Biomimetic CoUagen/Hydroxyapatite Composite Scaffolds： Fabrication and Characterizations

Biomimetic collagen/hydroxyapatite scaffolds have been prepared by microwave assisted co-titration of phosphorous acid-containing collagen solution and calcium hydroxide-containing solution. The resultant scaffolds have been characterised with respect to their mechanical properties, composition and microstructures. It was observed that the in situ precipitation process could combine collagen fibril formation and hydroxyapatite （HAp） formation in one process step. Collagen fibrils guided hydroxyapatite precipitation to form bone-mimic collagen/hydroxyapatite composite containing both intrafibrillar and interfibrillar hydroxyapatites. The mineral phase was determined as low crystalline calcium-deficient hydroxyapatite with calcium to phosphorus ratio （Ca/P） of 1.4. The obtained 1% （collagen/HAp = 75/25） scaffold has a porosity of 72% and a mean pore size of 69.4 ~tm. The incorporation of hydroxyapatite into collagen matrix improved the mechanical modulus of the scaffold significantly. This could be attributed to hydroxyapatite crystallites in collagen fibrils which restricted the deformation of the collagen fibril network, and the load transfer of the collagen to the higher modulus mineral component of the composite.     

A study of the growth of normal and iodinated collagen fibrils in vitro using electron microscope autoradiography

Electron microscopic autoradiographic observations on collagen fibrils grown in vitro allow growth rates in the N- and C-terminal directions to be measured on individual fibrils. Such observations, made on normal and iodinated collagen, show that normal fibrils grow at both ends (although rather more rapidly at the N-terminal end), whereas fully-iodinated collagen fibrils grow only at the N-terminal end. Measurements of growth rates at different temperatures provide estimates of the activation enthalpy (ΔH^≠) and entropy (ΔS^≠) of precipitation for the two types of collagen. Solubility measurements have also yielded values for the thermodynamic enthalpy (ΔH) and entropy (ΔS) of precipitation. Results show that the activated (rate-limiting) state is characterized by a large positive ΔH^≠ and ΔS^≠ similar in magnitude to the ΔH and ΔS of transition from solution to fibril. It is also concluded that the different rates of precipitation of normal and iodinated collagen cannot be explained in terms of fibril formation requiring ionization of the tyrosine residues.     

13C/1H high power double magnetic resonance investigation of collagen backbone motion in fibrils and in solution

${}^{13}\text{C}{}^1\text{H}$ high power double magnetic resonance spectroscopy was used to investigate the mobility of the collagen peptide backbone. [1-¹³C]- and [2-¹³C]-glycine-labeled collagen samples (with >50% enrichment in ¹³C) were prepared via chick calvaria culture. ¹³C n.m.r.² spectra of labeled reconstituted collagen fibrils, of labeled helical collagen in solution, and of unlabeled bovine Achilles tendon collagen were obtained with scalar decoupling and with dipolar decoupling of protons. Proton-enhanced spectra were also obtained using cross-polarization techniques. n.m.r. parameters (linewidths, lineshapes, T₁ values, nuclear Overhauser enhancements, and cross polarization enhancements) were measured for the labeled samples and for collagen in natural abundance. Comparison of ¹³C n.m.r. parameters for bovine Achilles tendon fibrils and for reconstituted chick calvaria collagen fibrils established that chick calvaria collagen is a good model for the molecular dynamics of collagen in vivo.Spin-lattice relaxation times and nuclear Overhauser enhancements for [1-¹³C]- and [2-¹³C]glycine-labeled collagen indicated that R₁ ~2 × 10⁷s^?1 in solution, where R₁ is the diffusion constant for reorientation about the long axis of the molecule. A substantially smaller value for R₁ (2.6 × 10⁶s^?1) was calculated for an axially symmetric ellipsoid of revolution having dimensions appropriate to the collagen helix. The discrepancy between the rigid ellipsoid and n.m.r. values of R₁ suggests that the collagen molecule undergoes torsional reorientation, as well as rod-like reorientation, about its long axis.The T₁ and NOE values measured in the glycine-labeled fibrils show that rapid axial motion (R₁ ~ 10⁷s^?1) persists in the fibrillar state. In the collagen fibril the full width of the glycyl carbonyl powder pattern is 103 p.p.m. This value is substantially smaller than the rigid lattice value, 144 p.p.m., which provides further evidence for motion in the fibril. The observed powder pattern is axially asymmetric, which shows that certain azimuthal orientations are energetically preferred in the fibril. Taken together, the n.m.r. data provide strong evidence that rapid reorientation of the helix backbone occurs in the fibrils. This result shows that formation of a fibrillar structure does not require the existence of a unique set of intermolecular interactions at the helical surfaces.     

