Cation-specific vacuum ultraviolet circular dichroism behaviour of alginate solutions,gels and solid films

The vacuum ultraviolet circular dichroism of alginate solutions, gels and solid films is reported. Two previously observed bands at ～215 and ～203 nm are assigned to $\text{n → π}{}^1$ transitions of carboxy groups under different conditions of local environment. Three bands not previously observed are at ～185 nm, assigned to carboxy $\text{π → π}{}^1$ transitions, and at ～169 and ～149 nm, assigned to transitions of the polymer backbone. In the course of the sol (Na⁺)-gel (Ca²⁺), the sol (Na⁺-film (Na⁺) and the gel (Ca²⁺)-film (Ca²⁺) transitions, intensity changes are observed in both the low energy and high energy bands. The c.d. changes during the three transitions differ in magnitude, but are qualitatively the same, from which we conclude that the chain conformations in the gel and films are similar, and that the principal spectral changes have their origin in perturbation of chromophores by site-bound cations.     

Luminescence of the near‐ultraviolet blue‐emitting Ba9Al2Si6O24:Ce3+ phosphor

A near‐ultraviolet (NUV) blue‐emitting phosphor Ba₉Al₂Si₆O₂₄:Ce³⁺ (BAS:Ce³⁺) was synthesized using a high‐temperature solid‐state reaction. BAS:Ce³⁺ had an excitation band peak at about 328 nm and showed a blue emission band. The NUV‐blue emission band had a peak at about 386 nm with a band width of about 60 nm, attributed to the 5d–4f transition of Ce³⁺. Fluorescent decay showed an exponential model with a lifetime of 27.2 nsec. At 150°C, the luminescence intensity decreased to 68.7% compared with the intensity at room temperature.     

Energy transfer by chlorophyllb in detergent micelles

The concentration-dependent depolarization, concentration-dependent quenching, absorption and fluorescence spectra in solutions of chlorophyllb-containing detergent micelles with Triton X-100 were studied in a concentration range ofc = 0.4 μM–0.6mM chlorophyllb andc_d = 0.4–7.0mM Triton X-100. The concentration-dependent depolarization obeys Fo¨rster's theory of depolarization of fluorescence with a transfer distance parameterR₀ = 43 ± 2A?. The concentration-dependent quenching is described by an empirical formula for the relative fluorescence yieldη/η₀=sol1[1 + (cc_1/2)²] given by Kelly and Porter (Kelly A. R. and Porter, G. (1970) Proc. R. Soc. Lond. Ser. A. 315, 149–161). With increasing chlorophyll b concentration the red absorption band at 650 nm is shifted toward a longer wavelength and its width increases by 10 nm, the intensity of the long wave fluorescence band increases about 720 nm. The results analysed in terms of these findings lead to the conclusions that chlorophyllb molecules are (a) locally concentrated in the micelles up to the concentration range of in vivo conditions, (b) partly in an aggregated state capable for fluorescence, (c) the chlorophyllb →chlorophyllb homotransfer may be about 3–26 % of the homotransfer chlorophylla →chlorophyll-a depending on the ratio of their concentrations.     

The rate of formation of P700+—A0 - in photosystem I particles from spinach as measured by picosecond transient absorption spectroscopy

Photosystem I particles containing 30–40 chlorophyll a molecules per primary electron donor P700 were subjected to 1.5 ps low density laser flashes at 610 nm resulting in excitation of the antenna chlorophyll a molecules followed by energy transfer to P700 and subsequent oxidation of P700. Absorbance changes were monitored as a function of time with 1.5 ps time resolution. P700 bleaching (decrease in absorbance) occurred within the time resolution of the experiment. This is attributed to the formation of ¹P700.^* This observation was confirmed by monitoring the rise of a broad absorption band near 810 nm due to chlorophyll a excited singlet state formation. The appearance of the initial bleach at 700 nm was followed by a strong bleaching at 690 nm. The time constant for the appearance of the 690 nm bleach is 13.7±0.8 ps. In the near-infrared region of the spectrum, the 810 nm band (which formed upon the excitation of the photosystem I particles) diminished to about 60% of its original intensity with the same 13.7 ps time constant as the formation of the 690 nm band. The spectral changes are interpreted as due to the formation of the charge separated state P700⁺—A₀ ^-, where A₀ is the primary electron acceptor chlorophyll a molecule.     

