Ultrasonic absorption studies of poly-benzyl-L-aspartate in mixed solvents, in relation to the helix-cell transition

Ultrasonic absorption measurements were carried out on solutions of polybenzyl-L -aspartate (PBLA) in chloroform–dichloroacetic acid (DCA) and in 1,2-dichloroethane (DCE)–DCA, in the range 3.9–155 MHZ . The helix–coil transition of PBLA produces an increase of absorption which is larger in CHCl₃–DCA than in DCE–DCA solutions. The influence of the solvent on the excess ultrasonic absorption suggests that solvation processes may be involved in these changes of absorption. The plots of the absorption vs. the volume fraction of DCA do not show any absorption maximum. This indicates that the ultrasonic absorption is not sensitive to the helix–coil equilibrium of PBLA in the frequency range investigated. A maximum value of 10⁹ S ^?1 has been obtained for the rate constant of growth of a helix region.     

Intensities and other spectral parameters of infrared amide bands of polypeptides in the alpha-helical form

Intensities and other spectral parameters of infrared amide I and II bands of α-helical polypeptides in solutions have been determined for poly(γ-benzylglutamate), poly(γ-ethylglutamate), and polymethionine in chloroform, polylysine, poly(glutamic acid), and fibrillar protein tropomyosin from rabbit muscles in heavy water. The majority of spectral parameters are characteristic. The half-width of the amide I band was found to vary in the range of 15–40 cm^?1 for different polypeptides in the different solutions. The correlation between this parameter of the amide I band and the stability of the α-helix was estimated. A new weak band near 1537 cm^?1 of unknown origin was observed for the hydrogen form of polypeptides in the α-helical state.     

Health risk assessment of heavy metals via dietary intake of wheat in Golestan Province,Iran

Concentration of five heavy metals including lead (Pb), cadmium (Cd), copper (Cu), iron (Fe), and zinc (Zn) in wheat collected from silages of Golestan Province, Iran, was determined using atomic absorption spectroscopy. Dry ashing method was applied for precise determination of the five heavy metal contents. The concentrations of heavy metals were recorded as the following: Pb (0.013–0.14), Cd (0.008–0.031) by graphite furnace method and Cu (0.48–6.2), Fe (58.50–406.9), and Zn (3.41–32.75) by flame method, all in mg.kg^?1. The mean concentration of all the aforementioned heavy metals was (0.057 ± 0.003), (0.016 ± 0.005), (2.7 ± 0.17), (111.2 ± 21), and (5.7 ± 0.22) mg.kg^?1, respectively. The level of heavy metals decreased in the order of Fe>Zn>Cu>Pb > Cd. Highest amount was related to Fe and the lowest amount to Cd. Concentrations of heavy metals in all the wheat samples were below the permissible limits set by the Food and Agriculture Organization/World Health Organization and Iranian National Standard Organization and did not pose any threat to the health of consumers.     

Phytoremediation of Wastewater with Limnocharis Flava,Thalia Geniculata and Typha Latifolia in Constructed Wetlands

Phytoremediation is thought to be the most sustainable wastewater treatment option for developing countries. However, its application is often limited by unavailability of suitable candidate species. In the present study, the potentials of Limnocharis flava, Thalia geniculata and Typha latifolia for remediation of heavy metal contaminated wastewater with a constructed wetland system were evaluated. The wetland consisted of three treatment lines each planted with sufficient and equal number of a species. Duplicate plant and water samples were collected bi-monthly and analyzed for Fe, Cu, Zn, Pb, and Hg using the atomic absorption spectrophotometer over a six month period. Bioaccumulation rates generally increased over time and varied among plants for these metals, with Fe (456–1549 mg kg¹ roots; 20–183 mg kg^?1 shoot) being the most sequestered and Pb (1.2–7.6 mg kg^?1 roots; 1.55–3.95 mg kg^?1 shoot) the least. Translocation factors differed among the species but generally remained stable over time. L. flava showed potential for hyperaccumulating Hg. Removal efficiencies varied for the studied metals (～ 20–77 %) and were generally related to metal uptake by the plants. These results demonstrate the suitability of the species for phytoremediation, and the usefulness of the technique as an option for improving irrigation water quality in Ghana.