Interaction of the dye Congo red with fibrils of lysozyme,beta2-microglobulin,and transthyretin

Interaction of the dye Congo red (CR) with fibrils of three model proteins—hen egg lysozyme, recombinant human beta 2-microglobulin (b2M), and recombinant human transthyretin (TTR)—has been investigated using spectrophotometry. Considerable amounts of impurities were detected in the commercial dye formulation. A procedure of dye purification has been developed. The molar extinction coefficient of the dye at 490 nm (ε₄₉₀) has been measured; the coefficient was 3.3 × 10⁴ M^–1 cm^–1 at pH > 6.0. The formation of a complex between CR and the fibrils was accompanied by a change in the absorption spectrum of the dye in the visible wavelength range. Titration of fibril solutions with excessive amounts of dye showed that the number of CR molecules bound to a protein monomer within the lysozyme fibrils was close to five, whereas the respective ratio for b2M was close to four, and the ratio for TTR fibrils was close to four molecules per protein subunit.     

Magnetic resonance microscopy of collagen mineralization

A model mineralizing system was subjected to magnetic resonance microscopy to investigate how water proton transverse (T₂) relaxation times and magnetization transfer ratios can be applied to monitor collagen mineralization. In our model system, a collagen sponge was mineralized with polymer-stabilized amorphous calcium carbonate. The lower hydration and water proton T₂ values of collagen sponges during the initial mineralization phase were attributed to the replacement of the water within the collagen fibrils by amorphous calcium carbonate. The significant reduction in T₂ values by day 6 (p < 0.001) was attributed to the appearance of mineral crystallites, which were also detected by x-ray diffraction and scanning electron microscopy. In the second phase, between days 6 and 13, magnetic resonance microscopy properties appear to plateau as amorphous calcium carbonate droplets began to coalesce within the intrafibrillar space of collagen. In the third phase, after day 15, the amorphous mineral phase crystallized, resulting in a reduction in the absolute intensity of the collagen diffraction pattern. We speculate that magnetization transfer ratio values for collagen sponges, with similar collagen contents, increased from 0.25 ± 0.02 for control strips to a maximum value of 0.31 ± 0.04 at day 15 (p = 0.03) because mineral crystals greatly reduce the mobility of the collagen fibrils.     

Molecular structure and functional morphology of echinoderm collagen fibrils

The collagenous tissues of echinoderms, which have the unique capacity to rapidly and reversibly alter their mechanical properties, resemble the collagenous tissues of other phyla in consisting of collagen fibrils in a nonfibrillar matrix. Knowledge of the composition and structure of their collagen fibrils and interfibrillar matrix is thus important for an understanding of the physiology of these tissues. In this report it is shown that the collagen molecules from the fibrils of the spine ligament of a seaurchin and the deep dermis of a sea-cucumber are the same length as those from vertebrate fibrils and that they assemble into fibrils with the same repeat period and gap/overlap ratio as do those of vertebrate fibrils. The distributions of charged residues in echinoderm and vertebrate molecules are somewhat different, giving rise to segment-long-spacing crystallites and fibrils with different banding patterns. Compared to the vertebrate pattern, the banding pattern of echinoderm fibrils is characterized by greatly increased stain intensity in the c₃ band and greatly reduced stain intensity in the a₃ and b₂ bands. The fibrils are spindle-shaped, possessing no constant-diameter region throughout their length. The shape of the fibrils is mechanically advantageous for their reinforcing role in a discontinuous fiber-composite material.     