Synthesis, mesomorphism and luminescence properties of palladium(II) and platinum(II) complexes with dimeric Schiff base liquid crystals

A series of ortho-metallated Pd and Pt complexes containing dimeric liquid crystals Schiff base as cyclometallated ligands and N-benzoyl thiourea derivatives as co-ligands were prepared and investigated for their liquid crystalline properties. Their structures were assigned based on elemental analysis, IR and ¹H NMR spectroscopy while the mesogenic properties were investigated by DSC and polarising optical microscopy. The complexes show either monotropic or enantiotropic transitions with nematic and smectic A phases being displayed, with the mesomorphic behaviour strongly related to the type of N-benzoyl thiourea as well as the metal center used. The structure of a palladium(II) complex has been solved by X-ray diffraction.The platinum(II) complexes show photoluminescence properties both in solution and in solid state at room temperature, with the emission band centered around 600 nm. These are the first examples of metallomesogens based on Schiff base cyclometallated ligands that display luminescence properties.     

Circular Dichroism is Sensitive to Monovalent Cation Binding in Monensin Complexes

Monensin is a natural antibiotic that exhibits high affinity to certain metal ions. In order to explore its potential in coordination chemistry, circular dichroism (CD) spectra of monensic acid A (MonH) and its derivatives containing monovalent cations (Li⁺, Na⁺, K⁺, Rb⁺, Ag⁺, and Et₄N⁺) in methanolic solutions were measured and compared to computational models. Whereas the conventional CD spectroscopy allowed recording of the transitions down to 192 nm, synchrotron radiation circular dichroism (SRCD) revealed other bands in the 178–192 nm wavelength range. CD signs and intensities significantly varied in the studied compounds, in spite of their similar crystal structure. Computational modeling based on the Density Functional Theory (DFT) and continuum solvent model suggests that the solid state monensin structure is largely conserved in the solutions as well. Time‐dependent Density Functional Theory (TDDFT) simulations did not allow band‐to‐band comparison with experimental spectra due to their limited precision, but indicated that the spectral changes were caused by a combination of minor conformational changes upon the monovalent cation binding and a direct involvement of the metal electrons in monensin electronic transitions. Both the experiment and simulations thus show that the CD spectra of monensin complexes are very sensitive to the captured ions and can be used for their discrimination. Chirality 28:420–428, 2016. © 2016 Wiley Periodicals, Inc.     

Total optical activity of agarose: relation to observable transitions in the vacuum ultraviolet

The changes in optical activity that accompany and characterize the coil-helix and helix-coil transitions of agarose in aqueous solutions and gels have been investigated by combined quantitative analysis of data from vacuum ultraviolet circular dichroism (VUCD) and optical rotary dispersion (ORD). VUCD of agarose in the high-temperature coil state shows a single accessible Gaussian band centered at ～183 nm. In the helix state this band is blue-shifted by ～9 nm, and the intensity is increased by a factor of ～2.6. Spectra at intermediate temperatures can be fitted to within experimental error by linear combination of coil and helix spectra, the relative proportions required providing an index of the extent of conformational ordering. ORD spectra throughout the conformational transition have a common form and differ only in absolute magnitude. The temperature course of conformational ordering derived from ORD intensity is in close agreement with the values obtained from VUCD. In both the coil and helix states the accessible VUCD band is positive, while the overall ORD is negative, indicating strong negative CD activity at lower wavelength. The ORD contribution corresponding to the positive VUCD band was calculated by Kronig–Kramers transform, and it was subtracted from the total ORD to give the residual ORD from all other optically active transitions of the molecule. In both the coil and helix states, this residual ORD could be fitted to within experimental error by a single Gaussian CD band at ～149 nm. A negative band at this wavelength has been reported previously for agarose films, but the observed intensity, relative to that of the lower energy positive band, is substantially smaller than the fitted value under hydrated conditions. In both the coil and helix states the total optical activity of agarose, characterized by observed ORD spectra, can be matched to within experimental error by Kronig-Kramers transform of the 149-nm negative band and the smaller positive band at higher wavelength, with no necessary involvement of deeper-lying transitions. The significance of this conclusion for fundamental understanding of carbohydrate optical activity is discussed.     

