Adsorption of -histidine on copper surface as evidenced by surface-enhanced Raman scattering spectroscopy

The adsorption of -histidine on a copper electrode from H₂O- and D₂O-based solutions is studied by means of surface-enhanced Raman scattering (SERS) spectroscopy. Different adsorption states of histidine are observed depending upon pH, potential, and the presence of the SO²⁻₄ and Cl⁻ ions. In acidic solutions of pH 1.2 the imidazole ring of the adsorbed histidine remains protonated and is not involved in the chemical coordination with the surface. The SO²⁻₄ and Cl⁻ ions compete with histidine for the adsorption sites. In solutions of pH 3.1 three different adsorption states of histidine are observed depending on the potential. Histidine adsorbs with the protonated imidazole ring oriented mainly perpendicularly to the surface at potentials more positive than −0.2 V. Transformation of that adsorption state occurs at more negative potentials. As this takes place, histidine adsorbs through the α-NH₂ group and the neutral imidazole ring. The Cl⁻ ions cause the protonation and detachment of the α-NH₂ group from the surface and the formation of the ion pair NH⁺₃ … Cl⁻ can be observed. In the neutral solution of pH 7.0 histidine adsorbs through the deprotonated nitrogen atom of the imidazole ring and the α-COO⁻ group at E ≥ −0.2 V. However, this adsorption state is transformed into the adsorption state in which the α-NH₂ group and/or neutral imidazole ring participate in the anchoring of histidine to the surface, once the potential becomes more negative. In alkaline solutions of pH 11.9 histidine is adsorbed on the copper surface through the neutral imidazole ring.     

Electrochemical and in situ Raman spectroscopic study on the stability of poly(<Emphasis Type="Italic">N</Emphasis>-methylaniline)

The stability of poly(N-methylaniline) (PNMA) as electrode material has been studied in aqueous solutions of sulfuric acid with the use of electrochemical and in situ Raman spectroscopic techniques. It has been shown that the electrochemical decomposition of electrodeposited PNMA films follows a first-order reaction kinetics. The decomposition rate constants vary between 1.2 × 10⁻⁵ and 2.0 × 10⁻³ s⁻¹ for electrode potential varying between 0.2 and 1.0 V vs Ag/AgCl, respectively. In situ Raman spectroscopy has been applied in obtaining kinetic data at selected electrode potentials, and good correlation of these data with the corresponding data obtained by cyclic voltammetry has been found. As compared to polyaniline, the decomposition of PNMA proceeds at nearly the same rate at electrode potentials not exceeding 0.5 V. The decomposition of PNMA proceeds faster within the potential limits of 0.5 to 0.8 V and slower at electrode potentials exceeding 0.8 V as compared to polyaniline. This article is dedicated to Professor Algirdas Vaškelis (Institute of Chemistry, Vilnius, Lithuania) on the occasion of his 70th birthday and in honour of his contributions to electrochemistry and physical chemistry.     

Aqueous sol–gel synthesis and thermoanalytical study of the alkaline earth molybdate precursors

The preparation and characterization of the M′–Mo–O nitrate–tartrate (M′ = Mg, Ca, Sr, and Ba) gels, which were produced by the simple aqueous sol–gel method and calcined at 500, 600, 700, 800, 900, and 1,000 °C temperatures are reported. The crystalline alkaline earth metal molybdates (MgMoO₄, CaMoO₄, SrMoO₄, and BaMoO₄) and as-prepared M′–Mo–O nitrate–tartrate gels investigated by thermal analysis (TG/DSC), X-ray diffraction (XRD), and scanning electron microscopy (SEM). TG/DSC analysis showed the possible decomposition mechanism of synthesized gels. XRD studies allowed the identification of main types of crystalline structures in the MgMoO₄, CaMoO₄, SrMoO₄, and BaMoO₄ systems. Moreover, SEM analysis revealed the changes of surface morphology of the final compounds depending on annealing temperatures.     

