present work, we have studied ion-pair states of matrix-isolated I2 with vacuum-UV absorption and UV-vis-NIR emission, where the matrix environment is systematically changed by mixing Kr with Xe, from pure Kr to a more polarizable Xe host. Particular emphasis is put on low doping levels of Xe that yield a binary complex I2–Xe, as verified by coherent anti-Stokes Raman scattering (CARS) measurements. Associated with interaction of I2 with Xe we can observe strong new absorption in vacuum-UV, redshifted 2400 cm−1 from the X → D transition of I2. Observed redshift can be explained by symmetry breaking of ion-pair states within the I2–Xe complex. Systematic Xe doping of Kr matrices shows…

Optically Forged Diffraction-Unlimited Ripples in Graphene

In nanofabrication, just as in any other craft, the scale of spatial details is limited by the dimensions of the tool at hand. For example, the smallest details for direct laser writing with far-field light are set by the diffraction limit, which is approximately half of the used wavelength. In this work, we overcome this universal assertion by optically forging graphene ripples that show features with dimensions unlimited by diffraction. Thin sheet elasticity simulations suggest that the scaled-down ripples originate from the interplay between substrate adhesion, in-plane strain, and circular symmetry. The optical forging technique thus offers an accurate way to modify and shape two-dimens…

Structure and dielectric breakdown strength of nano calcium carbonate/polypropylene composites

Nanodielectrics, a 21st-century phenomena, is envisioned to be the answer for material challenges in progressive high-voltage technology. It is well known that the proper dispersion of nanoparticles plays a key role in improving the dielectric properties of a material, but to understand where changes in the properties of a material originate, it is also essential to reveal the multiscale structure of the material. In this study, the dielectric permittivity, breakdown strength, and structure of nano calcium carbonate (nano-CaCO3)/polypropylene composites with 1.8-8.1 wt % doping were characterized systematically. The combined results from transmission electron microscopy, Raman microscopy, a…

Matrix isolation and quantum chemical studies on the H2O2–SO2complex

Complexation and photochemical reactions of hydrogen peroxide and sulfur dioxide have been studied in solid Ar, Kr and Xe. Complexes between H2O2 and SO2 are characterized using Fourier transform infrared spectroscopy and ab initio calculations. In solid Ar, the H2O2–SO2 complex absorptions are found at wavenumbers of 3572.8, 3518.7, 3511.2, 3504.3, 1340.3, 1280.2 and 1149.9 cm−1. In Kr and Xe matrices, the bonded OH stretching frequencies deviate from the values in Ar, and we propose that the matrix surrounding influences the structure of the H2O2–SO2 complex. UV photolysis of the H2O2–SO2 was also studied in solid Ar, Kr and Xe. This photolysis produces mainly a complex between sulfur tri…

Electronic spectroscopy of I2–Xe complexes in solid Krypton

In the present work, we have studied ion-pair states of matrix-isolated I(2) with vacuum-UV absorption and UV-vis-NIR emission, where the matrix environment is systematically changed by mixing Kr with Xe, from pure Kr to a more polarizable Xe host. Particular emphasis is put on low doping levels of Xe that yield a binary complex I(2)-Xe, as verified by coherent anti-Stokes Raman scattering (CARS) measurements. Associated with interaction of I(2) with Xe we can observe strong new absorption in vacuum-UV, redshifted 2400 cm(-1) from the X → D transition of I(2). Observed redshift can be explained by symmetry breaking of ion-pair states within the I(2)-Xe complex. Systematic Xe doping of Kr ma…

Laser-induced tuning of graphene field-effect transistors for pH sensing

Here we demonstrate, using pulsed femtosecond laser-induced two-photon oxidation (2PO), a novel method of locally tuning the sensitivity of solution gated graphene field-effect transistors (GFETs) without sacrificing the integrity of the carbon network of chemical vapor deposition (CVD) grown graphene. The achieved sensitivity with 2PO was (25 ± 2) mV pH−1 in BIS-TRIS propane HCl (BTPH) buffer solution, when the oxidation level corresponded to the Raman peak intensity ratio I(D)/I(G) of 3.58. Sensitivity of non-oxidized, residual PMMA contaminated GFETs was 20–22 mV pH−1. The sensitivity decreased initially by 2PO to (19 ± 2) mV pH−1 (I(D)/I(G) = 0.64), presumably due to PMMA residue remova…

Covalently linked multimers of gold nanoclusters Au102(p-MBA)44 and Au∼250(p-MBA)n

We present the synthesis, separation, and characterization of covalently-bound multimers of para-mercaptobenzoic acid (p-MBA) protected gold nanoclusters. The multimers were synthesized by performing a ligand-exchange reaction of a pre-characterized Au102(p-MBA)44 nanocluster with biphenyl-4,4′-dithiol (BPDT). The reaction products were separated using gel electrophoresis yielding several distinct bands. The bands were analyzed by transmission electron microscopy (TEM) revealing monomer, dimer, and trimer fractions of the nanocluster. TEM analysis of dimers in combination with molecular dynamics simulations suggest that the nanoclusters are covalently bound via a disulfide bridge between BP…

Revealing lattice disorder, oxygen incorporation and pore formation in laser induced two-photon oxidized graphene

Abstract Laser induced two-photon oxidation has proven to be a reliable method to pattern and control the level of oxidation of single layer graphene, which in turn allows the development of graphene-based electronic and optoelectronic devices with an all-optical method. Here we provide a full structural and chemical description of modifications of air-suspended graphene during the oxidation process. By using different laser irradiation doses, we were able to show via transmission electron microscopy, electron energy loss spectroscopy, electron diffraction and Raman spectroscopy how graphene develops from its pristine form up to a completely oxidized, porous and amorphous carbon layer. Furt…