Supplemental materials are available for this article. Go to the publisher's online edition of International Journal of Phytoremediation to view the supplemental file.     

Fluctuation of an -helix structure. Difference between the central and terminal portions

Four samples of poly-l-glutamic acid with different degrees of polymerization, 30, 60, 73 and 96, have been prepared. By optical rotatory dispersion and infrared absorption measurements, the random-coil and α-helix contents were estimated in heavy water plus dioxane solutions with various pD values. In the same solvent, the kinetics of hydrogen-deuterium exchange in each sample was followed by an infrared absorption measurement. It was found that the rate of exchange depends appreciably on the degree of polymerization; the rate is lower for the polymers with higher degrees of polymerization, so that the rate constant is considered to become lower on going from the terminals towards the inner portions of the polymer chain. An analysis of this lowering has been made by taking the random-coil content estimated by the optical rotatory dispersion measurement into account. It is suggested that the rate constant of the helix-coil fluctuation in the central portions of the chain is as low as 4 × 10⁻⁶ sec⁻¹.     

A novel fluorescent sensor based on electrosynthesized benzene sulfonic acid‐doped polypyrrole for determination of Pb(II) and Cu(II)

To develop conducting organic polymers (COPs) as luminescent sensors for determination of toxic heavy metals, a new benzene sulfonic acid‐doped polypyrrole (PPy‐BSA) thin film was electrochemically prepared by cyclic voltammetry (CV) on flexible indium tin oxide (ITO) electrode in aqueous solution. PPy‐BSA film was characterized by FTIR spectrometry, X‐ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). The optical properties of PPy‐BSA were investigated by ultraviolet (UV)‐visible absorption and fluorescence spectrometry in dimethylsulfoxide (DMSO) diluted solutions. PPy‐BSA fluorescence spectra were strongly quenched upon increasing copper(II) ion (Cu²⁺) and lead(II) ion (Pb²⁺) concentrations in aqueous medium, and linear Stern–Volmer relationships were obtained, which indicated the existence of a main dynamic fluorescence quenching mechanism. BSA‐PPy sensor showed a high sensitivity for detection of both metallic ions, Cu²⁺ and Pb²⁺, with very low limit of detection values of 3.1 and 18.0 nM, respectively. The proposed quenching‐fluorimetric sensor might be applied to the determination of traces of toxic heavy metallic ions in water samples.     

Spectroscopic properties of protochlorophyll forms in Triton X-100 detergent micelles

Protochlorophyll (PChl) forms were performed in Triton X-100 detergent micelles. The concentration of Triton X-100 was 7·10^?4 M (above the critical micellar concentration); the concentration of PChl varied between 1.6·10^?5 and 1.8·10^?4 M. Absorption, fluorescence and circular dichroism (CD) spectra were registered. The absorption spectra were resolved into Gaussian components by computer analysis. PChl forms with absorption bands at 632–634, 638, 652–654, 663–664, 668 and 676 nm and with fluorescence emission bands at 634–636, 640–644, 652–655, 677–678, 686 and 694–696 nm were observed in micellar solutions of different PChl concentrations. The CD spectra showed a strong dependence on the concentration of PChl: positive CD signals or positive Cotton effects were observed in the vicinity of 650 nm. The intensity of these signals increased in parallel with increasing concentration of PChl. No CD signals were found in the region of the longer wavelength absorption bands. These data show that the PChl exists in many different forms in this system, and the spectroscopic properties of these forms are determined by different molecular interactions viz., interactions of PChl with Triton X-100 or water molecules and/or by the aggregation of PChl.     