Fabrication and characterization of magnetic ferrofluids by the co-precipitation way using diglycolic acid

Developing of a simple method for the fabrication of superparamagnetic iron oxide nanoparticles (Nps) is still a challenge for materials scientists. This work reveals a way to fabricate especially stable ferrofluids from spherical Nps of magnetite using the co-precipitation method, for which a new (diglycolic acid) stabilizer was applied. The Nps of the average size of ~7.4–16.5 nm were characterized by means of high resolution transmission electron microscopy (HRTEM), atomic force microscopy (AFM), selective area electron diffraction (SAED), Raman, FTIR and Mössbauer spectroscopy. The stabilization effect of the diglycolic acid for the growth of superparamagnetic Nps growth was discussed on the basis of experimental results.     

Raman spectroelectrochemical study of Meldola blue, adsorbed and electropolymerized at a gold electrode

Surface-enhanced Raman spectroscopy (SERS) was used to probe the structure of adsorbed and electropolymerized Meldola blue (MB) films on roughened gold surfaces in solutions with pH 1.0 and 7.0 by using 785 nm excitation wavelength. Spectral bands were assigned based on density functional theory (DFT) calculations at B3LYP/6-311+G(2d, p) level. The most characteristic band of the oxidized MB form was found to be the breathing vibration of the central ring containing heteroatoms at 596 cm(-1). Based on a red shift of bands assigned to vibrations of double C=N(C(2)H(6)) bonds and adjacent ring C=C bonds in surface spectra as compared with solution 1 it was suggested that polymerization and interaction with an electrode surface proceed through these moieties. The presence of out-of-plane bands in SERS spectra was attributed to "flat" or slightly "tilted" orientation of aromatic rings at the interface. Potential-dependent spectral changes were followed by SERS spectroscopy. Raman spectra of the reduced MB form were obtained in both pH 1.0 and pH 7.0 solutions by analysis of the potential-difference SERS spectra. Reduced MB form can be recognized by characteristic bands near 1620, 1574, 1374, and 1234 cm(-1). By comparing the intensities of 1637 cm(-1) (oxidized MB form) and 1374 cm(-1) (reduced MB form) bands in experimental spectra of polymerized MB in pH 1.0 solution, a reduction-induced decrease by factor of 7 was estimated. A similar tendency in intensity changes showed calculations indicating that this effect is associated with reduction-induced changes in the molecular structure of the dye.     

2-Methyl-1,4-naphthoquinones containing 3-[N-(ω-mercaptoalkyl)alkanamide] chains: synthesis, self-assembling, and electrochemical properties

2-Methyl-1,4-naphthoquinone derivatives containing 3-[N-(ω-mercaptoalkyl)alkanamide] chains were synthesized from ω-bromoalkylamine salts of 2-methyl-3-carboxyalkyl-1,4-naphthoquinones in the presence of N,N′-dicyclohexylcarbodiimide at ambient temperature, and then transformed into the corresponding mercapto derivatives. Their self-assembling and electrochemical properties on gold were studied. The influence of an intrachain amide group on the structure and electron transfer properties of self-assembled monolayers were evaluated by comparison with analogous ester and alkyl chain-containing 2-methyl-1,4-naphthoquinones.     

Probing of lipase activity at air/water interface by sum-frequency generation spectroscopy

