Monomer Absorption Research Articles

Photochromic switchable pendant indolyl fulgimide polypyrrole

The photochromic switchable 2-indolyl fulgimide functionalized pyrrole monomer is synthesized and ascertained by spectroscopic techniques. The absorption and emission band of monomer due to intramolecular charge transfer (ICT) state exhibit typical bathochromic shift from nonpolar to polar solvents. The molecular geometry and bandgap energy of monomer in open form as well as closed form are calculated by B3LYP/6-31 G (d) with Gaussian 03 program package. The functionalized pyrrole monomer is electropolymerized by cyclicvoltammetric method on an electrode. The polymer indicated a completely reversible photoswitching between two isomers of open and closed form 2-indolyl fulgimide moiety, which are stable over many cycles of operation by UV/visible light sources. The closed form of polymer exhibit fluorescence quenching attributed to the energy transfer from conductance band of polypyrrole to closed form of 2-indolyl fulgimides unit. This fluorescence quenching system controls the conductance of conducting polymer in molecular electronics and molecular switches.

Circular dichroism of anthocyanidin 3-glucoside self-aggregates

Self-association constants for the flavylium cations of the six most common anthocyanidin 3-glucosides were determined by circular dichroism (CD) and UV-Vis spectroscopy. Along with previous (1)H NMR results, all measurements were consistent with a monomer-dimer model. The CD spectra of the anthocyanidin 3-glucosides were similar to the analogues 3,5-diglucosides. All dimers of the anthocyanidin 3-glucosides exhibited left-handed CD signals, with petunidin-3-glucoside and myrtillin having the most intense signals. In addition, the magnitude of the molar ellipticity, [θ], was generally higher for the 3-glucosides than for the 3,5-diglucosides. For all six anthocyanins studied, the CD absorption spectra of their dimers showed evidence of the splitting of the monomer absorption into lower (J aggregates) and higher (H aggregates) energy bands. The angle and the distance between the dipolar moments of the two monomers comprising the dimer were obtained from the lower energy absorption band. While the angle was more or less similar in all six dimers, the separation distance between the monomer dipole moments differed dramatically. The intensity of the CD signal displayed a linear dependence with the inverse square of the dipole moment distances.

Fluctuation statistical theory of nucleation in water vapors at near-critical temperatures

The Monte Carlo method has been used to study the evolution of the statistical behavior of density fluctuations in water vapors when approaching the critical isotherm from low temperatures. The free energy, work, and entropy of the formation of the nanosize density fluctuations have been calculated numerically. The spontaneous formation of the critical nucleus of the condensed phase is possible only against the back-ground of the density fluctuations with dimensions exceeding a certain threshold value n*, which increases rapidly when the critical temperature is approached. One should expect a qualitative change in the mechanism of the growth of nuclei of the condensed phase in the region of near critical temperatures from the statistically independent acts of the absorption of monomers by the surface of a microdroplet to the strongly correlated density fluctuations of expanding spatial dimensions.

J-aggregation of a squaraine dye and its application in organic photovoltaic cells

In this paper, we investigated the aggregation behavior of a squaraine dye in solid films, as well as the effects on its optical and electrical properties. We observed a strong intermolecular interaction in thin films, which can be controlled via processing solvents. Two typical aggregation behaviors, i.e. H- and J- aggregation, can be selectively formed via the proper selection of solvents, resulting in a significant difference in material properties and the resultant photovoltaic performance. In addition to the monomer absorption between 600 nm and 700 nm, the H-aggregation mainly absorbs green light around 500–600 nm, while the J-aggregation shows a strong absorption in the near infrared range up to 850 nm. Therefore in squaraine/fullerene bi-layer hetero-junction photovoltaic cells, we demonstrated a significant contribution of J-aggregation to the photocurrent. Furthermore the J-aggregation films have a deeper ionization potential, most likely due to the intermolecular charge-transfer interaction, and thus gave rise to a larger open circuit voltage than those of the H-aggregation based devices. The J-aggregation formation shall be considered as an effective approach to tune the optical/electrical properties in organic optoelectronic devices.