Covalently linked multimers of gold nanoclusters Au102(p-MBA)44and Au∼250(p-MBA)n

We present the synthesis, separation, and characterization of covalently-bound multimers of para-mercaptobenzoic acid (p-MBA) protected gold nanoclusters. The multimers were synthesized by performing a ligand-exchange reaction of a pre-characterized Au102(p-MBA)44 nanocluster with biphenyl-4,4′-dithiol (BPDT). The reaction products were separated using gel electrophoresis yielding several distinct bands. The bands were analyzed by transmission electron microscopy (TEM) revealing monomer, dimer, and trimer fractions of the nanocluster. TEM analysis of dimers in combination with molecular dynamics simulations suggest that the nanoclusters are covalently bound via a disulfide bridge between BP…

Time-resolved coherent anti-Stokes Raman-scattering measurements of I2 in solid Kr: vibrational dephasing on the ground electronic state at 2.6-32 K.

Time-resolved coherent anti-Stokes Raman-scattering (CARS) measurements are carried out for iodine (I2) in solid krypton matrices. The dependence of vibrational dephasing time on temperature and vibrational quantum number v is studied. The v dependence is approximately quadratic, while the temperature dependence of both vibrational dephasing and spectral shift, although weak, fits the exponential form characteristic of dephasing by pseudolocal phonons. The analysis of the data indicates that the frequency of the pseudolocal phonons is approximately 30 cm(-1). The longest dephasing times are observed for v = 2 being approximately 300 ps and limited by inhomogeneous broadening. An increase in…

Vibrational relaxation of matrix-isolated carboxylic acid dimers and monomers.

Femtosecond mid-IR transient absorption spectroscopy was used to probe the vibrational dynamics of formic acid and acetic acid isolated in solid argon following excitation of the fundamental transition of the carbonyl stretching mode. Carboxylic acids form extremely stable H-bonded dimers, hindering the study of the monomeric species at equilibrium conditions. The low-temperature rare-gas matrix isolation technique allows for a unique control over aggregation enabling the study of the monomer vibrational dynamics, as well as the dynamics of two distinct dimer structures (cyclic and open chain). This study provides insight into the role of the methyl rotor and hydrogen bonding in the vibrati…

Time resolved CARS measurements of I2 in solid Kr

Dephasing is a central concept in condensed phase spectroscopy. It determines how long a system will maintain its coherence. The dephasing time of a system is determined by dynamic intermolecular interactions, and therefore measurements of dephasing time can provide information on interactions and couplings between a molecule and its environment. This chapter illustrates the application of the femtosecond coherent anti-Stokes Raman scattering (CARS) method to investigate the vibrational dephasing of I 2 in solid krypton. Dephasing of vibrational states between v = 2 and v = 16 is studied in the temperature range T = 2.6–32 K. The low vibrational states show dephasing times on the order of a…

Real-time monitoring of graphene patterning with wide-field four-wave mixing microscopy

The single atom thick two-dimensional graphene is a promising material for various applications due to its extraordinary electronic, optical, optoelectronic, and mechanical properties. The demand for developing graphene based applications has entailed a requirement for development of methods for fast imaging techniques for graphene. Here, we demonstrate imaging of graphene with femtosecond wide-field four-wave mixing microscopy. The method provides a sensitive, non-destructive approach for rapid large area characterization of graphene. We show that the method is suitable for online following of a laser patterning process of microscale structures on single-layer graphene. peerReviewed

Deterministic Modification of CVD Grown Monolayer MoS2 with Optical Pulses

| openaire: EC/H2020/820423/EU//S2QUIP | openaire: EC/H2020/834742/EU//ATOP Transition metal dichalcogenide monolayers have demonstrated a number of exquisite optical and electrical properties. Here, the authors report the optical modification of topographical and optical properties of monolayer MoS2 with femtosecond pulses under an inert atmosphere. A formation of three-dimensional structures on monolayer MoS2 with tunable height up to ≈20 nm is demonstrated. In contrast to unmodified monolayer MoS2, these optically modified structures show significantly different optical properties, such as lower photoluminescence intensity and longer fluorescence lifetime. The results suggest a novel way…

Temperature Dependence of Electronic Transitions of Single-Wall Carbon Nanotubes:  Observation of an Abrupt Blueshift in Near-Infrared Absorption

Near-infrared (NIR) absorption spectra of single-wall carbon nanotube (SWNT) films are studied between 10 and 293 K. The most prominent effect is the shift of bands with temperature. Some nanotubes show a redshift of transition upon increasing temperature while some show blueshift and others show no shift. The shift is interpreted to originate mainly from the effect of strain induced in the tubes because of interaction with the environment. In particular, at temperatures T = 175−225 K, for some bands, there is an abrupt large blueshift, which is interpreted to originate from interaction of the nanotubes with water. Two models could be considered to explain the effect:  (1) strain induced by…

Second-harmonic Generation Microscopy of Carbon Nanotubes

We image an individual single-walled carbon nanotube (SWNT) by second-harmonic generation (SHG) and transmission electron microscopy and propose that SHG microscopy could be used to probe the handedness of chiral SWNTs.