The infrared-visible sum-frequency generation (SFG) vibrational spectroscopy was used to probe enzymatic activity of Thermomyces lanuginosus lipase (TLL) at air/water interface. A monolayer of amphiphilic O-palmitoyl-2,3-dicyanohydroquinone (PDCHQ), containing target ester group and two CN groups serving as vibrational markers, was utilized as an enzyme substrate. SFG data revealed the detailed molecular scale structure and properties of the PDCHQ layer at the interface. In particular, we demonstrate that hydrophilic headgroup of PDCHQ is mainly in the form of an oxyanion, and the enzyme-induced cleavage of the ester bond could be spectroscopically monitored by the disappearance of the intense C tripple bond N resonance at 2224 cm(-1). The enzymatic nature of the ester bond cleavage was confirmed by the control experiments with deactivated S146A mutant variant of TLL. By comparing action of wild type (WT) TLL and its inactive S146A mutant, it was shown that two effects take place at the interface: disordering of the lipid monolayer due to the adsorption of enzyme and enzymatic cleavage of the ester bond. The concentration of enzyme as low as 10 nM could be easily sensed by the SFG spectroscopy. We present spectroscopic evidence that upon hydrolysis one of the products, 2,3-dicyanohydroquinone, leaves the surface, while the other, palmitic acid, remains at air/water interface in predominantly undissociated form with the mono-hydrogen-bonded carbonyl group. Strong amide I (1662 cm(-1)) and amide A (3320 cm(-1)) SFG signals from TLL suggest that enzyme molecules position themselves at air/water interface in an orderly fashion. Presented work demonstrates the potential of SFG spectroscopy for in situ real-time monitoring of enzymatic processes at air/water interface.     

Diboraanthracene-Doped Polymer Systems for Colour-Tuneable Room-Temperature Organic Afterglow

Organic ultralong room temperature phosphorescence (RTP), or organic afterglow, is a unique phenomenon, gaining widespread attention due to its far-reaching application potential and fundamental interest. Here, two laterally expanded 9,10-dimesityl-dihydro-9,10-diboraanthracene (DBA) derivatives are demonstrated as excellent afterglow materials for red and blue-green light emission, which is traced back to persistent thermally activated delayed fluorescence and RTP. The lateral substitution of polycyclic DBA scaffold, together with weak transversal electron-donating mesityl groups, ensures the optimal molecular properties for (reverse) intersystem crossing and long-lived triplet states in a rigid poly(methyl methacrylate) matrix. The achieved afterglow emission quantum yields of up to 3 % and 15 %, afterglow lifetimes up to 0.8 s and 3.2 s and afterglow durations up to 5 s and 25 s (for red and blue-green emitters, respectively) are attributed to the properties of single molecules.     

Raman spectroelectrochemical study of electrode processes at Neutral red- and poly(Neutral red) modified electrodes

The redox dye Neutral red (NR), adsorbed and electropolymerized at a roughened gold electrode, has been studied by Raman spectroscopy at λ_ex of 676.4 nm in an electrochemical cell. Spectral bands have been assigned based on density functional theory (DFT) calculations. The number and position of the bands, as well as their intensity depend on electrode potential, allowing one to discern different redox forms of NR or its polymer. The observed changes in band positions and intensities have been analyzed. Electrooxidation of hydroquinone and ascorbic acid at a gold electrode modified with adsorbed or electropolymerized layer of NR has been studied with in situ Raman spectroelectrochemical technique. During electrooxidation of solution species, NR layer contains both oxidized and reduced forms of this modifier. It has been shown that the relative content of a reduced form of NR at electrode surface increases with increasing concentration of any of oxidizable species used. It has been concluded that anodic oxidation of ascorbic acid or hydroquinone at NR or polyNR modified electrode proceeds within the modifier layer rather than at a modifier/electrolyte interface. In this respect, electrooxidation follows a redox mechanism.     

THz photomixer with milled nanoelectrodes on LT-GaAs

A terahertz (THz) photomixer: (i) a meander type antenna with integrated nanoelectrodes on (ii) a low temperature grown GaAs has been fabricated and characterized. It was designed for spectral range of 0.3–0.4 THz where molecular fingerprinting and sensing are performed. By combination of electron beam lithography with post-processing using focused ion beam (FIB), milling the THz emitter was successfully fabricated. Nanogaps as small as 40 nm width in the active area of photomixer were milled by FIB. Nanocontacts enhance electric fields of the illuminated and THz radiation and contribute to a better collection of photo-electrons. THz emission was obtained and spectrally characterized.