Steady-State and Time-Resolved Investigations on Pyrene-Based Chemosensors

Two novel fluorescent probes bearing a single (P) and two (a podand-like structure, L) pyrene units derived from 1,5-bis(2-aminophenoxy)-3-oxopentane have been synthesized and investigated in dioxane using UV-vis absorption, and steady-state and time-resolved (in a picosecond time scale) emission spectroscopy; in the gas phase, matrix-assisted laser desorption ionization mass spectrometry was employed. In dioxane, the absorption and emission spectra of P present a unique band with maxima at 361 and 392 nm, which have been associated with the monomer absorption and emission bands, respectively. In dioxane, for compound L, an additional band with a maximum at ∼525 nm is observed; upon the addition of water, an emissive band (with maxima varying from 405 to 490 nm) appears in both P and L spectra; this is discussed in terms of the emission of a species with charge character. Upon metal addition (Cu(2+), Zn(2+), and Ag(+)) to P, a gradual quenching effect of the monomer emission is observed and found to be more pronounced with Cu(2+). In the case of L, upon the addition of metal cations, the long emission band (∼550 nm) decreases and the monomer emission band increases (with an isoemissive point at ∼450 nm) and no evidence for the intermediate band (at ∼405-490 nm) now exists. Time-resolved data in dioxane/water mixtures showed that for P and L these two fit double- and triple-exponential decay laws, respectively. With P, this has been attributed to a two-state system, which involves the monomer and a charged species, with its emission maxima varying with the polarity of the media (here mirrored by its dielectric constant), which can potentially be addressed to an exciplex-like species, whereas with L, it has been attributed to a three-state system involving, in addition to these two species, an excimer. From absorption and fluorescence excitation and time-resolved data, evidence is given for the presence of intramolecular dimer formation in the ground state.

On π-stacking, C-H/π, and halogen bonding interactions in halobenzene clusters: Resonant two-photon ionization studies of chlorobenzene

Noncovalent interactions such as hydrogen bonding, π-π stacking, CH/π interactions, and halogen bonding play crucial roles in a broad spectrum of chemical and biochemical processes, and can exist in cooperation or competition. Here we report studies of the homoclusters of chlorobenzene, a prototypical system where π-π stacking, CH/π interactions, and halogen bonding interactions may all be present. The electronic spectra of chlorobenzene monomer and clusters (Clbz)(n) with n = 1-4 were obtained using resonant 2-photon ionization in the origin region of the S(0)-S(1) (ππ*) state of the monomer. The cluster spectra show in all cases a broad spectrum whose center is redshifted from the monomer absorption. Electronic structure calculations aid in showing that the spectral broadening arises in large part from inhomogeneous sources, including the presence of multiple isomers and Franck-Condon (FC) activity associated with geometrical changes induced by electronic excitation. Calculations at the M06-2x/aug-cc-pVDZ level find in total five minimum energy structures for the dimer, four π-stacked structures, and one T-shaped, and six representative minimum energy structures were found for the trimer. The calculated time-dependent density functional theory spectra using range-separated and meta-GGA hybrid functionals show that these isomers absorb over a range that is roughly consistent with the breadth of the experimental spectra, and the calculated absorptions are redshifted with respect to the monomer transition, in agreement with experiment. Due to the significant geometry change in the electronic transition, where for the dimer a transition from a parallel displaced to sandwich structure occurs with a reduced separation of the two monomers, significant FC activity is predicted in low frequency intermolecular modes.

Collective degrees of freedom involved in absorption and desorption of surfactant molecules in spherical non-ionic micelles

Dynamics of absorption and desorption of a surfactant monomer into and out of a spherical non-ionic micelle is investigated by coarse-grained molecular dynamics (MD) simulations. It is shown that these processes involve a complex interplay between the micellar structure and the monomer configuration. A quantitative model for collective dynamics of these degrees of freedom is developed. This is accomplished by reconstructing a multi-dimensional free energy landscape of the surfactant-micelle system using constrained MD simulations in which the distance between the micellar and monomer centers of mass is held constant. Results of this analysis are verified by direct (unconstrained) MD simulations of surfactant absorption in the micelle. It is demonstrated that the system dynamics is likely to deviate from the minimum energy path on the energy landscape. These deviations create an energy barrier for the monomer absorption and increase an existing barrier for the monomer desorption. A reduced Fokker-Planck equation is proposed to model these effects.