From Seeds to Islands: Growth of Oxidized Graphene by Two-Photon Oxidation

The mechanism of two-photon induced oxidation of single-layer graphene on Si/SiO2 substrates is studied by atomic force microscopy (AFM) and Raman microspectroscopy and imaging. AFM imaging of areas oxidized by using a tightly focused femtosecond laser beam shows that oxidation is not homogeneous but oxidized and nonoxidized graphene segregate into separate domains over the whole irradiated area. The oxidation process starts from point-like “seeds” which grow into islands finally coalescing together. The size of islands before coalescence is 30–40 nm, and the density of the islands is on the order of 1011 cm–2. Raman spectroscopy reveals growth of the D/G band ratio along the oxidation. Sha…

Iodine−Benzene Complex as a Candidate for a Real-Time Control of a Bimolecular Reaction. Spectroscopic Studies of the Properties of the 1:1 Complex Isolated in Solid Krypton

The properties of the 1:1 iodine-benzene complex isolated in a solid Kr matrix at low temperatures have been studied using UV-vis absorption, FTIR, resonance Raman, and femtosecond coherent anti-Stokes Raman spectroscopy (fs-CARS). The use of all these techniques on similar samples provides a wide view on the spectroscopic properties of the complex and allows comparison and combination of the results from different methods. The results for the complex cover its structure, the changes in the iodine molecule's vibrational frequencies and electronic absorption spectrum upon complexation, and the dynamics of the complexed I(2) molecule on both ground and excited electronic states. In addition, …

Photolysis of HCOOH monomer and dimer in solid argon: Raman characterization of in situ formed molecular complexes

Raman spectroscopy combined with the matrix isolation technique was employed to study the 193-nm photodecomposition products of formic acid in an argon matrix. The Raman-active fundamentals belonging to the CO(2) + H(2) and CO + H(2)O photoproducts were assigned. Also, bands due to Fermi resonance between the stretching vibration (nu(1)) and the overtone of the bending mode (2nu(2)) of CO(2) were identified. Both ortho- and para-H(2) molecules were identified from their rotational lines S(0)(1) and S(0)(0), respectively. These bands appeared upon matrix annealing as well as after prolonged photolysis. Additionally, photolysis of FA dimers produces oxalic acid and its secondary photoproducts…

Dielectric properties and partial discharge endurance of polypropylene-silica nanocomposite

This paper presents the results of the dielectric properties and partial discharge endurance measurements conducted on polypropylene (PP)-silica nanocomposite. The material compounds were analyzed with micro-Raman spectroscopy, X-ray tomography and transmission electron microscopy (TEM). ac and dc breakdown strength of the materials was measured. Dielectric response, capacitance and loss factor of the film samples were measured as a function of temperature and frequency. Partial discharge (PD) endurance of the reference PP and PP Silica nanocomposite was studied as a function of ac voltage. Material surfaces were analyzed after PD stress with optical microscopy. All dielectric measurements …

From Monomer to Bulk: Appearance of the Structural Motif of Solid Iodine in Small Clusters

Formation of iodine clusters in a solid krypton matrix was studied using resonance Raman spectroscopy with a 1 cm(-1) resolution. The clusters were produced by annealing of the solid and recognized by appearance of additional spectral transitions. Two distinct regions, red-shifted from the fundamental vibrational wavenumber of the isolated I(2) at 211 cm(-1), were observed in the signal. The intermediate region spans the range 196-208 cm(-1), and the ultimate region consists of two peaks at 181 and 190 cm(-1) nearly identical to crystalline I(2). The experimental results were compared to DFT-D level electronic structure calculations of planar (I(2))(n) clusters (n = 1-7). The dimer, trimer,…

Ultrafast electronic relaxation and vibrational cooling dynamics of Au 144(SC2H4Ph)60 nanocluster probed by transient mid-IR spectroscopy

Energy relaxation dynamics of a gold nanocluster with atomically precise composition, Au144(SC2H4Ph)60, is studied by transient mid-IR spectroscopy. The experiment is designed to simultaneously pro...

Molecular coupling of light with plasmonic waveguides.

We use molecules to couple light into and out of microscale plasmonic waveguides. Energy transfer, mediated by surface plasmons, from donor molecules to acceptor molecules over ten micrometer distances is demonstrated. Also surface plasmon coupled emission from the donor molecules is observed at similar distances away from the excitation spot. The lithographic fabrication method we use for positioning the dye molecules allows scaling to nanometer dimensions. The use of molecules as couplers between far-field and near-field light offers the advantages that no special excitation geometry is needed, any light source can be used to excite plasmons and the excitation can be localized below the d…

Ultrastiff graphene

Graphene has exceptionally high in-plane strength, which makes it ideal for various nanomechanical applications. At the same time, its exceptionally low out-of-plane stiffness makes it also flimsy and hard to handle, rendering out-of-plane structures unstable and difficult to fabricate. Therefore, from an application point of view, a method to stiffen graphene would be highly beneficial. Here we demonstrate that graphene can be significantly stiffened by using a laser writing technique called optical forging. We fabricate suspended graphene membranes and use optical forging to create stable corrugations. Nanoindentation experiments show that the corrugations increase graphene bending stiffn…

Chemically selective imaging of overlapping C-H stretching vibrations with time-resolved coherent anti-stokes Raman scattering (CARS) microscopy.