Health Risk Assessment of Exposure to Metals in a Nigerian Water Supply

This article reports the health risk associated with chronic intake of metals in the municipal water supplies of Eleyele and neighboring towns in the Ibadan metropolitan area of Nigeria. A total of 42 composite samples, consisting of treated water from the water treatment facility and residential areas receiving personal-use water (i.e., tap water) directly from the facility, as well as raw water from the treatment facility's water supply dam were sampled twice every month for 7 months. Concentrations of the metals were determined by atomic absorption spectrophotometry. Among the metals studied, Cd, Co, Cr, and Pb were detected at concentrations higher than maximum regulatory limits. Cd, Co, Cr, and Pb concentrations in treated water at the treatment facility ranged from 0.08–0.10, 0.14–0.16, 0.04–0.22 and 0.07–0.36 mg L^?1, respectively, while personal-use water ranged from 0.08–0.11, 0.15–0.29, 0.02–0.29, and 0.12–0.65 mg L¹, respectively. Likewise, concentrations of the metals at the dam ranged from 0.06–0.08, 0.17–0.20, 0.13–0.37, and 0.03–0.15 mg L¹, respectively. It is estimated that exposure to the metals in the water supply results in oncological and non-oncological systemic health risks higher than is generally acceptable for drinking water.     

A highly selective fluorescence and absorption sensor for rapid recognition and detection of Cu2+ ions in aqueous solution and film

A fluorescence and absorption chemosensor (SAAT) based on 5-(hydroxymethyl)-salicylaldehyde (SA) and o-aminothiophenol (AT) was designed and synthesized. SAAT in DMSO–HEPES (20.0 mM, v/v, 1:99, pH = 7.0) solution shows a highly selective and sensitive absorption and an ‘on–off’ fluorescence response to Cu²⁺ ions in aqueous solutions over all other competitive metal ions including Na⁺, Ag⁺, Ba²⁺, Ca²⁺, Cd²⁺, Mg²⁺, Zn²⁺, Cr³⁺, Al³⁺, Hg²⁺, K⁺, Mn²⁺, Ni²⁺, Sr²⁺, Tb³⁺ and Co²⁺. SAAT exhibits ratiometric absorption sensing ability for Cu²⁺ ions. Importantly, SAAT also can sense Cu²⁺ ions using fluorescence quenching, the fluorescence intensity of SAAT showed a good linear relationship with Cu²⁺ concentration, and the detection limit of Cu²⁺ was 0.34 μM. The results of Job's plot, Benesi–Hildebrand plot, mass spectra, and density functional theory calculations confirmed that the selective absorption and fluorescence response were attributed to the formation of a 1:1 complex between SAAT and Cu²⁺. SAAT in test film could identify Cu²⁺ in water samples using the intuitive fluorescence colour change under a UV lamp. SAAT has great application value as a selective and sensitive chemosensor to discriminate and detect Cu²⁺ ions.     

Dielectric studies on water in solutions of purified lecithin vesicles

The complex permittivity of sonicated aqueous solutions of purified dimyristoylphosphatidylcholine has been measured as a function of frequency between 3 kHz and 40 GHz. The dielectric spectrum of the samples shows two dispersion/absorption regions, one centered at about 80 MHz the other at about 20.GHz (30°C). Otherwise than in previous studies no additional dispersion/absorption process has been found at frequencies below 10 MHz.The complex dielectric spectrum of the samples is discussed with respect to the dynamical state of solvent water in solutions of single-bilayer vesicles. The main relaxation time of the solvent water, τ₁ ((2πτ₁)^?1 ≈ 20 GHz), is smaller than that of pure water, τ_W, at the same temperature. This effect results from the action of internal depolarizing fields which obviously overcompensate and enhancement of τ₁ due to specific solute/solvent interactions (hydration) as had been previously found with micellar solutions of lysolecithins.It cannot be excluded, that some solvent water shows unusual dynamical behaviour. If there exists a substantial amount of such motionally perturbed water, however, it must be characterized by a relaxation time close to that of the phosphorylcholine zwitterions, τ₂ ((2πτ₂)^?1 ≈ 80 MHz).     