Raman spectroscopic investigations on intermolecular interactions in aggregates and crystalline forms of trans‐astaxanthin

Astaxanthin is a carotenoid naturally found in microbial organisms, microalgae, and many crustaceans. Its consumption has led to beneficial effects such as pigmentation of marine animals, and it favorably addresses several human health issues as a result of its high important antioxidant property. Several companies produce synthetic trans‐astaxanthin for dietary purposes in aquaculture, where it is mainly used for pigmentation. It is known that trans‐astaxanthin manifests itself as a monomer in organic solvents, as aggregates in aqueous solutions of organic solvents, or as crystalline solids. These forms display unique optical and structural properties, which have an impact on biological systems. In this work, we report on detailed Raman investigations, in conjunction with optical absorption spectroscopy, of monomer, aggregates, and crystalline forms of trans‐astaxanthin. The Raman and optical absorption spectroscopic investigations of trans‐astaxanthin aggregates were performed as a function of time, showing the formation of card‐packed aggregates after 2 h, and head‐to‐tail aggregates after 24 h in a 10% acetone–water astaxanthin solution. For the crystalline trans‐astaxanthin, a pointwise Raman mapping evidenced the presence of two distinct crystal structures. The Raman modes of these crystal structures (A and B) were correlated with the intermolecular interactions present in chloroform solvated (AXT‐Cl) and unsolvated (un‐AXT) trans‐astaxanthin single crystals. Both crystal structure A and the card‐packed aggregates have similar intermolecular π stacking interactions as AXT‐Cl. The crystal structure B and the head‐to‐tail aggregates showed linear chain features as in un‐AXT. This work also clearly demonstrates that Raman spectroscopy is a powerful tool to distinguish the crystal structures present in crystalline powder of trans‐astaxanthin. Copyright © 2012 John Wiley & Sons, Ltd.

Absolute high spectral resolution measurements of surface solar radiation for detection of water vapour continuum absorption

Solar-pointing Fourier transform infrared (FTIR) spectroscopy offers the capability to measure both the fine scale and broadband spectral structure of atmospheric transmission simultaneously across wide spectral regions. It is therefore suited to the study of both water vapour monomer and continuum absorption behaviours. However, in order to properly address this issue, it is necessary to radiatively calibrate the FTIR instrument response. A solar-pointing high-resolution FTIR spectrometer was deployed as part of the 'Continuum Absorption by Visible and Infrared radiation and its Atmospheric Relevance' (CAVIAR) consortium project. This paper describes the radiative calibration process using an ultra-high-temperature blackbody and the consideration of the related influence factors. The result is a radiatively calibrated measurement of the solar irradiation at the ground across the IR region from 2000 to 10 000 cm(-1) with an uncertainty of between 3.3 and 5.9 per cent. This measurement is shown to be in good general agreement with a radiative-transfer model. The results from the CAVIAR field measurements are being used in ongoing studies of atmospheric absorbers, in particular the water vapour continuum.