Chemically selective imaging of spectrally overlapping compounds is studied with a time-resolved, femtosecond approach on coherent anti-Stokes Raman scattering (CARS) microscopy taking advantage of time-dependent oscillating CARS amplitude which is sensitive to different chemical components at different time points. Chemically selective imaging is demonstrated for composite material of polypropylene (PP) matrix and om-POSS (octamethyl polyhedral oligomeric silsesquioxane) microparticles having partly overlapping CH stretching vibrations. Inverse Fourier transformation (IFT) was applied to Raman spectra of PP and om-POSS, indicating that the oscillatory structures of the vibrational decays d…

Reduction-oxidation dynamics of oxidized graphene: Functional group composition dependent path to reduction

Micrometer-sized oxidation patterns containing varying composition of functional groups including epoxy, ether, hydroxyl, carbonyl, carboxyl, were created in chemical vapor deposition grown graphene through scanning probe lithography and pulsed laser two-photon oxidation. The oxidized graphene films were then reduced by a focused x-ray beam. Through in-situ x-ray photoelectron spectroscopy measurement, we found that the path to complete reduction depends critically on the total oxygen coverage and concentration of epoxy and ether groups. Over the threshold concentrations, a complex reduction-oxidation process involving conversion of functional groups of lower binding energy to higher bindin…

Synthesis and photophysical properties of hyperbranhced polyfluorenes containing 2,4,6-tris(tiophen-2-yl)-1,3,5-triazine as the core

A series of new hyperbranched polymers containing a 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine core unit and polyfluorene chain arms have been synthesized via Suzuki coupling, and characterized by NMR, IR and GPC. All the polymers exhibit good thermal stability with a high decomposition temperature. By changing the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine/fluorene ratio the UV-vis absorption and emission spectra can be partially tuned. It has been found that the polymers containing a low ratio of 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine units (P1-P3) have an absorption maximum around 385 nm, localized in the polyfluorene chain, and a shoulder around 425 nm ascribable to a charge transfer stat…

Synthesis of carbon nanotubes on FexOy doped Al2O3-ZrO2 nanopowder

Carbon nanotubes (CNTs) were synthesized on liquid flame sprayed (LFS) powder substrate of iron oxide doped Al2O3-ZrO2. Iron oxide doped Al2O3-ZrO2 nanopowder was produced by injecting the liquid precursor of aluminium-isopropoxide, zirconium-n-propoxide, ferrocene and p-xylene into a high temperature (similar to 3000 K) flame. The precursor solution was atomized by high-velocity H-2 flow and injected into the flame where nanopartides were formed. The collected sample was used as a substrate material for the synthesis of CNTs. The CNTs were formed on the surfaces of the substrate powder by catalyzed decomposition of CH4. The particle morphology, size, phase composition and the nature of CNT…

Dynamic Stabilization of the Ligand-Metal Interface in Atomically Precise Gold Nanoclusters Au68 and Au144 Protected by meta-Mercaptobenzoic Acid

Ligand-stabilized, atomically precise gold nanoclusters with a metal core of a uniform size of just 1–3 nm constitute an interesting class of nanomaterials with versatile possibilities for applications due to their size-dependent properties and modifiable ligand layers. The key to extending the usability of the clusters in applications is to understand the chemical bonding in the ligand layer as a function of cluster size and ligand structure. Previously, it has been shown that monodispersed gold nanoclusters, stabilized by meta-mercaptobenzoic acid (m-MBA or 3-MBA) ligands and with sizes of 68–144 gold atoms, show ambient stability. Here we show that a combination of nuclear magnetic reson…

Vacuum Rabi splitting for surface plasmon polaritons and Rhodamine 6G molecules

We report on strong coupling between surface-plasmon polaritons and Rhodamine 6G molecules at room temperature. As a reference to compare with, we first determine the dispersion curve of (uncoupled) surface plasmon polaritons on a 50 nm thick film of silver. Consequently, we determine the dispersion curve of surface plasmon polaritons strongly coupled to Rhodamine 6G molecules, which exhibits vacuum Rabi splitting. Depending on the Rhodamine 6G concentration, we find splitting energies between 0.05 eV and 0.13 eV.

Photoactive Yellow Protein Chromophore Photoisomerizes around a Single Bond if the Double Bond Is Locked

Photoactivation in the Photoactive Yellow Protein, a bacterial blue light photoreceptor, proceeds via photo-isomerization of the double C=C bond in the covalently attached chromophore. Quantum chemistry calculations, however, have suggested that in addition to double bond photo-isomerization, the isolated chromophore and many of its analogues, can isomerize around a single C-C bond as well. Whereas double bond photo-isomerization has been observed with x-ray crystallography, experimental evidence for single bond photo-isomerization is currently lacking. Therefore, we have synthesized a chromophore analogue, in which the formal double bond is covalently locked in a cyclopentenone ring and ca…

A study on stabilization of HHeF molecule upon complexation with Xe atoms

In the present work, we computationally study energetic stabilization of HHeF by its complexation with Xe atoms. For the studied HHeF ��� Xen systems ðn ¼ 1–4; 6Þ, we found a large complexation-induced decrease of energy of HHeF with respect to its dissociation into atoms. As a working hypothesis, we assume that this stabilization effect continues for the larger systems (n > 6) as well. This suggests that dissociation of HHeF via the H–He stretching coordinate might be suppressed and its lifetime might be increased by inserting it into large Xe clusters or matrices. 2004 Elsevier B.V. All rights reserved.

Raman spectroscopy and crystal-field split rotational states of photoproducts CO and H2 after dissociation of formaldehyde in solid argon

Raman signal is monitored after 248 nm photodissociation of formaldehyde in solid Ar at temperatures of 9–30 K. Rotational transitions J = 2 ← 0 for para-H2 fragments and J = 3 ← 1 for ortho-H2 are observed as sharp peaks at 347.2 cm−1 and 578.3 cm−1, respectively, which both are accompanied by a broader shoulder band that shows a split structure. The rovibrational spectrum of CO fragments has transitions at 2136.5 cm−1, 2138.3 cm−1, 2139.9 cm−1, and 2149 cm−1. To explain the observations, we performed adiabatic rotational potential calculations to simulate the Raman spectrum. The simulations indicate that the splitting of rotational transitions is a site effect, where H2 molecules can resi…

Raman Spectroscopy and Low-Temperature Transport Measurements of Individual Single-Walled Carbon Nanotubes with Varying Thickness