Natural chelators in sea water: Detoxification of Zn2+ by brown algal polyphenols

We have examined growth responses of several species of marine phytoplankton, cultured with and without heavy metal stress, to supplements of polymeric polyphenols from the brown algae Ascophyllum nodosum (L.) Le Jol. and Fucus vesiculosus L. In the absence of additional heavy metals. supplements of up to 4000 μg. 1 of polyphenols had a small effect on initial growth rates for three of these microalgae and had no effect on maximum cell densities for four species. One very common, heavy metal-sensitive diatom, Skeletonema costatum (Grev.) Cl., showed significantly increasing maximum cell density in the cultures, with increasing addition of polyphenols to the medium. The toxicity of Zn²⁺ (0.5–2.0 mg·1 ¹) to cultures of the diatom Phaeodactylum tricornutum Bohlin was relieved by supplements (100–200 μg·1 ¹) of the brown algal polyphenols. Exudation of these polyphenols from brown seaweeds may contribute to the natural chelating capacity of inshore sea water.     

Physicochemical and elemental contamination assessment in groundwater samples of Khairpur Mir's,Pakistan

Drinking water contaminated with arsenic poses serious threat to the human health. The present study was aimed for quality assessment of the groundwater of Khairpur Mir's in respect with arsenic and other elemental contamination like Fe, Cu, Co, and Ni. The presence of the trace elements in groundwater from different sources in the study area was measured by using atomic absorption spectroscopy. For arsenic analysis hydride generation technique (MHS-15) was used with detection limit of 0.02 µg l^?1. Elevated level of arsenic was observed in most of the samples as compared to recommended value of World Health Organization (WHO) guidelines (10 µg l^?1). However, levels of Fe, Cu, Co, and Ni in hand pump (HP) water samples was found in the range of 4–1610 µg l^?1, 0–556 µg l^?1, 0–230 µg l^?1, and 0–700 µg l^?1, respectively. Whereas in tube well (TW) water samples the observed values are 5–1620 µg l^?1, 0–50 µg l^?1, 4–110 µg l^?1, and 0–360 µg l^?1 for Fe, Cu, Co, and Ni, respectively. Significant difference was observed between TW and HP water samples. It was concluded that the level of arsenic found was very high up to 13 fold more than the WHO recommended limit in study area. While the levels of other elements was noted within the safe limit.     

Acoustical properties of aqueous solutions of oxygenated and deoxygenated hemoglobin

The acoustical relaxation spectrum of aqueous solutions of oxygenated and deoxygenated hemoglobin solutions was investigated in the frequency range 0.5–1000 MHz. The abrupt high frequency cut off of the broad absorption spectrum is consistent with a heavily weighted, shortest relaxation time of 2 × 10^?9 sec. Both the high-frequency cut-off and high frequency residual absorption appear to be slightly different for oxygenated and deoxygenated hemoglobin solution.     

Paradoxical influence of combined effect of Semax and ammonium molybdate on learning and memory in rats

The combined effect of Semax with water solutions of plumbum diacetate (10^–7 M) and ammonium molybdate (10^–5 M) on the two-way active avoidance learning in rats in the shuttle chamber was studied. It was established that both salts of heavy metals oppress the learning and memory; plumbum diacetate caused larger oppression. Semax slowed down the development of the conditioned response but counteracted the negative influence on this process from the side of both metals. The effect of Semax on the development of the avoidance reaction in the presence of ammonium molybdate, which oppressed the avoidance by itself, paradoxically intensified. During the combined effect of the peptide and ammonium molybdate, the development of the conditioned reaction occurred much faster than against the background of Semax without the combination with molybdenum. In total, data obtained indicate a counteraction of Semax to neurotoxic effect of plumbum and molybdenum salts. Since oxidative stress is the main mechanism of neurotoxic effect of heavy metals, the indicated positive effect of Semax can, in our opinion, confirm the presence of antioxidant properties in the spectrum of the peptide pharmacological activity.     

