Effect of EDTA and Citric Acid Additive on the Polymorph, Morphology, and Photocatalytic Activity of Iron Oxyhydroxide.

Iron oxyhydroxide [FeO(OH)] is a promising photocatalyst owing to its simple synthesis at mild temperatures and narrow band gap, which allows for the efficient harvesting of visible light. The selective production of FeO(OH) polymorphs and the modulation of their morphology by changing the iron salts, salt concentration, and additives have been widely reported. This study focuses on overcoming fast charge-carrier recombination by developing FeO(OH)-based heterostructure materials. The role of a chelating ligand (EDTA and citrate) in determining the polymorph type, morphology, and photocatalytic activity of FeO(OH) was studied. The findings revealed the additive produced of nanosized α-FeO(OH)/EDTA and layered γ-FeO(OH)/citrate with superior catalytic activities.

Density Functional Theory Study on the 193Ir Mössbauer Spectroscopic Parameters of Vaska's Complexes and Their Oxidative Adducts.

In the present study, density functional theory (DFT) calculation was applied to Vaska's complexes of formula trans-[IrIX(CO)(PPh3)2] and their oxidative adducts with small molecules (YZ) including H2, i.e., trans-[IrIIIClYZ(CO)(PPh3)2], to successfully correlate the electronic states of the complexes with the corresponding 193Ir Mössbauer spectroscopic parameters. After confirming the reproducibility of the DFT methods for elucidating the equilibrium structures and 193Ir Mössbauer isomer shifts of the octahedral Ir complexes, the isomer shifts and quadrupole splitting values of Vaska's complexes and their oxidative adducts were calculated. A bond critical point analysis revealed that the tendency in the isomer shifts was correlated with the strength of the covalent interaction in the coordination bonds. In an electric field gradient (EFG) analysis of the oxidative adducts, the sign of the principal axis was found to be positive for the complex with YZ = Cl2 and negative for the complex with YZ = H2. This reversal of the sign of the EFG principal axis was caused by the difference in the electron density distribution for the coordination bonds between Ir and YZ, according to a density of states analysis.

Density Functional Theory (DFT)-Based Bonding Analysis Correlates Ligand Field Strength with 99Ru Mössbauer Parameters of Ruthenium-Nitrosyl Complexes.

We applied density functional theory calculations to ruthenium-nitrosyl complexes, which are known to exist in high-level radioactive waste generating during reprocessing of spent nuclear fuel, to give a theoretical correlation between 99Ru Mössbauer spectroscopic parameters and ligand field strength for the first time. The structures of the series of complexes, [Ru(NO)L5] (L = Br-, Cl-, NH3, CN-), were modeled based on the corresponding single-crystal X-ray coordinates. The comparisons of the geometries and total energies between the different spin states suggested that the singlet spin state of [Ru(II)(NO+)L5] complexes were the most stable. This result was supported by the benchmark calculations of the 99Ru Mössbauer isomer shift (δ) and quadrupole splitting (ΔEQ) values. The calculated results of both the δ and ΔEQ values reproduced the experimental results by reported previously and increased in the order of L = Br-, Cl-, NH3, CN-. Finally, we estimated the ligand field strength (Δo) based on molecular orbitals, assuming C4v symmetry and showed the increase of Δo values in that order, being consistent with well-known spectrochemical series of ligands. The increase attributes to the strengthening of the abilities of σ-donor and π-acceptor of the L-ligands to the Ru atom, resulting in the increase of the δ values. Furthermore, the increase of the σ-type donation into Ru dx2-y2 orbital and the π-type back-donation from Ru dxz, dyz orbitals in that order caused the decrease of the electron density along the Ru-NO axis, resulting in the increase of the ΔEQ values. This study is expected to contribute to the ligand design for the ruthenium-nitrosyl complexes, leading to the drug design for NO carrier and the decontamination of radioactive ruthenium from the ecological system, as well as the recovery of platinum-group metals from high-level radioactive waste.

Water adsorption with relative humidity changes for keratin and collagen as studied by infrared (IR) micro-spectroscopy.