Protoplast isolation and culture from carob (Ceratonia siliqua) hypocotyls: ability of regenerated protoplasts to produce mannose-containing polysaccharides

The aim of this study was to isolate protoplasts from carob (Ceratonia siliqua L.) embryonic tissues with the ability to regenerate cell walls, divide and synthesize galactomannan, a valuable polysaccharide for industry. Protoplasts isolated from carob hypocotyl hooks regenerated cell walls within 24 h. The first divisions of the regenerated cells were observed after 2 days of culture. The highest percentage that successfully divided was achieved when the seedlings were grown under diffuse light, the hypocotyl hooks were plasmolysed for 1 h before incubation in the protoplast isolation solution and the protoplasts were cultured under diffuse light. After 9 days of culture, cell clusters, consisting of eight cells, had been produced, which underwent further mitotic divisions and which were expected to lead to callus formation. Polysaccharide and oligosaccharide synthesis during protoplast regeneration was studied by radiolabelling with exogenous d ‐[U‐¹⁴C]glucose, d ‐[U‐¹⁴C]mannose or d ‐[2‐³H]mannose, which gave rise to uniform, moderately specific and highly specific labelling, respectively. As revealed by the radioactivity distribution in cell wall monosaccharides, the regenerants deposited new wall polymers that differed markedly from those being synthesized by the hypocotyls from which the protoplasts had been isolated. The regenerants deposited large amounts of callose and smaller amounts of galactose‐, arabinose‐ and mannose‐containing polymers. The latter included glucuronomannan, as demonstrated by a new method involving partial acid hydrolysis followed by β‐glucuronidase (EC 3.2.1.31) digestion. The regenerating protoplasts also released soluble extracellular carbohydrates: polysaccharides which appeared to be mainly acidic arabinogalactans, and oligosaccharides which were mainly neutral and contained glucose, galactose and mannose. We conclude that regenerating carob protoplasts are a useful system for studying carbohydrate secretion, including mannose‐rich poly‐ and oligosaccharides.     

Vacuum ultraviolet circular dichroism of (1 → 6)-β-d-glucan

V.u.c.d. spectra recorded for freshly prepared aqueous solutions of (1 → 6)-β)-D-glucan(pustulan) contained a single positive band near 177 nm. This band was similar in position and magnitude to the single positive band observed in the spectrum of (1 → 6)-α-D-glucan (dextran). Pustulan solutions (20 mg/ml) were observed to gel with time at 10 C. Concurrently, a negative band at 190 nm developed in the pustulan v.u.c.d. spectrum followed by a blue shift of both bands with continued aging. Crystalline films of pustulan yield spectra which resembled the blue shifted spectra of aged gels. The time dependent development of the negative band was attributed to pustulan attaining a helical conformation in solution, and the blue shift to aggregation of helices, Na⁺ and Ca²⁺ were found to accelerate gelation presumably by decreasing the activity of the aqueous solvent.     