Investigation of labeled amino acid side-chain motion in collagen using 13C nuclear magnetic resonance

¹³C¹H double magnetic resonance was used to study the interactions and mobility of certain amino acid side-chains of collagen. Samples of collagen, labeled with [3-¹³C]alanine (a small hydrophobic amino acid), [methyl-¹³C]-methionine (a large hydrophobic), [6-¹³C]lysine (positively charged at physiological pH), and [5-¹³C]glutamic acid (negatively charged), were prepared via chick calvaria culture. ¹³C linewidths, lineshapes, NOE² values, and T₁ values were measured for each sample as fibrils and as native (helical) material in solution.The measured T₁ and NOE values for [3-¹³C]alanine-labeled collagen in solution, in conjunction with an ellipsoid model for collagen, indicate that the methyl rotation rate is 2 × 10¹⁰ s^?1 and that the overall rate of diffusion about the long axis is 4× 10⁶ s^?1. These values agree with values for model compounds which undergo internal methyl rotation (Lyerla & Horikawa, 1976) and with previous n.m.r. measurements of the rate of rotational diffusion of backbone ([1-¹³C]- and [2-¹³C]glycine)-labeled collagen (Jelinski & Torchia, 1979). In addition, the n.m.r. data indicate that the terminal carbons of lysine, methionine and glutamic acid in labeled collagen (both in solution and as fibrils) are characterized by reorientation rates of approximately 10⁹ to 10¹⁰ s^?1.Taken together, the n.m.r. data provide strong evidence that the contact regions between the helices in collagen fibrils are fluid and that there is not a unique set of interactions between amino acid side-chains. In this respect, these n.m.r. results support current concepts of globular protein structure which suggest that a variety of conformations, in dynamic equilibrium, are responsible for the structure and function of proteins.     

Ultraviolet circular dichroism of polyproline and oriented collagen

The ultraviolet absorption, linear dichroism, circular dichroism, and oriented circular dichroism of collagen are reported and the spectra are resolved into a self-consistent set of bands in accord with exciton theory. The parallel band at 200 nm has 40% of the π → π* intensity; the perpendicular band is placed at 189 nm yielding a splitting of 2700 cm^?1. The circular dichroism is resolved into two Gaussians at λ_∥ and λ_τ (rotational strengths +14 × 10^?40 and ?32 × 10^?40 esu². cm²) plus a large non-Gaussian (“helix”) band with ampplitude ?25,000° at 201 nm. These data appear to be in reasonably good accord with recent calculations. Measurements of the absorption, linear dichroism and circular dichroism of polyproline I and II are also reported and are resolved into their component bands. Polyproline I is in good accord with exciton theory, whereas polyproline II remains unsatisfactory.     

Rare earth activated yttrium aluminate phosphors with modulated luminescence

Yttrium aluminate (Y₃A₅O₁₂) was doped with different rare earth ions (i.e. Gd³⁺, Ce³⁺, Eu³⁺ and/or Tb³⁺) in order to obtain phosphors (YAG:RE) with general formula,Y_3‐x‐aGd_xRE_aAl₅O₁₂ (x = 0; 1.485; 2.97 and a = 0.03). The synthesis of the phosphor samples was done using the simultaneous addition of reagents technique. This study reveals new aspects regarding the influence of different activator ions on the morpho‐structural and luminescent characteristics of garnet type phosphor. All YAG:RE phosphors are well crystallized powders containing a cubic‐Y₃Al₅O₁₂ phase as major component along with monoclinic‐Y₄Al₂O₉ and orthorhombic‐YAlO₃ phases as the impurity. The crystallites dimensions of YAG:RE phosphors vary between 38 nm and 88 nm, while the unit cell slowly increase as the ionic radius of the activator increases. Under UV excitation, YAG:Ce exhibits yellow emission due to electron transition in Ce³⁺ from the 5d level to the ground state levels (²F_5/2, ²F_7/2). The emission intensity of Ce³⁺ is enhanced in the presence of the Tb³⁺ ions and is decreased in the presence of Eu³⁺ ions due to some radiative or non‐radiative processes that take place between activator ions. By varying the rare earth ions, the emission colour can be modulated from green to white and red. Copyright © 2015 John Wiley & Sons, Ltd.     