BACKGROUND: Natures and amounts of water retained at the surface of stratum corneum (SC) of human skins, affecting skin health and penetration of chemical components, remain unclear. METHODS: A keratin film, a main component of human SC surface, was measured by IR micro-spectroscopy combined with a quartz crystal microbalance (QCM) and a relative humidity (RH) control system. RESULTS: Water contents increased with RH up to about 19 wt% and were correlated linearly with the OH + NH band areas in IR spectra of the keratin film. The OH + NH band areas for the triple helix collagen film are about twice as large as those for the keratin film (double helix). The free water component increases with RH by keeping the bound water component minor for the keratin film. About twice of water retention capacity of the collagen film can be due to increasing adsorption of free water, interacting possibly with hydrophobic aliphatic CH surfaces. CONCLUSION: The present results suggest relatively low water contents less than about 19 wt% of outermost SC layers of human skin composed mostly of keratin exposed to ambient RH conditions. The triple helix collagen can be used as an effective moisturizing agent.

Correction to: Assessment of natural radioactivity in coals and coal combustion residues from a coal-based thermoelectric plant in Bangladesh: implications for radiological health hazards.

The original version of this article unfortunately contained an error in eq. 1. The denominator Ɛ of Eq. (1) was missing.

Assessment of natural radioactivity in coals and coal combustion residues from a coal-based thermoelectric plant in Bangladesh: implications for radiological health hazards.

To study the level of radioactivity concentrations from a coal-based power plant (Barapukuria, Bangladesh) and to estimate the associated radiological hazards, coal and associated combustion residuals from the power plant were analyzed by gamma-ray spectrometry with high-purity germanium (HPGe) detector. The results reveal that the mean radioactivity (Bq kg-1) concentrations in feed coal samples are 66.5 ± 24.2, 41.7 ± 18.2, 62.5 ± 26.3, and 232.4 ± 227.2 for U-238, Ra-226, Th-232, and K-40, respectively, while in coal combustion residuals (CCRs), they are 206.3 ± 72.4, 140.5 ± 28.4, 201.7 ± 44.7, and 232.5 ± 43.8, respectively. With the exception of K-40, all the determined natural radionuclides are considerably higher in the investigated feed coal and associated combustion residues as compared with the world soil and world coal mean activities. On the average, CCRs contains 3.10-3.37 times more natural radionuclides than the feed coal, except for K-40. The radioactivity of fly ash and bottom ash is fractionated, and ratio ranges from 1.40 to 1.57. The mean values of the radiological hazard indices in the coal and their associated residuals are 153.1 and 446.8 Bq kg-1 for radium equivalent activity, 0.41 and 1.21 for the external hazard index, 70 and 200.1 nGy h-1 for the absorbed gamma dose rate, 0.09 and 0.25 mSv year-1 for the annual effective dose rate, and 3.0 × 10-4 and 8.6 × 10-4 Sv-1 for the excess lifetime cancer risk, respectively, most of which exceed the UNSCEAR-recommended respective threshold limits. The outcome of this study suggests a potential radiological threat to the environment as well as to the health of occupational workers and nearby inhabitants from the examined samples.

UV and IR Spectroscopy of Cryogenically Cooled, Lanthanide-Containing Ions in the Gas Phase.

We measure UV and IR spectra in the gas phase for EuOH+, EuCl+, and TbO+ ions, which are produced by an electrospray ionization source and cooled to ∼10 K in a cold, 22-pole ion trap. The UV photodissociation (UVPD) spectra of these ions show a number of sharp, well-resolved bands in the 30000-38000 cm-1 region, although a definite assignment of the spectra is difficult because of a high degree of congestion. We also measure an IR spectrum of the EuOH+ ion in the 3500-3800 cm-1 region by IR-UV double-resonance spectroscopy, which reveals an OH stretching band at 3732 cm-1. We perform density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations of these ions in order to examine the nature of the transitions. The DFT results indicate that the states of highest-spin multiplicity (octet for EuOH+ and EuCl+ and septet for TbO+) are substantially more stable than other states of lower-spin multiplicity. The TD-DFT calculations suggest that UV absorption of the EuOH+ and EuCl+ ions arises from Eu(4f) → Eu(5d,6p) transitions, whereas electronic transitions of the TbO+ ion are mainly due to the electron promotion of O(2p) → Tb(4f,6s). The UVPD results of the lanthanide-containing ions in this study suggest the possibility of using lanthanide ions as "conformation reporters" for gas-phase spectroscopy for large molecules.