Pathways of electron transfer photosensitized by thiacyanine dimers

Pathways of electron transfer reaction between p-nitroacetophenone (p-NAP) and ascorbic acid (AA) photosensitized by dimers of 3,3'-disulfopropyl-5,5'-dichlorothiacyanine triethylammonium (TC) and 3,3'-disulfopropyl-5,5'-dichloro-9,11-[ββ-dimethyltrimethylene]thiadicarbocyanine triethylammonium (TDC) are considered. In aqueous solution the dyes are present as an equilibrated mixture of monomers (M(-)) and dimers (M(2)(2-)). In contrast to monomers, the dimers of TC are characterized by a noticeable yield of intersystem crossing, whereas for TDC the triplet-triplet absorption of both monomers and dimers is easily observed upon ns-laser pulse. In the presence of p-NAP and AA the triplet state of the dimers of both dyes is mostly quenched by p-NAP yielding the radical pair [M(2)(-)˙p-NAP(-)˙] with subsequent dissociation of M(2)(-)˙ into M(-) and M˙ followed by one-electron reduction of M˙ by AA. These steps constitute a pathway of photosensitization by the dimers. For TDC an additional pathway of photosensitization was found to occur. The primary step consists of electron transfer in the excited singlet state of the dimer resulting in the formation of the radicals M˙ and M(2-)˙. The next steps involve one-electron reduction of M˙ by AA and one-electron oxidation of M(2-)˙ by p-NAP which results in the formation of M(-) followed by dimerization.

Bioavailability and Brain Deposition of Proanthocyanidin (PAC), Anthocyanin and Flavonoid in Combi‐Phenol Treated Rats on High Fat (HF) or Low Fat (LF) Diet

Consumption of grape derived polyphenols is associated with the prevention of neurodegenerative diseases such as Alzheimer's disease (AD). HF diet, on the other hand, has been shown to be a risk factor on AD onset and progression. To further understand the physiological impact of these compounds ingested as a grape polyphenolic preparation termed ‘Combi‐Phenol’ and the influence of dietary fat on absorption and metabolism of PAC monomer, flavonoid, and anthocyanin, studies were conducted with Sprague‐Dawley rat fed on HF or LF diet. Rats were divided into four groups: LF‐control, HF‐control, LF‐Combi‐Phenol, HF‐Combi‐Phenol and fed on individual diet for 2 weeks prior to Combi‐Phenol treatment. Plasma pharmacokinetics was determined after dosing of Combi‐Phenol or water for 10 days. LC‐MS/MS analysis showed that glucuronide and methylated glucuronide are the main metabolites for (epi)catechin, quercetin, and resveratrol. Glucosides were the major derivatives for anthocyanins present in plasma and brains following Combi‐Phenol consumption regardless fat content in the diet. These data illustrate that dietary fat content did not affect the bioavailability of Combi‐Phenol and their access to the brain was also not influenced.Supported by NIH Grant: P01AT004511Grant Funding Source: NIH

Polypyrrole top-contact electrodes patterned by inkjet printing assisted vapor deposition polymerization in flexible organic thin-film transistors

Highly conductive polymer, polypyrrole (PPy) was successfully patterned as source and drain (S/D) electrodes for flexible pentacene thin film transistors in top-contact structure by combining inkjet printing and vapor deposition polymerization. Facile inkjet printing of initiator and subsequent exposure of pyrrole monomers resulted in selective absorption and polymerization of pyrrole monomers on the patterned initiator region. Pentacene transistors based on printed PPy electrodes exhibited higher electrical characteristics than that of the devices with thermally evaporated Au electrodes. Improved performance of the devices based on PPy electrodes could be attributed to the reduction of contact resistance at the interface between polymer and organic semiconductor. For the replacement of metal electrodes, vapor deposition polymerization assisted inkjet printing technique can provide a versatile method to utilize highly conductive polymer as a functional electrode of flexible organic electronic devices.

A Photophysical Study of the α‐Carboline (1‐Azacarbazole) Aggregation Process

This paper reports a comprehensive photophysical study of the aggregation process of 1-azacarbazole, or α-carboline (9H-pyrido[2,3-b]indole), AC, in low polar aprotic solvents by using absorption, steady state and time-resolved fluorescence spectroscopic techniques. To ascertain the characteristics of the aggregation process we have studied the changes produced by the increase of the AC concentration and the decrease of the temperature on the absorption and fluorescence spectra of the AC monomer. Previously, to aid the interpretation of these results, the hydrogen bonding interactions of the AC monomer with pyridine, PY, and indole, IND, have been also analyzed. The results obtained from these studies reveal that, under our experimental conditions, AC does not form doubly hydrogen bonded cyclic dimers, (AC)(2), but singly hydrogen bonded open dimers, AC-AC, and open higher aggregates, (-AC-)(n). The formation of these species shifts to the red the absorption spectrum of the AC monomer and quenches its fluorescence.