Solution-state characteristics of the ultraviolet A-induced visible fluorescence from proteins

In response to illumination by ultraviolet-A (UV-A) light, proteins in solid form are now known to display a visible blue fluorescence, ostensibly on account of excitation transitions of loosely-held electrons within peptide bond orbitals engaged in hydrogen bonding. Because the CO and NH atom groups in peptide bonds are generally engaged in extensive hydrogen bonding in globular proteins even in aqueous solution, one could argue that proteins in solution must also display this novel blue fluorescence. Here, using high concentrations to enhance detectability, two globular proteins, γ-crystallin, and lysozyme, are shown to fluoresce visibly, exhibiting: (a) two excitation maxima, at ∼315 nm and ∼385 nm, (b) maximal emission at 425 nm in 100 mg/ml lysozyme and 465 nm in 100 mg/ml γ-crystallin, (c) a time-resolved emission decay that is best fitted by a sum of three exponentials with lifetimes of 3.14, 0.46, and 9.08 ns, respectively, and comparable relative amplitudes of around 30--40 percent each, and (d) a weak CD spectrum displaying a positive band at ∼385 nm and a negative band at ∼465 nm. While the wavelength of maximal emission (^emλ_max) in lysozyme is the same for all protein concentrations, the ^emλ_max of γ-crystallin varies with protein concentration, suggesting a certain degree of conformation dependence.     

Luminescence properties of Tb3+ doped Sr2SnO4 green phosphor in UV/VUV regions

Polycrystalline Sr₂SnO₄ phosphors doped with Tb³⁺ were prepared by conventional solid‐state reaction method. Materials were characterized by powder XRD and EDS techniques. The luminescence properties of these materials were investigated under UV and VUV excitation. Upon excitation at 272 nm, phosphors exhibited intense emissions at 492 and 543 nm due to ⁵D₄ → ⁷ F₆ and ⁵D₄ → ⁷ F₅ transitions of Tb³⁺ ions, respectively. Materials also exhibited strong emissions from these transitions under VUV excitation at 147, 173 and 230 nm. Quantitative analysis of the spectra indicated probable applications of these phosphors for PDP and other display devices as green emitting phosphors. Copyright © 2012 John Wiley & Sons, Ltd.     

Sol‐gel synthesis and luminescent properties of red‐emitting Y(P,V)O4:Eu3+ phosphors

Eu³⁺‐activated Y(P,V)O₄ phosphors were prepared by the EDTA sol‐gel method, and the corresponding morphologies and luminescent properties were investigated. The sample particles were relatively spheroid with size of 2–3 µm and had a smooth surface. The excitation spectra for Y(P,V)O₄:Eu³⁺ consisted of three strong excitation bands in the 200–350 nm range, which were attributed to a Eu³⁺‐ O^2? charge‐transfer band and ¹A₁?¹ T₁/¹ T₂ transitions in VO₄^3?. The as‐synthesized phosphors exhibited a highly efficient red luminescence at 613 nm due to the Eu^{3+ 5}D₀?⁷ F₂ electric dipole transition. With the increase in the V⁵⁺/P⁵⁺ ratio, the luminescence intensity of the red phosphor under UV excitation was greatly improved due to enhanced VO₄^3? → Eu³⁺ energy transfer. Copyright © 2015 John Wiley & Sons, Ltd.     

Characterization and luminescence properties of CaMgSi2O6:Eu2+ blue phosphor

A blue CaMgSi₂O₆:Eu²⁺ phosphor was prepared by the solid‐state reaction method and the phosphor characterized in terms of crystal structure, particle size, photoluminescence (PL), thermoluminescence (TL) and mechanoluminescence (ML) properties using X‐ray diffraction (XRD), transmission electron microscopy (TEM), PL spectroscopy, TLD reader and ML impact technique. The XRD result shows that phosphor is formed in a single phase and has a monoclinic structure with the space group C2/c. Furthermore, the PL excitation spectra of Eu²⁺‐doped CaMgSi₂O₆ phosphor showed a strong band peak at 356 nm and the PL emission spectrum has a peak at 450 nm. The depths and frequency factors of trap centers were calculated using the TL glow curve by deconvolution method in which the trap depths were found to be 0.48 and 0.61 eV. The formation of CaMgSi₂O₆:Eu²⁺ phosphor was confirmed by Fourier transform infrared spectroscopy. The ML intensity increased linearly with the impact velocity of the piston used to deform the phosphor. It was shown that the local piezoelectricity‐induced electron bombardment model is responsible for the ML emission. Finally, the optical properties of CaMgSi₂O₆:Eu²⁺ phosphors are discussed. Copyright © 2015 John Wiley & Sons, Ltd.     