Glycine Polymerization on Oxide Minerals.

It has long been suggested that mineral surfaces played an important role in peptide bond formation on the primitive Earth. However, it remains unclear which mineral species was key to the prebiotic processes. This is because great discrepancies exist among the reported catalytic efficiencies of minerals for amino acid polymerizations, owing to mutually different experimental conditions. This study examined polymerization of glycine (Gly) on nine oxide minerals (amorphous silica, quartz, α-alumina and γ-alumina, anatase, rutile, hematite, magnetite, and forsterite) using identical preparation, heating, and analytical procedures. Results showed that a rutile surface is the most effective site for Gly polymerization in terms of both amounts and lengths of Gly polymers synthesized. The catalytic efficiency decreased as rutile > anatase > γ-alumina > forsterite > α- alumina > magnetite > hematite > quartz > amorphous silica. Based on reported molecular-level information for adsorption of Gly on these minerals, polymerization activation was inferred to have arisen from deprotonation of the NH3+ group of adsorbed Gly to the nucleophilic NH2 group, and from withdrawal of electron density from the carboxyl carbon to the surface metal ions. The orientation of adsorbed Gly on minerals is also a factor influencing the Gly reactivity. The examination of Gly-mineral interactions under identical experimental conditions has enabled the direct comparison of various minerals' catalytic efficiencies and has made discussion of polymerization mechanisms and their relative influences possible Further systematic investigations using the approach reported herein (which are expected to be fruitful) combined with future microscopic surface analyses will elucidate the role of minerals in the process of abiotic peptide bond formation.

Infrared and Raman spectroscopic investigation of the reaction mechanism of cytochrome c oxidase.

Recent progress in studies on the proton-pumping and O2reduction mechanisms of cytochrome c oxidase (CcO) elucidated by infrared (IR) and resonance Raman (rR) spectroscopy, is reviewed. CcO is the terminal enzyme of the respiratory chain and its O2reduction reaction is coupled with H⁺ pumping activity across the inner mitochondrial membrane. The former is catalyzed by heme a3 and its mechanism has been determined using a rR technique, while the latter used the protein moiety and has been investigated with an IR technique. The number of H⁺ relative to e⁻ transferred in the reaction is 1:1, and their coupling is presumably performed by heme a and nearby residues. To perform this function, different parts of the protein need to cooperate with each other spontaneously and sequentially. It is the purpose of this article to describe the structural details on the coupling on the basis of the vibrational spectra of certain specified residues and chromophores involved in the reaction. Recent developments in time-resolved IR and Raman technology concomitant with protein manipulation methods have yielded profound insights into such structural changes. In particular, the new IR techniques that yielded the breakthrough are reviewed and assessed in detail. This article is part of a Special Issue entitled: Vibrational spectroscopies and bioenergetic systems.

Bonding Study on the Chemical Separation of Am(III) from Eu(III) by S-, N-, and O-Donor Ligands by Means of All-Electron ZORA-DFT Calculation.

We performed a theoretical investigation for the selectivity of Eu(III)/Am(III) ions depending on the donor atoms by means of all-electron ZORA-DFT calculation. We estimated their selectivity as the relative stability in the complex formation reaction. The B2PLYP functional reproduced the experimental selectivity in which S- and N-donor ligands favor Am(III) ion, but O-donor ligand favors Eu(III) ion. Mulliken's bond overlap population analysis revealed that the contribution of the f orbital to the bonding was small or zero for Eu complex, whereas it was large for Am complex. The bonding nature of the f orbital for Am ion was the bonding type to S- and N-donor ligands, while it was the antibonding type to O-donor ligand. It was suggested that the difference in the bonding nature between the f orbital in the metal and the donor atoms determines the selectivity of Eu(III)/Am(III) by donor ligands.