Capturing a Reactive State of Amyloid Aggregates: NMR-BASED CHARACTERIZATION OF COPPER-BOUND ALZHEIMER DISEASE AMYLOID β-FIBRILS IN A REDOX CYCLE*

The interaction of redox-active copper ions with misfolded amyloid β (Aβ) is linked to production of reactive oxygen species (ROS), which has been associated with oxidative stress and neuronal damages in Alzheimer disease. Despite intensive studies, it is still not conclusive how the interaction of Cu⁺/Cu²⁺ with Aβ aggregates leads to ROS production even at the in vitro level. In this study, we examined the interaction between Cu⁺/Cu²⁺ and Aβ fibrils by solid-state NMR (SSNMR) and other spectroscopic methods. Our photometric studies confirmed the production of ∼60 μm hydrogen peroxide (H₂O₂) from a solution of 20 μm Cu²⁺ ions in complex with Aβ(1–40) in fibrils ([Cu²⁺]/[Aβ] = 0.4) within 2 h of incubation after addition of biological reducing agent ascorbate at the physiological concentration (∼1 mm). Furthermore, SSNMR ¹H T₁ measurements demonstrated that during ROS production the conversion of paramagnetic Cu²⁺ into diamagnetic Cu⁺ occurs while the reactive Cu⁺ ions remain bound to the amyloid fibrils. The results also suggest that O₂ is required for rapid recycling of Cu⁺ bound to Aβ back to Cu²⁺, which allows for continuous production of H₂O₂. Both ¹³C and ¹⁵N SSNMR results show that Cu⁺ coordinates to Aβ(1–40) fibrils primarily through the side chain N_δ of both His-13 and His-14, suggesting major rearrangements from the Cu²⁺ coordination via N_ϵ in the redox cycle. ¹³C SSNMR chemical shift analysis suggests that the overall Aβ conformations are largely unaffected by Cu⁺ binding. These results present crucial site-specific evidence of how the full-length Aβ in amyloid fibrils offers catalytic Cu⁺ centers.     

Luminescence investigation of a cerium‐doped yttrium vanadate phosphor

Cerium (Ce³⁺)‐doped (1, 3, and 7 mol%) yttrium vanadate phosphors were prepared using a co‐precipitation technique. The structural and optical properties of the synthesized samples were studied using X‐ray diffraction (XRD), Fourier transform infrared spectroscopy, scanning electron microscopy (SEM), high‐resolution transmission electron microscopy (HR‐TEM), optical absorption, and photoluminescence (PL) spectroscopy techniques. The tetragonal structure and the formation of the nanosized crystallites in the YVO₄:Ce phosphor were confirmed using XRD analysis. HR‐TEM morphology showed rod‐like nanoparticles of different sizes. Optical absorption spectra demonstrated strong absorption bands at 268 and 276 nm. PL spectra showed strong peaks at 546, 574, and 691 nm following excitation at 300 nm. The calculated CIE chromaticity coordinates demonstrated that YVO₄:Ce could be used as a novel phosphor for the development of light‐emitting diode lamps.     

The molecular structure and solution conformation of an acidic heteropolysaccharide from Auricularia auricula-judae

A water soluble acidic heteropolysaccharide named WAF was isolated from Auricularia auricula‐judae by extracting with 0.9% NaCl solution. By using gas chromatography, gas chromatography‐mass spectrometry, and NMR, its chemical structure was determined to be composed of a backbone of α‐(1→3)‐linked D ‐mannopyranose residues with pendant side groups of β‐D ‐xylose, β‐D ‐glucose, or β‐D ‐glucuronic acid at position O6 or O2. Six fractions prepared from WAF with a weight‐average molecular mass (M_w) between 5.9 × 10⁴ and 64.7 × 10⁴ g/mol were characterized with laser light scattering and viscometry in 0.1M NaCl at 25°C. The dependence of intrinsic viscosity ([η]) and radius of gyration (R_g) on M_w for this polysaccharide were found to be [η] = 1.79 × 10^?3M_w^0.96 cm³ g^?1 and R_g = 6.99 × 10^?2 M_w^0.54 nm. The molar mass per unit contour length (M_L) and the persistence length (L_p) were estimated to be 1124 nm^?1 and 11 nm, respectively. The WAF exhibited a semirigid character typical of linear polysaccharides. Molecular modeling was then used to predict the ordered and disordered states of WAF; the simulated M_L and L_p were however much smaller than the experimental values. Taken altogether, the results suggested that WAF formed a duplex in solution. © 2010 Wiley Periodicals, Inc. Biopolymers 95: 217–227, 2011.     