Peripheral and Structural Effects on the Band Gap of Acceptor–Donor Type Conducting Polymers Containing Pendant Bisfulleroid Groups

In this computational study, the band gap energy of an acceptor–donor type conducting polymer consisting of terthiophene repeating units with a fused bisfulleroid group was estimated by extrapolating excitation energies approximated by the HOMO–LUMO energy differences as well as the TDDFT method with respect to the inverse number of monomer units. Optimizations were performed both in vacuum and in o-dichlorobenzene (as solvent) using the B3LYP and MPW1B95 functionals. The calculated optical band gap was found to be in good agreement with experimentally reported band gaps in the literature. However, different band gaps with different experimental techniques were reported in the referred experimental study for the same system. To understand the reasons behind this behavior, effects of the structural (inter- and intramolecular stacking) and environmental (explicit and implicit solvation and acidic doping) factors on the absorption of the terthiophene monomer with fused bisfulleroid were investigated. Acid doping was found to be very important in terms of the present system.

Contrasting Behavior of Classical Salts versus Ionic Liquids toward Aqueous Phase J-Aggregate Dissociation of a Cyanine Dye

The effect of addition of ionic liquids (ILs) on the aggregation behavior of a cyanine dye, 5,5',6,6'-tetrachloro-1,1'-diethyl-3,3'-di(4-sulfobutyl)-benzimidazolocarbocyanine (TDBC), was investigated. In basic aqueous buffer solutions (pH ≥ 10), TDBC preferably exists in its J-aggregated form. Addition of hydrophilic ILs > 5 wt % is observed to disrupt the TDBC J-aggregates, converting them to monomer form most likely because of the interaction between bulky IL cation and the J-aggregates in a time-dependent fashion. This is evidenced by the observed increase in monomer band absorbance at the expense of the absorbance band due to J-aggregates over time. Inorganic salts at similar molar concentrations do not cause this phenomenon but instead induce TDBC precipitation. At low concentrations (<5 wt %), the added IL acts similarly to the inorganic salts, reducing the overall absorbance of TDBC in the solution most likely due to cation exchange causing TDBC precipitation. Addition of a molecular solvent, ethanol, at 15 wt % results in an initial increase in monomer absorbance, albeit to a much lesser extent than for the corresponding molar fraction of IL, which then decreases over time with recovery of J-aggregate absorbance--quite opposite the time-dependent behavior seen for TDBC in PB at pH 12.0 with >5 wt % IL. The unique and dual behavior of ILs as an additive toward affecting cyanine dye aggregation is demonstrated.

Competitive absorption of epoxy monomers on carbon nanotube: A molecular simulation study

AbstractPosition restrained (PR) molecular dynamics (MD) simulations were carried out on the bulk models for the two composite systems including epoxy monomers and carbon nanotube (CNT). The pair energies and the radial distribution functions (RDFs) were computed to evaluate the relative strength of the epoxy monomers binding to the CNT. It is found that the aromatic amine binds more strongly to the CNT than does the aliphatic amine. A vivid view indicates the aromatic rings tend to form π‐stacking with the CNT, and the compounds with aromatic rings prefer to wrap the CNT. These simulated results are in good agreement with those obtained previously from the vacuum models. This work demonstrates that curing agents affect the interactions between epoxy resin and CNT. Other comparisons of relative binding strength of epoxy monomers also depend upon the temperature. Further analyses suggest that the aliphatic amine exhibits more strong interactions with epoxy resin than does the aromatic amine, mainly due to the presence of hydrogen bonds (HBs) between them. Thus, the ultimate performance of epoxy‐CNT polymer nanocomposites should be affected by the two reverse interactions. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011.