Effective pumping proton collection facilitated by a copper site (CuB) of bovine heart cytochrome c oxidase, revealed by a newly developed time-resolved infrared system.

X-ray structural and mutational analyses have shown that bovine heart cytochrome c oxidase (CcO) pumps protons electrostatically through a hydrogen bond network using net positive charges created upon oxidation of a heme iron (located near the hydrogen bond network) for O2 reduction. Pumping protons are transferred by mobile water molecules from the negative side of the mitochondrial inner membrane through a water channel into the hydrogen bond network. For blockage of spontaneous proton back-leak, the water channel is closed upon O2 binding to the second heme (heme a3) after complete collection of the pumping protons in the hydrogen bond network. For elucidation of the structural bases for the mechanism of the proton collection and timely closure of the water channel, conformational dynamics after photolysis of CO (an O2 analog)-bound CcO was examined using a newly developed time-resolved infrared system feasible for accurate detection of a single C=O stretch band of α-helices of CcO in H2O medium. The present results indicate that migration of CO from heme a3 to CuB in the O2 reduction site induces an intermediate state in which a bulge conformation at Ser-382 in a transmembrane helix is eliminated to open the water channel. The structural changes suggest that, using a conformational relay system, including CuB, O2, heme a3, and two helix turns extending to Ser-382, CuB induces the conformational changes of the water channel that stimulate the proton collection, and senses complete proton loading into the hydrogen bond network to trigger the timely channel closure by O2 transfer from CuB to heme a3.

Site-specific protein dynamics in communication pathway from sensor to signaling domain of oxygen sensor protein, HemAT-Bs: Time-resolved Ultraviolet Resonance Raman Study.

HemAT-Bs is a heme-based signal transducer protein responsible for aerotaxis. Time-resolved ultraviolet resonance Raman (UVRR) studies of wild-type and Y70F mutant of the full-length HemAT-Bs and the truncated sensor domain were performed to determine the site-specific protein dynamics following carbon monoxide (CO) photodissociation. The UVRR spectra indicated two phases of intensity changes for Trp, Tyr, and Phe bands of both full-length and sensor domain proteins. The W16 and W3 Raman bands of Trp, the F8a band of Phe, and the Y8a band of Tyr increased in intensity at hundreds of nanoseconds after CO photodissociation, and this was followed by recovery in ∼50 µs. These changes were assigned to Trp-132 (G-helix), Tyr-70 (B-helix), and Phe-69 (B-helix) and/or Phe-137 (G-helix), suggesting that the change in the heme structure drives the displacement of B- and G-helices. The UVRR difference spectra of the sensor domain displayed a positive peak for amide I in hundreds of nanoseconds after photolysis, which was followed by recovery in ∼50 µs. This difference band was absent in the spectra of the full-length protein, suggesting that the isolated sensor domain undergoes conformational changes of the protein backbone upon CO photolysis and that the changes are restrained by the signaling domain. The time-resolved difference spectrum at 200 µs exhibited a pattern similar to that of the static (reduced - CO) difference spectrum, although the peak intensities were much weaker. Thus, the rearrangements of the protein moiety toward the equilibrium ligand-free structure occur in a time range of hundreds of microseconds.

Investigation of enhanced Am selectivity for Eu in solvent extraction using a BTPhen ligand substituted with halogen.

The effect of bromine (Br) on the separation of Am/Eu using BTPhen was investigated using DFT calculations. The simulated results agreed well with the reported experimental result of Br substitution. It is concluded that the contribution of the d orbital becomes less important by increasing the number of Br atoms, that is, the relative contribution of the f orbital becomes important. The Am f orbital contributed to both bonding and antibonding interactions with the ligand, whereas the Eu f orbital contributed to the antibonding interaction with the ligand. To study the halogen effect systematically, we introduced a series of new halogen atoms (chlorine, fluorine, iodine) into BTPhen. When the electronegativity of the halogen atom increases, the ΔG for complex formation shifts to the positive direction, and the ΔΔG which shows the difference in ΔG between Am and Eu becomes a large negative value, suggesting that the Am selectivity is larger. This is due to the increased Δρ BCP (= ρ BCP(Am) - ρ BCP(Eu)) between the metal and the ligating nitrogen atom with an increase of electronegativity of the halogen atom.