On singularities of molecular relaxation in water solutions

In this paper, we analyzed spectra of liquid water and water solutions in a frequency domain, characteristic of the collective dynamics of water molecules (from 0 to 200 cm^?1). Particular attention is paid to the relaxation processes, one of which is observed in the terahertz region of the spectrum (～5–50 cm^?1). The physical essence of this process at the molecular level is still unclear. Based on data obtained this process is strongly suggested to interpret as a monomolecular relaxation of unbound water molecules.     

Technical Note: Phytoremediation of Hg and Cd from Industrial Effluents using an Aquatic Free Floating Macrophyte Azolla Pinnata

The level of heavy metal pollution in Singrauli, an industrial region in India, was assessed and the phytoremediation capacity of a small water fern, Azolla pinnata R.Br (Azollaceae), was observed to purify waters polluted by two heavy metals, i.e., mercury (Hg) and cadmium (Cd) under a microcosm condition. Azolla pinnata is endemic to India and is an abundant and easy-growing free-floating water fern usually found in the rice fields, polluted ponds, and reservoirs of India. The fern was grown in 24 40-L aquariums containing Hg²⁺ and Cd²⁺ ions each in concentrations of 0.5, 1.0, and 3.0 mgL^?1 during the course of this study. The study revealed an inhibition of Azolla pinnata growth by 27.0–33.9% with the highest in the presence of Hg (II) ions at 0.5 mgL^?1 in comparison to the control. After 13 days of the experiment, metal contents in the solution were decreased up to 70–94%. In the tissues of Azolla pinnata, the concentration of selected heavy metals during investigation was recorded between 310 and 740 mgKg^?1 dry mass, with the highest level found for Cd (II) treatment at 3.0 mgL^?1 containing a metal solution.     

Recrystallization of Ice Crystals in Trehalose Solution at Isothermal Condition

An isothermal ice recrystallization behavior in trehalose solution was investigated. The isothermal recrystallization rate constants of ice crystals in trehalose solution were obtained at ?5 °C, ?7 °C, and ?10 °C. Then the results were compared to those of a sucrose solution used as a control sample. Simultaneous estimation of water mobility in the freeze-concentrated matrix was conducted by ¹H spin–spin relaxation time T₂ to investigate mechanisms causing the different ice crystal recrystallization behaviors of sucrose and trehalose. At lower temperatures, lower recrystallization rates were obtained for both trehalose and sucrose solutions. The ice crystallization rate constants in trahalose solution tended to be smaller than those in sucrose solution at the same temperature. Although different ice contents (less than 3.6%) were observed between trehalose and sucrose solutions at the same temperature, the recrystallization behaviors of ice crystals were not markedly different. The ¹H spin–spin relaxation time T₂ of water components in a freeze-concentrated matrix for trehalose solution was shorter than in a sucrose solution at the same temperature. Results show that the water mobility of trehalose solutions in freeze-concentrated matrix was less than that of sucrose solutions, which was suggested as the reason for retarded ice crystal growth in a trehalose solution. Results of this study suggest that the replacement of sucrose with trehalose will not negatively affect deterioration caused by ice crystal recrystallization in frozen foods and cryobiological materials.     

Biodegradation and kinetics of organic compounds and heavy metals in an artificial wetland system (AWS) by using water hyacinths as a biological filter