Structural alteration of glycosaminoglycan side chains and spatial disorganization of collagen networks in the skin of patients with mcEDS-CHST14

Musculocontractural Ehlers-Danlos syndrome (mcEDS) due to CHST14/D4ST1 deficiency (mcEDS-CHST14) is a recently delineated type of EDS caused by biallelic loss-of-function mutations in CHST14, which results in the depletion of dermatan sulfate (DS). Clinical characteristics of mcEDS-CHST14 consist of multiple malformations and progressive fragility-related manifestations, including skin hyperextensibility and fragility. Skin fragility is suspected to result from the impaired assembly of collagen fibrils caused by alteration of the glycosaminoglycan (GAG) chain of decorin-proteoglycan (PG) from DS to chondroitin sulfate (CS). This systematic investigation of the skin pathology of patients with mcEDS-CHST14 comprised both immunostaining of decorin and transmission electron microscopy-based cupromeronic blue staining to visualize GAG chains. Collagen fibrils were dispersed in the affected papillary to reticular dermis; in contrast, they were regularly and tightly assembled in controls. Moreover, the fibrils exhibited a perpendicular arrangement to the affected epidermis, whereas fibrils were parallel to control epidermis. Affected GAG chains were linear, stretching from the outer surface of collagen fibrils to adjacent fibrils; in contrast, those of controls were curved, maintaining close contact with attached collagen fibrils. This is the first observation of compositional alteration, from DS to CS, of GAG side chains, which caused structural alteration of GAG side chains and resulted in spatial disorganization of collagen networks; this presumably disrupted the ring-mesh structure of GAG side chains surrounding collagen fibrils. McEDS-CHST14 provides a critical example of the importance of DS in GAG side chains of decorin-PG during assembly of collagen fibrils in maintenance of connective tissues.     

The influence of H2 partial pressure on biogenic palladium nanoparticle production assessed by single-cell ICP-mass spectrometry

The production of biogenic palladium nanoparticles (bio-Pd NPs) is widely studied due to their high catalytic activity, which depends on the size of nanoparticles (NPs). Smaller NPs (here defined as <100 nm) are more efficient due to their higher surface/volume ratio. In this work, inductively coupled plasma-mass spectrometry (ICP-MS), flow cytometry (FCM) and transmission electron microscopy (TEM) were combined to obtain insight into the formation of these bio-Pd NPs. The precipitation of bio-Pd NPs was evaluated on a cell-per-cell basis using single-cell ICP-MS (SC-ICP-MS) combined with TEM images to assess how homogenously the particles were distributed over the cells. The results provided by SC-ICP-MS were consistent with those provided by “bulk” ICP-MS analysis and FCM. It was observed that heterogeneity in the distribution of palladium over an entire cell population is strongly dependent on the Pd²⁺ concentration, biomass and partial H₂ pressure. The latter three parameters affected the particle size, ranging from 15.6 to 560 nm, and exerted a significant impact on the production of the bio-Pd NPs. The TEM combined with SC-ICP-MS revealed that the mass distribution for bacteria with high Pd content (144 fg Pd cell⁻¹) indicated the presence of a large number of very small NPs (D50 = 15.6 nm). These results were obtained at high cell density (1 × 10⁵ ± 3 × 10⁴ cells μl⁻¹) and H₂ partial pressure (180 ml H₂). In contrast, very large particles (D50 = 560 nm) were observed at low cell density (3 × 10⁴ ± 10 × 10² cells μl⁻¹) and H₂ partial pressure (10–100 ml H₂). The influence of the H₂ partial pressure on the nanoparticle size and the possibility of size-tuned nanoparticles are presented.     

The luminescent properties and crystal structure of Sr(1.5‐x)‐(1.5y)Mg0.5SiO4:xEu2+,yCe3+ blue phosphor synthesized by co‐precipitation method

In order to improve the luminescent performance of silicate blue phosphors, Sr_{(1.5‐x)‐(1.5y)}Mg_0.5SiO₄:xEu²⁺,yCe³⁺ phosphors were synthesized using one‐step calcination of a precursor prepared by chemical co‐precipitation. The crystal structure and luminescent properties of the phosphors were analyzed using X‐ray diffraction and fluorescence spectrophotometry, respectively. Because the activated ions (Eu²⁺) can occupy two different types of sites (Sr₁ and Sr₂), the emission spectrum of Eu²⁺ excited at 350 nm contains two single bands (EM₁ and EM₂) in the wavelength range 400–550 nm, centered at 463 nm, and the emission intensity first increases and then decreases with increasing concentrations of Eu²⁺ ions. Co‐doping of Ce³⁺ ions can greatly enhance the emission intensity of Eu²⁺ by transferring its excitation energy to Eu²⁺. Because of concentration quenching, a higher substitution concentration of Ce³⁺ can lead to a decrease in the intensity. Meanwhile, the quantum efficiency of the phosphor is improved after doping with Ce³⁺, and a blue shift phenomenon is observed in the CIE chromaticity diagram. The results indicate that Sr_{(1.5‐x)‐(1.5y)}Mg_0.5SiO₄:xEu²⁺,yCe³⁺ can be used as a potential new blue phosphor for white light‐emitting diodes.     