We have investigated two metallic and one semiconducting individual single-walled carbon nanotubes (SWNT) and one bundle of two semiconducting nanotubes with a diameter range 1.1−2.9 nm with Raman spectroscopy and low-temperature electric transport measurements. With these two methods, we obtain mutually independent measurements on the basic properties of a specific nanotube. In particular, we obtain data on metallic and semiconducting properties. Evidence of a small band gap for one metallic tube was obtained. For the semiconducting SWNTs with diameters of 2.7−2.9 nm, a special resonance condition was observed which causes an anomalous intensity ratio for the two components of the G-band. …

Site-specific targeting of enterovirus capsid by functionalized monodisperse gold nanoclusters

Development of precise protocols for accurate site-specific conjugation of monodisperse inorganic nanoparticles to biological material is one of the challenges in contemporary bionanoscience and nanomedicine. We report here a successful site-specific covalent conjugation of functionalized atomically monodisperse gold clusters with 1.5-nm metal cores to viral surfaces. Water-soluble Au102(para-mercaptobenzoic acid)44 clusters, functionalized by maleimide linkers to target cysteines of viral capsid proteins, were synthesized and conjugated to enteroviruses echovirus 1 and coxsackievirus B3. Quantitative analysis of transmission electron microscopy images and the known virus structures showed …

Electron microscopy of gold nanoparticles at atomic resolution

Detailed structure of a gold nanoparticle Adding only a few atoms or changing the capping ligand can dramatically change the structure of individual metal nanoparticles. Azubel et al. used aberration-corrected transmission electron microscopy to derive a three-dimensional reconstruction of water-soluble gold nanoparticles. Small-angle x-ray scattering and other techniques have also corroborated this model. They used this to determine the atomic structure, which compared favorably with density functional theory calculations, without assuming any a priori structural knowledge or the use of model fitting. Science , this issue p. 909

Measurement of optical second-harmonic generation from an individual single-walled carbon nanotube

We show that optical second-harmonic generation (SHG) can be observed from individual single-walled carbon nanotubes (SWCNTs) and, furthermore, allows imaging of individual tubes. Detailed analysis of our results suggests that the structural noncentrosymmetry, as required for SHG, arises from the non-zero chiral angle of the SWCNT. SHG thus has potential as a fast, non-destructive, and simple method for imaging of individual nanomolecules and for probing their chiral properties. Even more, it opens the possibility to optically determine the handedness of individual SWCNTs.

Role of Vibrational Dynamics in Electronic Relaxation of Cr(acac)3

Ultrafast energy relaxation of Cr(acac)3 dissolved in tetrachloroethylene (TCE) is studied by time-resolved infrared (TRIR) spectroscopy by using electronic and vibrational excitation. After electronic excitation at 400 or 345 nm, the ground state recovers in two time scales: 15 ps (major pathway) and 800 ps (minor pathway), corresponding to fast electronic transition to the ground state and intermediate trapping on the long-lived (2)E state followed by intersystem crossing (ISC) to the ground state. The quantum yield for the fast recovery of the ground state depends on the excitation wavelength, being higher for 345 nm. Vibrational cooling (VC) occurs on the electronic excited states with …

Electronic and vibrational signatures of the Au102p-MBA44 cluster

Optical absorption of a gold nanocluster of 102 Au atoms protected by 44 para-mercaptobenzoic acid (p-MBA) ligands is measured in the range of 0.05-6.2 eV (mid-IR to UV) by a combination of several techniques for purified samples in solid and solution phases. The results are compared to calculations for a model cluster Au(102)(SMe)(44) based on the time-dependent density functional theory in the linear-response regime and using the known structure of Au(102)(p-MBA)(44). The measured and calculated molar absorption coefficients in the NIR-vis region are comparable, within a factor of 2, in the absolute scale. Several characteristic features are observed in the absorption in the range of 1.5-…

Acid–Base Properties and Surface Charge Distribution of the Water-Soluble Au102(pMBA)44 Nanocluster

The pKa of the p-mercaptobenzoic acid (pMBA) ligands in the Au102(pMBA)44 nanocluster was measured by using acid–base and IR titration. The observed macroscopic pKa = 6.18 ± 0.05 is significantly more basic than that of free pMBA (pKa = 4.16), and the protonation behavior is anticooperative according to the Hill coefficient n = 0.64 ± 0.04. The cluster is truly water-soluble when more than 22 and insoluble when fewer than 7 ligands are in the deprotonated state. In order to obtain more insight into the anticooperative character, the cluster was modeled at pH ∼6.2 using constant pH molecular dynamics simulations. The pKa values of the individual pMBAs are in the range of 5.18–7.58, depending…

Tuning protein adsorption on graphene surfaces via laser-induced oxidation

An approach for controlled protein immobilization on laser-induced two-photon (2P) oxidation patterned graphene oxide (GO) surfaces is described. Selected proteins, horseradish peroxidase (HRP) and biotinylated bovine serum albumin (b-BSA) were successfully immobilized on oxidized graphene surfaces, via non-covalent interactions, by immersion of graphene-coated microchips in the protein solution. The effects of laser pulse energy, irradiation time, protein concentration and duration of incubation on the topography of immobilized proteins and consequent defects upon the lattice of graphene were systemically studied by atomic force microscopy (AFM) and Raman spectroscopy. AFM and fluorescence…

Femtosecond coherent anti-Stokes Raman-scattering polarization beat spectroscopy of I2–Xe complex in solid krypton