In Situ Visible Spectroscopic Daily Monitoring of Senescence of Japanese Maple (Acer palmatum) Leaves.

The degradation of green leaves in autumn after their photosynthetic activities is associated with decreases in chlorophylls and increases in anthocyanins. However, the sequential orders of these processes are not well understood because of a lack of continuous monitoring of leaves in the same positions. Therefore, the senescence processes of Japanese maple (Acer palmatum) leaves were followed daily in the same positions for approximately 60 days using visible spectroscopy with an original handheld visible-near-infrared spectrometer. The obtained reflection spectra were converted to absorption spectra and band areas of chlorophyll a and anthocyanins were determined. Decreases in the chlorophyll a band area with time show two-step exponential decreases corresponding to slow and fast first-order decrease rates. A rapid decrease in chlorophyll a started after an increase in anthocyanin. Therefore, the leaf senescence started through a slow decrease in chlorophyll a (20-30 days), followed by a rapid increase in anthocyanins (~20 days), followed by a rapid decrease in chlorophyll a (10-20 days). The formation of anthocyanins has been proposed to protect leaf cells from losing chlorophylls through solar radiation damage. The obtained sequential changes of pigments support this light screen hypothesis. (199 words < 200 words).

Synthesis, characterization, and reactivity of hypochloritoiron(III) porphyrin complexes.

A hypochloritoiron(III) porphyrin species has been proposed as a key intermediate in an antimicrobial defense system in neutrophils and in heme-catalyzed chlorination reactions. We report herein the preparation, spectroscopic characterization, and reactivity of the bis(hypochlorito)iron(III) porphyrin complex [(TPFP)Fe(III)(OCl)(2)](-) (1) and the imidazole-hypochloritoiron complexes (TPFP)Fe(III)(OCl)(1-R-Im) [R = CH(3) (2), H (3), CH(2)CO(2)H (4)], in which TPFP is 5,10,15,20-tetrakis(pentafluorophenyl)porphyrinate. The structures of 1-4 were confirmed by absorption, (2)H and (19)F NMR, EPR, and resonance Raman spectroscopy and electrospray ionization mass spectrometry at low temperature. The reactions of 1 and 2 with various organic substrates show that 1 and 2 are capable of chlorination, sulfoxidation, and epoxidation reactions and that 1 is much more reactive with these substrates than 2.

Broadband near-field mid-infrared spectroscopy and application to phonon resonances in quartz.

Infrared (IR) spectroscopy is a versatile analytical method and nano-scale spatial resolution could be achieved by scattering type near-field optical microscopy (s-SNOM). The spectral bandwidth was, however, limited to approximately 300 cm(-1) with a laser light source. In the present study, the development of a broadband mid-IR near-field spectroscopy with a ceramic light source is demonstrated. A much wider bandwidth (at least 3000 to 1000 cm(-1)) is achieved with a ceramic light source. The experimental data on quartz Si-O phonon resonance bands are well reproduced by theoretical simulations indicating the validity of the present broadband near-field IR spectroscopy.

Improvement of Cs detection performance and formation of CsCl and Cs nanoparticles by tuning graphene oxide quantum dot-based nanocomposite.