The alpha-helix,an overlooked molecular motor

Summary. At first sight the alpha-helix appears as a rigid scaffold braced by hydrogen bonds nearly parallel to the helix axis. Looked at more closely it turned out to be highly dynamic and able to transform chemical into mechanical energy. The hydrogen bonds are fairly weak and compliant bonds. Their length, usually between 0.267 and 0.291 nm (mean value, 0.28 nm), depends on the interaction of the side chains. The most important strong interaction is the electrostatic repelling force between equally charged side chains (Glu⁻, Asp⁻, Lys⁺, Arg⁺), well known by experiments with polyamino acids. In proteins with different amino acids, repelling forces between charged side chains work in the axial direction and stretch the hydrogen bonds. Extreme shortening of the hydrogen bonds occurs when ions, e.g., Ca²⁺, H⁺, or PO₃⁻, are added and discharge side chains. This means a cooperative pitch decrease of the alpha-helix (pitch range between 0.52 and more than 0.55 nm; mean value, 0.54 nm). This pitch change is absolutely connected by steric reasons with torque generation and torsional rotations, as demonstrated by molecular and tubular alpha-helix models. Thus, charged alpha-helices are molecular motors propelled by the electrostatic energy of added ions. The motor effect is most striking with highly charged alpha-helical coiled coils, e.g., tropomyosin, myosin, and alpha-actinin that can rotate actin filaments by winding and unwinding. For example, the shortening of muscle depends on the sliding (drilling) motion of the Ca²⁺-activated helical actin filaments into the cross-bridges of the A-band. Here, models are presented for the in vitro sliding of actin filaments and for cytoplasmic streaming by winding and unwinding of myosin chains, and for membrane proteins that contain nonhelical domains between membrane-penetrating alpha-helices. They may transport molecules by the described torsional rotations if they perform supercoiling. Winding and supercoiling can lead to displacement of bound ions and to a feed-back-regulated oscillation between two different coiling stages E₁ and E₂ that explain “eversion”. The models need the torque for 1–2 rotations. They explain active and passive transports, the driving-effects of ion gradients, ATP hydrolysis by unwinding, ATP synthesis by winding up of the supercoils, etc. Correspondence and reprints: Linzerstrasse 72, 4810 Gmunden, Austria.     

Characterization of laser produced plasma using laser induced breakdown spectroscopy

The plasma parameter studies of the Nd:YAG (neodymium-doped yttrium aluminum garnet, Nd:Y₃Al₁₅O₁₂) crystal by using the fundamental (1064 nm) and second (532 nm) harmonics of Nd:YAG laser are reported. The electron temperature (T _e ) and electron number density (N _e) were determined using the Boltzmann plot method and the Stark-broadened line profile, respectively. An increase in the plasma parameters have been observed with an increase in the laser irradiance for both laser modes. The electron temperatures were calculated in the range of 0.53–0.66 eV for 1064 nm and 0.47–0.60 eV for 532 nm, and the electron number densities were determined in the range of 7.43 × 10¹⁵–3.27 × 10¹⁶ cm^?3 for 1064 nm and 1.35 × 10¹⁶–3.97 × 10¹⁶ cm^?3 for 532 nm in the studied irradiance range of 1.19–12.5 GW/cm². However, the spatial evolution of the plasma parameters investigated up to 2.75 mm away from the target surface at a fixed laser irradiance of 6.51 GW/cm2 showed a decreasing trend. In addition, the estimated values of the inverse bremsstrahlung (IB) absorption coefficients at both laser wavelengths showed that the IB process is dominant for the 1064-nm laser.     