A temperature-induced absorption band centred in the region of 666 nm related to the configuration of the active site in frozen cytochrome oxidase

The existence of a temperature-induced absorption band centred in the region of 666 nm is demonstrated for both membrane-bound and soluble cytochrome oxidase in the fronze state.The 666 nm band is generated solely by an increase in temperature of both fully reduced and mixed valence state cytochrome oxidase in the presence of CO or O₂ within the ‘pocket’ containing the active site; it is not formed in the absence of both CO and O₂ from the sample.The formation of the 666 nm band is entirely reversible when the temperature is decreased again and its formation is not dependent on the presence of liganded CO at the sixth coordination site of haem a₃ in the low temperature range (below ?120°C) prior to photolysis.The shape and intensity of the 666 nm band are not affected by the extent of CO recombination following flash and photolysis and temperature increase and are not affected by changes in the valence states of the four metal centres when the O₂ reaction is in progress.     

Triplet-minus-singlet absorbance difference spectra of reaction centers of Rhodopseudomonas sphaeroides R-26 in the temperature range 24–290 K measured by Magneto-Optical Difference Spectroscopy (MODS)

The recently developed technique of Magneto-Optical Difference Spectroscopy (MODS) [10] has been applied to reaction centers (RC) of the photosynthetic bacterium Rhodopseudomonas sphaeroides R-26. Absorbance changes induced by a magnetic field are measured as a function of wavelength yielding the triplet-minus-singlet (T-S) absorbance difference spectrum. (T-S) spectra thus obtained have been measured from 24–290 K. Going from low to high temperature the (T-S) spectra show the following features:

1. A rapid decrease of positive absorption bands at 809 and 819 nm.
2. A slow appearance of a band shift at 798 nm.
3. A shift of the peak wavelength of the Q_y absorbance band of the primary donor P-860 from 992 to 861 nm, and of its Q_x band from 603 to 600 nm.

The spectra at 24, 66, 116, and 290 K have been analyzed by Gaussian deconvolution. The 800 nm region of the spectrum at 24 K can be decomposed in a combination of two band shifts and an appearing band. The temperature dependence of the spectra in this region is well explained by spectral broadening of the two shifting bands combined with a decrease in intensity of the appearing band when the temperature increases. The two shifting bands in the 800 nm region are identified as the two bands at 803 and 813 nm which together make up the 800 nm band in the absorption spectrum and are assigned to the two accessory RC bacteriochlorophylls (BChls). The band shift of the 813 nm pigment is appreciably larger than that of the 803 nm pigment. The appearing band at 808 nm is attributed to monomeric absorption of ³P-860, the triplet state being localized on one BChl. We find no evidence for admixture of a charge transfer (CT) state of ³P-860 with one of the accessory BChls at higher temperature.     

Effect of temperature on intense green emitting Na2Ca(PO4)F:Mn2+ phosphor

An intense green luminescent Na₂Ca(PO₄)F:Mn²⁺ phosphor has been prepared at high temperature by reduction treatment in a charcoal environment. The emission band of Mn²⁺ was obtained at around 522 nm (green) under 259 nm excitation. Enhancement in emission intensity arising from the thermal treatment is reported. The intense emission of the spectrum was assigned to electronic transitions ⁴T₁ → ⁶A₁ of Mn²⁺ ions. Intense PL emission suggested that temperature employed plays an important role in the present matrix. X‐ray diffraction pattern, photoluminescence and morphology by SEM of the host lattice of phosphors at different temperatures have been reported in this paper. The results obtained show that the present phosphor has potential for application in green emitting phosphors for the lamp industry. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis and luminescent properties of a novel bluish‐white afterglow phosphor,b‐Zn3(PO4)2:Hf4+