Time-resolved coherent anti-Stokes Raman-scattering (CARS) measurements are carried out to study the interaction between xenon atom and iodine molecule in a solid krypton matrix. Interference between the CARS polarizations of the "free" and complexed iodine molecules is observed, while the quantum beats of the complex are not detected due to low concentration. Vibrational analysis based on the polarization beats yields accurate molecular constants for the I2-Xe complex. The harmonic frequency of the I2-Xe complex is found to be redshifted by 0.90 cm-1 when compared to the free I2, whereas the anharmonicity is approximately the same. The dephasing rate of the complex is found to be somewhat …

Rotational Isomerism in Acetic Acid: The First Experimental Observation of the High-Energy Conformer

The high-energy conformer of acetic acid (cis-AA) is produced in an Ar matrix by vibrational excitation of the OH stretching overtone of the ground conformational state (trans-AA). IR-absorption spectroscopy provides a clear identification of the reaction product. cis-AA converts back to trans-AA in a time scale of minutes at 8 K by tunneling. http://dx.doi.org/10.1021/ja038341a

Raman spectroscopy of acetic acid monomer and dimers isolated in solid argon

Acetic acid (AA) monomer and its dimers were studied by means of Raman spectroscopy combined with the matrix isolation technique. All fundamental bands of CH3COOH monomer were identified, including the CH3 torsional mode. Additionally, three overtone or combination modes were observed as a result of their enhanced intensities by Fermi resonance (FR). Twenty bands of the cyclic dimer (C2h) were identified and assigned, among which appear all intermolecular modes. Bands due to two different higher energy forms of the dimer were also identified. The experimental assignments are supported by ab initio calculations. Copyright © 2011 John Wiley & Sons, Ltd.

From Seeds to Islands: Growth of Oxidized Graphene by Two-Photon Oxidation

The mechanism of two-photon induced oxidation of single-layer graphene on Si/SiO2 substrates is studied by atomic force microscopy (AFM) and Raman microspectroscopy and imaging. AFM imaging of areas oxidized by using a tightly focused femtosecond laser beam shows that oxidation is not homogeneous but oxidized and nonoxidized graphene segregate into separate domains over the whole irradiated area. The oxidation process starts from point-like “seeds” which grow into islands finally coalescing together. The size of islands before coalescence is 30–40 nm, and the density of the islands is on the order of 1011 cm–2. Raman spectroscopy reveals growth of the D/G band ratio along the oxidation. Sha…

Shaping graphene with optical forging: from a single blister to complex 3D structures

Properties of graphene, such as electrical conduction and rigidity can be tuned by introducing local strain or defects into its lattice. We used optical forging, a direct laser writing method, under an inert gas atmosphere, to produce complex 3D patterns of single layer graphene. We observed bulging of graphene out of the plane due to defect induced lattice expansion. By applying low peak fluences, we obtained a 3D-shaped graphene surface without either ablating it or deforming the underlying Si/SiO2 substrate. We used micromachining theory to estimate the single-pulse modification threshold fluence of graphene, which was 8.3 mJ cm−2, being an order of magnitude lower than the threshold for…

Multimodal nonlinear imaging of suspended carbon nanotubes using circular polarizations

In this work, multimodal nonlinear microscopy of suspended CNTs using circular polarizations (CP) was reported. Significant variations in the SHG and THG signals of the CNTs between left hand circular polarization (LHCP) and right hand circular polarization (RHCP) were observed. The variations in the nonlinear signals can be associated to the unique properties of the CNTs such as chirality.

Influence of low amounts of nanostructured silica and calcium carbonate fillers on the large-area dielectric breakdown performance of bi-axially oriented polypropylene

Influence of low amounts (1.0-2.0wt-%) of nanostructured silica and calcium carbonate fillers on the large area dielectric breakdown performance of bi-axially oriented polypropylene (BOPP) is analyzed. A multi-breakdown measurement method based on the self-healing breakdown capability of metallized film is utilized for the breakdown characterization in order to cover relatively large total film areas, thus leading to results of higher relevance from the practical point-of-view. The dispersion and distribution qualities of filler particles at the nanoscale are evaluated with transmission electron microscopy (TEM) imaging. Weibull statistical analysis suggests that the breakdown distribution …

Tailoring the interaction between a gold nanocluster and a fluorescent dye by cluster size : creating a toolbox of range-adjustable pH sensors

We present a novel strategy for tailoring the fluorescent azadioxatriangulenium (KU) dye-based pH sensor to the target pH range by regulating the pKa value of the gold nanoclusters. Based on the correlation between the pKa and surface curvature of ligand-protected nanoparticles, the pKa value of the gold nanoclusters was controlled by size. In particular, three different-sized para-mercaptobenzoic acid (p-MBA) protected gold nanoclusters, Au25(p-MBA)18, Au102(p-MBA)44, and Au210–230(p-MBA)70–80 were used as the regulator for the pH range of the KU response. The negatively charged gold nanoclusters enabled the positively charged KU to bind to the surface, forming a complex and quenching the …

Diversity at the nanoscale : laser-oxidation of single-layer graphene affects Fmoc-phenylalanine surface-mediated self-assembly

We report the effects of a laser-oxidized single layer graphene (SLG) surface on the self-assembly of amphiphilic gelator N-fluorenylmethoxycarbonyl-L-phenylalanine (Fmoc-Phe) towards an gel–SLG interface. Laser oxidation modulates the levels of hydrophobicity/hydrophilicity on the SLG surface. Atomic force, scanning electron, helium ion and scattering scanning nearfield optical microscopies (AFM, SEM, HIM, s-SNOM) were employed to assess the effects of surface properties on the secondary and tertiary organization of the formed Fmoc-Phe fibres at the SLG–gel interface. S-SNOM shows sheet-like secondary structures on both hydrophobic/hydrophilic areas of SLG and helical or disordered structu…