The objective of the present study was to investigate the ability of water hyacinth (Eichhornia crassipes) to absorb organic compounds (potassium hydrogen phthalate, sodium tartrate, malathion, 2,4-dichlorophenoxy acetic acid (2,4-D), and piroxicam). For the aforementioned purpose, an artificial wetland system (AWS) was constructed and filled with water hyacinth collected from the Valsequillo Reservoir, Puebla, Mexico. Potassium hydrogen phthalate and sodium tartrate were measured in terms of chemical oxygen demand (COD) and biological oxygen demand (BOD). The present study indicated that the water hyacinths absorbed nearly 1.8–16.6 g of COD kg^?1 dm (dry mass of water hyacinth), while the absorbance efficiency of BOD was observed to be 45.8%. The results also indicated that the maximum absorbance efficiency of malathion, 2,4-D, and piroxicam was observed to be 67.6%, 58.3%, and 99.1%, respectively. The kinetics of organic compounds fitted different orders as malathion followed a zeroth-order reaction, while 2,4-D and piroxicam followed the first-order reactions. Preliminary assessment of absorption of heavy metals by the water hyacinth in the AWS was observed to be (all values in mg g^?1) 7 (Ni), 13.4 (Cd), 16.3 (Pb), and 17.5 (Zn) of dry biomass, thus proving its feasibility to depurate wastewater.     

Heavy metals potential health risk assessment through consumption of wastewater irrigated wild plants: A case study

This study investigates the potential health risk assessment of heavy metals consumption through wild plants (WPs) irrigated with wastewater and fresh water in the Bannu district, Pakistan. Therefore, soil and WP samples were collected and analyzed for heavy metals by atomic absorption spectrophotometer (Varian FAAS-240). Wastewater irrigated soil showed an elevated level for Cd (5.05–14.50 mg/Kg) and Ni (99.35–104.85 mg/Kg), while Cd (3.35–4.84 mg/Kg) concentration in the fresh water irrigated soil also surpassed the maximum allowable limits (MAL) set by the World Health Organization. Similarly, selected wastewater irrigated plants and fresh water irrigated plants also exceeded the MAL set by the Food and Agriculture Organization for Cd, Pb, and Cr (except for Cr in Vicia sativa). Heavy metal concentrations through WPs consumption were evaluated for the health risk index (HRI). The HRI value for each selected WPs was <1. However, total HRI values through WPs consumption was >1. Therefore, WPs consumption of the study area may pose a potential threat to the local community.     

Concentrations and Distribution of Trace Metals in Water and Streambed Sediments of Orogodo River,Southern Nigeria

The distribution of Cd, Pb, Ni, Cr, Cu, Mn, Fe, and Zn in sediment and surface water, and some physico-chemical characteristics of Orogodo river sediments, were evaluated. The sediment pH ranged from 5.1–7.3; conductivity values ranged from 34.5 to 389.0 μScm^?1. Total nitrogen values ranged from 0.06–0.10%, NH₃-N values ranged from 0.25–0.44 mgkg^?1, percent total organic carbon ranged from 0.21–1.68%, and total phosphorus values ranged from 0.004–0.02% for dry and wet seasons. The sand fraction consists of 87–95%, silt fractions ranged from 0–2%, and clay fraction between 4–13%. The mean concentrations of metals (dry weight basis) in the streambed sediments ranged from 1.92–17.37 mgkg^?1 for Cu, 0.98–4.78 mgkg^?1 for Ni, 0.01–32.98 mgkg^?1 for Mn, 353.22–2045.64 mgkg^?1 for Fe, 69.96–100.16 mgkg^?1 for Zn, 0.21–1.32 mgkg^?1 for Cr, and Cd was less than 0.001 mgkg^?1 for wet and dry seasons. The mean concentrations of metals in the surface water ranged between 0.01–0.05–0.05 mg/L for Cu, nd-0.11 mg/L for Ni, 0.001–0.31 mg/L for Pb, 0.001–1.82 mg/L Mn, 0.01–3.52 mg/L for Fe, 0.16–0.61 mg/L for Zn, nd-0.007 mg/L for Cr, and <0.001 mg/L for Cd. Based on principal component analysis, two main sources of metals in the Orogodo River can be identified: (i) Cr, Cu, Pb, and Fe are mainly derived from industrial sources; (ii) Mn, Zn, and Ni associated with traffic activities. No element examined had a contamination/pollution index value greater than unity (pollution ranges). This implies that the multiple pollution indices obtained from the analysis showed that Orogodo River sediments were not polluted with heavy metals.