Characterisation of acidic sites of Pseudomonas biomass capable of binding protons and cadmium and removal of cadmium via biosorption

Summary The ability of Pseudomonas aeruginosa to accumulate Cd(II) ions from wastewater industries was experimentally investigated and mathematically modelled. From the potentiometric titration and non-ideal competitive analysis (NICA) model, it was found that the biomass contains three acidic sites. The values of proton binding (pK _i =1.66±3.26×10⁻³, 1.92±1.63×10⁻⁴ and 2.16±3.79×10⁻⁴) and binding constant of cadmium metal ions (pK _M1=1.99±2.45×10⁻³ and pK _M2=1.67±4.08×10⁻³) on the whole surface of biomass showed that protonated functional groups and biosorption of Cd(II) ions could be attributed to a monodentate binding to one acidic site, mainly the carboxylic group. From the isothermal sorption experimental data and Langmuir model, it was also found that the value of Langmuir equilibrium (pK _f) constant is 2.04±2.1×10⁻⁵ suggesting that the carboxyl group is the main active binding site. In addition, results showed that the maximum cadmium capacity (q _max) and affinity of biomass towards cadmium metal ions (b) at pH 5.1 and 20 min were 96.5±0.06 mg/g and 3.40×10⁻³± 2.10×10⁻³, respectively. Finally, interfering metal ions such as Pb(II), Cu(II), Cr(III), Zn(II), Fe(II), Mn(II), Ca(II) and Mg(II) inhibited Cd(II) uptake. Comparing the biosorption of Cd(II) by various Pseudomonas isolates from contaminated environment samples (soil and sewage treatment plant) showed that maximum capacities and equilibrium times were different, indicating that there was a discrepancy in the chemical composition between biomasses of different strains.     

Luminescence in Sr4Al14O25:Ce3+ aluminate phosphor

Cerium‐doped Sr₄Al₁₄O₂₅ phosphor is prepared using a single‐step combustion synthesis and its X‐ray diffraction (XRD), scanning electron microscopy (SEM), photoluminescence (PL) and thermoluminescence (TL) properties are characterized. XRD reveals the formation of the desired phase in the prepared sample. SEM micrographs of the prepared Sr₄Al₁₄O₂₅ phosphor show that the particle size is 10 µm. The prepared Sr₄Al₁₄O₂₅, along with Sr₄Al₁₄O₂₅:Ce_x (x = 0.5–5 mol%) shows a PL emission peak at 314 nm under UV excitation of 262 nm wavelength due to 5d → 4f transition. The phosphor is suitable for higher concentrations of Ce ions. The TL glow peak reveals three clearly visible distinct peaks at temperatures around 130, 231 and 336ºC. The three peaks are separated by deconvolution and kinetic parameters calculated using Chen's peak shape method. The calculation shows that the reaction follows second‐order kinetics with activation energy (E) values of 0.52, 0.81 and 1.12 eV, and frequency factor (s) values of 5.58 × 10⁵, 4.53 × 10⁷ and 4.57 × 10⁸ s^‐1 for the three individual peaks. Copyright © 2014 John Wiley & Sons, Ltd.     

Orange-red luminescence of samarium-doped bismuth–germanium–borate glass for light-emitting devices

Samarium (Sm³⁺)-doped glass has sparked a rising interest in demonstrating a noticeable emission in the range of 400–700, which is advantageous in solid-state lasers in the visible region, colour displays, undersea communication, and optical memory devices. This study reports the fabrication of Sm³⁺-doped bismuth–germanium–borate glasses were established using a standard melt-quenching technique and inspection by absorption, steady-state luminescence, and transient studies. The typical peaks of Sm³⁺ ions were detected in the visible range under 403 nm excitation. A strong emission band was detected at 599 nm that resembles the ⁴G_5/2→⁶H_7/2 transition of Sm³⁺ ions for BGBiNYSm_0.5 glass. Furthermore, a reddish-orange (coral) luminescence at 646 nm that resembles the ⁴G_5/2→⁶H_9/2 transition was also perceived. The stimulated emission cross-section of ⁴G_5/2 level for BGBiNYSm_0.5 glass was 0.39 × 10⁻²² cm². Lifetime of the ⁴G_5/2 level was enhanced for the BGBiNYSm_0.5 glass and decreased with an increase in active ion concentrations. The lifetime quenching of ions at the metastable state was because of energy transfer among Sm³⁺ ions by cross-relaxation channels. Commission Internationale de l'Éclairage (CIE) coordinates were evaluated from the emission spectra. Moreover, all the findings recommend these glass as light-emitting materials in the coral region at 599 nm for solid-state lighting applications.