A new nanocomposite was developed using functionalized graphene oxide quantum dots (GOQDs) with cesium green molecules for the first time. Although the cesium green molecule works effectively only in the solid-state, without water, and in basic conditions, the functionalized GOQDs with cesium green made the nanocomposite work well as a cesium (Cs) detector in mixed solution (distilled water/THF). The nanocomposite can be employed as a Cs detector in both acidic and basic conditions. The present study revealed that the nanocomposite of GOQDs with cesium green showed an enhanced photoluminescence in basic conditions, while the intensity of the photoluminescence in acidic conditions is the superposition of the photoluminescence of the corresponding components. The photoluminescence of the nanocomposite was quenched (turned OFF) after Cs treatment in basic conditions. On the other hand, in the acidic conditions it was found that the photoluminescence intensity of this nanocomposite was enhanced (turned ON) by the Cs addition in two different Cs concentrations, 0.06 mmol L-1 and 0.12 mmol L-1. In addition, the movement of the nanocomposite (after Cs addition) under the electron beams through TEM measurement was observed. The formation of CsCl and Cs nanoparticles was identified. Specifically, the Cs cluster occurrence is discussed by taking into account the mobility effect of the adatoms on the composite layer under electron beam irradiation.

Modulated near-field spectral extraction of broadband mid-infrared signals with a ceramic light source.

In order to obtain broadband near-field infrared (IR) spectra, a Fourier-transform IR spectrometer (FT-IR) and a ceramic light source were used with a scattering-type scanning near-field optical microscope (s-SNOM). To suppress the background (far-field) scattering, the distance between the scattering probe and the sample was modulated with frequency Ω by a piezo-electric actuator, and the Ω component was extracted from the signal with a lock-in detection. With Ω=30 kHz, a peak-to-peak modulation amplitude of 198 nm, and a probe with smooth surface near the tip, broadband near-field IR spectra could be obtained in the 1200-2500 cm(-1).

Cs Adsorption and CsCl Particle Formation Facilitated by Amino Talc-like Clay in Aqueous Solutions at Room Temperature.

Amino talc-like clay with an increased number of active sites and dispersion in a colloidal system has been synthesized and used for contaminant adsorption and support for nanoparticle formation. Amino talc-like clays having different number of layers and aminoalkyl ligands were synthesized and their Cs uptake behavior was examined. Cs uptake through Cs adsorption and CsCl particle formation facilitated by amino talc-like clay in a colloidal aqueous solution at room temperature are reported. The amino talc-like clay demonstrated better Cs uptake with a high initial Cs concentration than talc and montmorillonite. This might have been caused by a high concentration of trapped Cs and Cl ions in exfoliated amino clay, which eventually became CsCl particles. The formation of the CsCl particles in the amino clay depended on the clay concentration and ethanol treatment. The exfoliation of the basal sheets of the amino clay as a result of a high salt concentration and the protonation of amine induced by ethanol treatment was shown to be a precondition for CsCl particle formation. These results could promote amino talc-like clay for high-concentration Cs uptake and the green synthesis of Cs-halide particles in an aqueous solution.

Gas Cell Infrared and Attenuated Total Reflection Infrared Spectroscopic Studies for Organic-Inorganic Interactions in Adsorption of Fulvic Acid on the Goethite Surface Generating Carbon Dioxide.

The generation of carbon dioxide (CO2) from Nordic fulvic acid (FA) solution in the presence of goethite (α-FeOOH) was observed in FA-goethite interaction experiments at 25-80 ℃. CO2 generation processes observed by gas cell infrared (IR) spectroscopy indicated two steps: the zeroth order slower CO2 generation from FA solution commonly occurring in the heating experiments of the FA in the presence and absence of goethite (activation energy: 16-19 kJ mol-1), and the first order faster CO2 generation from FA solution with goethite (activation energy: 14 kJ mol-1). This CO2 generation from FA is possibly related to redox reactions between FA and goethite. In situ attenuated total reflection infrared (ATR-IR) spectroscopic measurements indicated rapid increases with time in IR bands due to COOH and COO- of FA on the goethite surface. These are considered to be due to adsorption of FA on the goethite surface possibly driven by electrostatic attraction between the positively charged goethite surface and negatively charged deprotonated carboxylates (COO-) in FA. Changes in concentration of the FA adsorbed on the goethite surface were well reproduced by the second order reaction model giving an activation energy around 13 kJ mol-1. This process was faster than the CO2 generation and was not its rate-determining step. The CO2 generation from FA solution with goethite is faster than the experimental thermal decoloration of stable structures of Nordic FA in our previous report possibly due to partial degradations of redox-sensitive labile structures in FA.