Optical Modification of Monolayer MoS 2 : Deterministic Modification of CVD Grown Monolayer MoS 2 with Optical Pulses (Adv. Mater. Interfaces 10/2021)

Dynamic Stabilization of the Ligand-Metal Interface in Atomically Precise Gold Nanoclusters Au68 and Au144 Protected by meta-Mercaptobenzoic Acid

Ligand-stabilized, atomically precise gold nanoclusters with a metal core of a uniform size of just 1-3 nm constitute an interesting class of nanomaterials with versatile possibilities for applications due to their size-dependent properties and modifiable ligand layers. The key to extending the usability of the clusters in applications is to understand the chemical bonding in the ligand layer as a function of cluster size and ligand structure. Previously, it has been shown that monodispersed gold nanoclusters, stabilized by meta-mercaptobenzoic acid (m-MBA or 3-MBA) ligands and with sizes of 68-144 gold atoms, show ambient stability. Here we show that a combination of nuclear magnetic reson…

Characterization of Iron−Carbonyl-Protected Gold Clusters

Ligand-stabilized nanometer-sized gold particles are interesting building blocks for molecular electronics, precursors for catalysts, optical labels for biomolecules and diagnosis, and potential nontoxic carriers for therapeutics. In this work we characterize for the first time, by means of near-infrared and Raman spectroscopy and time-dependent density functional calculations, gold clusters protected with iron-carbonyl ligands, such as {Au(22)[Fe(CO)(4)](12)}(6-) shown in the figure. Surprisingly, our results show that these novel compounds bear many analogues to another, well-studied, class of gold clusters, namely those of thiolate-monolayer-protected gold clusters. Our work adds a new d…

Raman spectroscopy of formic acid and its dimers isolated in low temperature argon matrices

Raman spectroscopy combined with matrix isolation technique was employed to study formic acid monomer and its dimers. Nine fundamentals of the HCOOH monomer were identified. Additionally, the OH torsion overtone is observed and it is engaged in Fermi resonance with the δCOH mode. Several bands of the cyclic (C2h) dimer were identified and assigned. The less stable open form (Cs) of the dimer was also present in the experiment. Three intermolecular modes for the cyclic and one mode for the open dimer were found in the low frequency region. The experimental studies were supported by harmonic and anharmonic DFT calculations.

Insights into localized manipulation of organogel-related microcrystalline spherulite formation

Abstract The formation processes of microcrystalline spherulitic fiber systems related to bile acid amides were determined to include dominant interface-related aspects, the role of which were studied in terms of potential manipulation and increased control over the overall structure of the networks. The nucleation and growth properties and aggregation of two lithocholyl amide derivatives were studied in several organic solvents using thermomicroscopy, as well as thermal control at macroscopic level. Nucleation/crystallization at interfaces was observed to act as the main route for the formation of microcrystalline fibers/solids in six gelator–solvent systems, in which spherulite formation …

Background-Free Second-Harmonic Generation Microscopy of Individual Carbon Nanotubes

We use polarized second-harmonic generation (SHG) microscopy to investigate pristine air-suspended carbon nanotubes (CNT). We show that SHG originates from CNT chirality, allowing also different response for the two circular polarizations of fundamental light.

Probing the Gelation Synergies and Anti-Escherichia coli Activity of Fmoc-Phenylalanine/Graphene Oxide Hybrid Hydrogel

The N-fluorenyl-9-methyloxycarbonyl (Fmoc)-protected amino acids have shown high antimicrobial application potential, among which the phenylalanine derivative (Fmoc-F) is the most well-known representative. However, the activity spectrum of Fmoc-F is restricted to Gram-positive bacteria only. The demand for efficient antimicrobial materials expanded research into graphene and its derivatives, although the reported results are somewhat controversial. Herein, we combined graphene oxide (GO) flakes with Fmoc-F amino acid to form Fmoc-F/GO hybrid hydrogel for the first time. We studied the synergistic effect of each component on gelation and assessed the material’s bactericidal activity on Gram…

Frequency conversion of propagating surface plasmon polaritons by organic molecules

We demonstrate frequency conversion of surface plasmon polaritons (SPP) by utilizing the coupling between organic dye molecules and SPP. Launching of SPPs into a plasmonic waveguide is done in two ways: by optically excited molecules and by quantum dots (QDs). QDs are demonstrated to overcome the major problem of bleaching occurring with molecules. The SPP propagates tens of micrometers and clear frequency conversion is observed in the SPP spectrum after passing an area of converter molecules. The use of molecules and QDs as elements of all-plasmonic devices has the potential for high integration and use of self-assembly in fabrication. Peer reviewed

Impulsive excitation of high vibrational states in I2–Xe complex on the electronic ground state

Abstract High vibrational states, up to ν  = 22, are excited and investigated on the ground electronic state of a 1:1 I 2 –Xe complex isolated in solid Kr using femtosecond CARS technique and spontaneous resonant Raman measurements. The results show that this system is a promising candidate for investigations of coherent control of bimolecular reactions by using vibrational wavepackets on the ground electronic state.