A new bluish‐white long‐lasting phosphorescent material, Hf⁴⁺‐doped b‐Zn₃(PO₄)₂, was prepared by the conventional high‐temperature solid‐state method. The photoluminescence (PL) spectrum reveals that it exhibits a strong blue emission band centred at 470 nm, with asymmetry on the long wavelength side; this material emits bluish‐white light and shows strong afterglow phosphorescence after it is excited with a 254 nm UV lamp. The phosphorescence lasts nearly 40 min in the light perception of the dark‐adapted human eye (0.32 mcd/m²). The possible phosphorescence mechanism is also analysed. Copyright © 2008 John Wiley & Sons, Ltd.     

The measurement of transmembrane helices by the deconvolution of CD spectra of membrane proteins: A review

The interpretation of the CD spectra of proteins to date requires additional secondary structural information of the proteins to be analyzed, such as x-ray or nmr data. Therefore, these methods are inappropriate for a CD data base whose secondary structures are unknown, as in the case of the membrane proteins. The Convex Constraint Analysis algorithm [A. Perczel, M. Hollósi, G. Tusnády, and G. D. Fasman (1991) Protein Engineering, Vol. 4, 669–679], on the other hand, operates only on a collection of spectral data to extract the common spectral components with their spectral weights. The linear combinations of these derived “pure” CD curves can reconstruct the original data set with great accuracy. For a membrane protein data set, the five-component spectra so obtained from the deconvolution consisted of two different types of α-helices (the α-helix in the soluble domain and the α_T-helix, for the transmembrane α-helix), a β-pleated sheet, a class C-like spectrum related to β-turns, and a spectrum correlated with the unordered conformation. The deconvoluted CD spectrum for the α_T-helix was characterized by a positive red-shifted band in the range 195–200 nm (+95,000 deg cm² dmol^?l), with the intensity of the negative band at 208 nm being slightly less negative than that of the 222 nm band (?50,000 and ?60,000 deg cm² dmol^?1, respectively) in comparison with the regular α-helix, with a positive band at 190 nm and two negative bands at 208 and 222 nm with magnitudes of + 70,000, ?30,000, and ?30,000 deg cm² dmol^?1, respectively. © 1994 John Wiley & Sons, Inc.     

The absence of a spectroscopically resolved intermediate state P+B− in bacterial photosynthesis

Reaction centers from the photosynthetic bacterium Rhodopseudomonas sphaeroides have been excited either in the bacteriopheophytin band at 760 nm or in the accessory bacteriochlorophyll (B) band around 800 nm with laser pulses of 150 fs duration. Upon monitoring in the absorption band of the primary donor (P) at 860 nm, ultrafast energy transfer is observed which leads to the excited state of P in less than 100 fs. A transient bleaching recovering in 400 ± 100 fs is specifically detected upon excitation and observation in the 800 nm absorption band of B. However, upon direct excitation of P in the near infrared and using either normal or borohydride-treated reaction centers, we have found no spectral or kinetic evidence indicating the presence of a transient intermediate state such as P⁺B⁻.     

A new Pr3+‐activated molybdate‐based phosphor for application to white LEDs with blue excitation

The novel red‐emitting phosphors K_xSr_1?2xMoO₄:Pr³⁺_x (0.00 ≤ x ≤ 0.04) were prepared by solid‐state reaction. The crystallization and particle sizes of samples were investigated by powder X‐ray diffraction (XRD) and transmission electron microscopy (TEM). TEM images were in good agreement with the theoretical calculation data from the XRD patterns. Photoluminescence analysis indicated that there were three excitation peaks under 430–500 nm, and all samples showed the intensely red emission at 648 nm corresponding to the ³P₀ → ³F₂ transition of Pr³⁺. The concentrations of doping ions, temperature and polyethylene glycol in the phosphor system can significantly influence the intensity of the red emission. The photoluminescence spectral intensity reached its maximum at x = 0.02. The results showed that the investigated phosphor is a potential red phosphor for white light‐emitting diodes. Copyright © 2010 John Wiley & Sons, Ltd.