An upper limit for water dimer absorption in the 750 nm spectral region and a revised water line list

Abstract. Absorption of solar radiation by water dimer molecules in the Earth's atmosphere has the potential to act as a positive feedback effect for climate change. There seems little doubt from the results of previous laboratory and theoretical studies that significant concentrations of the water dimer should be present in the atmosphere, yet attempts to detect water dimer absorption signatures in atmospheric field studies have so far yielded inconclusive results. Here we report spectral measurements in the near-infrared around 750 nm in the expected region of the | 0〈f | 4〉b|0 〉 overtone of the water dimer's hydrogen-bonded OH stretching vibration. The results were obtained using broadband cavity ringdown spectroscopy (BBCRDS), a methodology that allows absorption measurements to be made under controlled laboratory conditions but over absorption path lengths representative of atmospheric conditions. In order to account correctly and completely for the overlapping absorption of monomer molecules in the same spectral region, we have also constructed a new list of spectral data (UCL08) for the water monomer in the 750–20 000 cm−1 (13 μm–500 nm) range. Our results show that the additional lines included in the UCL08 spectral database provide an improved representation of the measured water monomer absorption in the 750 nm region. No absorption features other than those attributable to the water monomer were detected in BBCRDS experiments performed on water vapour samples containing dimer concentrations up to an order of magnitude greater than expected in the ambient atmosphere. The absence of detectable water dimer features leads us to conclude that, in the absence of significant errors in calculated dimer oscillator strengths or monomer/dimer equilibrium constants, the widths of any water dimer absorption features present around 750 nm are of the order of 100 cm−1 HWHM, and certainly greater than the 25–30 cm−1 HWHM reported in the literature for lower energy water dimer transitions up to 8000 cm−1.

Synthesis of crosslinked polystyrene particles by seeded batch polymerization with monomer absorption

A highly crosslinked, monodispersed polystyrene(PS) particle was prepared by a seeded batch dispersion polymerization with a monomer absorption method. Prior to polymerization, 1.9 μm monodispersed PS seed particles were treated under an optimum condition of monomer absorption. The effects of divinylbenzebe(DVB) concentration and polymerization temperature were examined for styrene(in PS seed)/styrene(in the second stage) mass ratio of 1:1 in the medium range of EtOH/water mass ratio of 100/0-80/20 and 2.3 μm uniform crosslinked PS particles containing 15%-20% (mass fraction) DVB were prepared at 60–70 °C. The results show that monomer absorption before the second stage of polymerization is more effective to prepare highly crosslinked monodispersed PS particles.

Vibronic line shapes of PTCDA oligomers in helium nanodroplets

Oligomers of the organic semiconductor 3,4,9,10-perylene-tetracarboxylic-dianhydride, C(24)H(8)O(6) (PTCDA) are studied by means of helium nanodroplet isolation spectroscopy. In contrast to the monomer absorption spectrum, which exhibits clearly separated, very sharp absorption lines, it is found that the oligomer spectrum consists of three main peaks having an apparent width orders of magnitude larger than the width of the monomer lines. Using a simple theoretical model for the oligomer, in which a Frenkel exciton couples to internal vibrational modes of the monomers, these experimental findings are nicely reproduced. The three peaks present in the oligomer spectrum can already be obtained taking only one effective vibrational mode of the PTCDA molecule into account. The inclusion of more vibrational modes leads to quasicontinuous spectra, resembling the broad oligomer spectra.

Side‐chain ferrocene‐containing (meth)acrylate polymers: Synthesis and properties

AbstractA comprehensive investigation on the synthesis and properties of a series of ferrocene‐containing (meth)acrylate monomers and their polymers that differ in the linkers between the ferrocene unit and the backbone was carried out. The side‐chain ferrocene‐containing polymers were prepared via atom transfer radical polymerization. The kinetic studies indicated that polymerization of most monomers followed a “controlled”/living manner. The polymerization rates were affected by the vinyl monomer structures and decreased with an increase of the linker length. Methacrylate polymerization was much faster than acrylate polymerization. The optical absorption of monomers and polymers was affected by the linkers. Thermal properties of these polymers can be tuned by controlling the length of the linker between the ferrocene unit and the backbone. By increasing the length of the linker, the glass transition temperature ranged from over 100 to −20 °C. Electrochemical properties of both monomers and polymers were characterized. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011