Revealing lattice disorder, oxygen incorporation and pore formation in laser induced two-photon oxidized graphene

Laser induced two-photon oxidation has proven to be a reliable method to pattern and control the level of oxidation of single layer graphene, which in turn allows the development of graphene-based electronic and optoelectronic devices with an all-optical method. Here we provide a full structural and chemical description of modifications of air-suspended graphene during the oxidation process. By using different laser irradiation doses, we were able to show via transmission electron microscopy, electron energy loss spectroscopy, electron diffraction and Raman spectroscopy how graphene develops from its pristine form up to a completely oxidized, porous and amorphous carbon layer. Furthermore, …

Large-area dielectric breakdown performance of polymer films

In this study, large-area dielectric breakdown performances of various bi-axially oriented polypropylene (BOPP)-silica nanocomposite films are studied by utilizing the self-healing multi-breakdown method presented in the Part I of this publication. In particular, the effects of silica filler content, pre-mixing method, co-stabilizer content and film processing on the large-area breakdown performance are analyzed. Nanostructural and film cross-sectional analyses are correlated to the breakdown responses. The optimum silica filler content is found to reside at the low fill fraction level (~1 wt-%) and automatic pre-mixing of the raw materials and the optimization of the orientation temperatur…

Vibrational Perturbations and Ligand–Layer Coupling in a Single Crystal of Au144(SC2H4Ph)60 Nanocluster

We have determined vibrational signatures and optical gap of the Au144(PET)60 (PET: phenylethylthiol, SC2H4Ph) nanocluster solvated in deuterated dichloromethane (DCM-D2, CD2Cl2) and in a single crystal. For crystals, solid-state (13)C NMR and X-ray diffraction were also measured. A revised value of 2200 cm(-1) (0.27 eV) was obtained for the optical gap in both phases. The vibrational spectra of solvated AU144(PET)60 closely resembles that of neat PET, while the crystalline-state spectrum exhibits significant inhomogeneous spectral broadening, frequency shifts, intensity transfer between vibrational modes, and an increase in the overtone and combination transition intensities. Spectral broa…

Vacuum Rabi Splitting and Strong-Coupling Dynamics for Surface-Plasmon Polaritons and Rhodamine 6G Molecules

We report on strong coupling between surface plasmon polaritons (SPP) and Rhodamine 6G (R6G) molecules, with double vacuum Rabi splitting energies up to 230 and 110 meV. In addition, we demonstrate the emission of all three energy branches of the strongly coupled SPP-exciton hybrid system, revealing features of system dynamics that are not visible in conventional reflectometry. Finally, in analogy to tunable-Q microcavities, we show that the Rabi splitting can be controlled by adjusting the interaction time between waveguided SPPs and R6G deposited on top of the waveguide. The interaction time can be controlled with sub-fs precision by adjusting the length of the R6G area with standard lith…

Electronic transport measurements and Raman spectroscopy on carbon nanotube devices

An individual single wall carbon nanotube (SWCNT) device has been fabricated and measured using both low temperature transport and Raman measurements. With these mutually independent methods we can study the correlation between the techniques on semiconducting or metallic behavior of the tube. Furthermore, we study the structure of the nanotube by probing Raman measurements at different spots along the tube axis.

Optical Forging of Graphene into Three-Dimensional Shapes

Atomically thin materials, such as graphene, are the ultimate building blocks for nanoscale devices. But although their synthesis and handling today are routine, all efforts thus far have been restricted to flat natural geometries, since the means to control their three-dimensional (3D) morphology has remained elusive. Here we show that, just as a blacksmith uses a hammer to forge a metal sheet into 3D shapes, a pulsed laser beam can forge a graphene sheet into controlled 3D shapes in the nanoscale. The forging mechanism is based on laser-induced local expansion of graphene, as confirmed by computer simulations using thin sheet elasticity theory. peerReviewed

Long-Lived Electronic Coherence of Iodine in the Condensed Phase: Sharp Zero-Phonon Lines in the B↔X Absorption and Emission of I2 in Solid Xe

Our study of B←X absorption of molecular iodine (I2) isolated in a low-temperature crystalline xenon has revealed an exceptionally long-lived electronic coherence in condensed phase conditions. The visible absorption spectrum shows prominent vibronic structure in the form of zero-phonon lines (ZPLs) and phonon side bands (PSBs). The resolved spectrum implies weak interaction of the chromophore to the lattice degrees of freedom. The coherence extends past the vibrational period of the excited state molecule, unlike that observed in any condensed phase environment for I2 so far. The ZP transitions from the relaxing B-state populations were resolved in the hot luminescence when the 532 nm lase…

Ultrafast Electronic and Vibrational Energy Relaxation of Fe(acetylacetonate)3 in Solution

Transient mid-infrared spectroscopy is used to probe the dynamics initiated by excitation of ligand-to-metal (400 nm) and metal-to-ligand (345 nm) charge transfer states of FeIII complexed with acetylacetonate (Fe(acac)3, where acac stands for deprotonated anion of acetylacetone) in solution. Transient spectra in the 1500-1600 cm-1 range show two broad absorptions red-shifted from the bleach of the nu(CO) (approximately 1575 cm-1) and nu(C=C) (approximately 1525 cm-1) ground state absorptions. Bleach recovery kinetics has a time constant of 12-19 ps in chloroform and tetrachloroethylene and it decreases by 30-40% in a 10% mixture of methanol in tetrachloroethylene. The transient absorptions…

Vibrational characterization of the 1:1 iodine-benzene complex isolated in solid krypton.

The structure and properties of a 1:1 iodine-benzene complex isolated in an inert krypton matrix at low temperature have been studied with infrared and resonance Raman spectroscopy and with MP2 calculations. The structure of the ground-state complex is found to be unsymmetric, and the I-I vibrational frequency is found to be red-shifted by 3.94 cm(-1) upon complexation. The experimental data agree well with computational results, leading to the conclusion that the I2-Bz complex structure is not axial but of above-bond type, identically with other halogen-benzene complexes.

Triggering a transient organo-gelation system in a chemically active solvent

A transient organo-gelation system with spatiotemporal dynamic properties is described. Here, the solvent actively controls a complex set of equilibria that underpin the dynamic assembly event. The observed metastability is due to the in situ formation of a secondary solvent, acting as an antagonist against the primary solvent of the organogel. peerReviewed