Electron spin relaxation times of perdeuterated tempone (PDT) 1 and of a nitronyl nitroxide 2-(4-carboxy-phenyl)-4,4,5,5-tetramethylimidazoline-3-oxide-1-oxyl) 2 in aqueous solution at room temperature were measured by 2-pulse electron spin echo (T2) or 3-pulse inversion recovery (T1) in the frequency range of 250 MHz to 34 GHz. At 9 GHz values of T1 measured by long-pulse saturation recovery were in good agreement with values determined by inversion recovery. Below 9 GHz for 1 and below 1.5 GHz for 2, T1~ T2, as expected in the fast tumbling regime. At higher frequencies T2 was shorter than T1 due to incomplete motional averaging of g and A anisotropy. The frequency dependence of 1/T1 is modeled as the sum of spin rotation, modulation of g and A-anisotropy, and a thermally-activated process that has maximum contribution at about 1.5 GHz. The spin lattice relaxation times for the nitronyl nitroxide were longer than for PDT by a factor of about 2 at 34 GHz, decreasing to about a factor of 1.5 at 250 MHz. The rotational correlation times, τR are calculated to be 9 ps for 1 and about 25 ps for 2. The longer spin lattice relaxation times for 2 than for 1 at 9 and 34 GHz are due predominantly to smaller contributions from spin rotation that arise from slower tumbling. The smaller nitrogen hyperfine couplings for the nitronyl 2 than for 1 decrease the contribution to relaxation due to modulation of A anisotropy. However...
The integration of discrete metal complexes has been attracting significant interest due to the potential of these materials for soft metal-metal interactions and supramolecular assembly. Additionally, block copolypeptide amphiphiles have been investigated concerning their capacity for self-assembly into structures such as nanoparticles, nanosheets and nanofibers. In this study, we combined these two concepts by investigating the self-assembly of discrete metal complexes in aqueous solution using block copolypeptides. Normally, discrete metal complexes such as [Au(CN)2]−, when molecularly dispersed in water, cannot interact with one another. Our results demonstrated, however, that the addition of block copolypeptide amphiphiles such as K183L19 to [Au(CN)2]− solutions induced one-dimensional integration of the discrete metal complex, resulting in photoluminescence originating from multinuclear complexes with metal-metal interactions. Transmission electron microscopy (TEM) showed a fibrous nanostructure with lengths and widths of approximately 100 and 20 nm, respectively, which grew to form advanced nanoarchitectures, including those resembling the weave patterns of Waraji (traditional Japanese straw sandals). This concept of combining block copolypeptide amphiphiles with discrete coordination compounds allows the design of flexible and functional supramolecular coordination systems in water.
The dependence of the interfacial tension of a phosphatidylethanolamine (PE) monolayer on the pH of the aqueous solution has been studied. A theoretical equation is derived to describe this dependence. A simple model of the influence of pH on the phosphatidylethanolamine monolayer at the air/hydrophobic chains of PE is presented. The contributions of additive phosphatidylethanolamine forms (both interfacial tension values and molecular area values) depend on pH. The interfacial tension values and the molecular area values for PEH+ and PEOH− forms of phosphatidylethanolamine were calculated. The assumed model was verified experimentally. The experimental results agreed with those derived from the theoretical equation in a whole range of pH values.
Although the treatment technology of sulfamethoxazole has been investigated widely, there are various issues such as the high cost, inefficiency, and secondary pollution which restricted its application. Bioflocculant, as a novel method, is proposed to improve the removal efficiency of PPCPs, which has an advantage over other methods. Bioflocculant MFX, composed by high polymer polysaccharide and protein, is the metabolism product generated and secreted by Klebsiella sp. In this paper, MFX is added to 1 mg/L sulfanilamide aqueous solution substrate, and the removal ratio is evaluated. According to literatures review, for MFX absorption of sulfanilamide, flocculant dosage, coagulant-aid dosage, pH, reaction time, and temperature are considered as influence parameters. The result shows that the optimum condition is 5 mg/L bioflocculant MFX, 0.5 mg/L coagulant aid, initial pH 5, and 1 h reaction time, and the removal efficiency could reach 67.82%. In this condition, MFX could remove 53.27% sulfamethoxazole in domestic wastewater, and the process obeys Freundlich equation. R2 value equals 0.9641. It is inferred that hydrophobic partitioning is an important factor in determining the adsorption capacity of MFX for sulfamethoxazole solutes in water; meanwhile...
Sonolysis and photochemical degradation of different compounds such as
chlorinated aliphatic hydrocarbons are among the recent advanced oxidation
processes. Perchloroethylene is one of these compounds that has been mainly used
as a solvent and degreaser. In this work, elimination of perchloroethylene in
aqueous solution by ultrasonic irradiation, andphotochemical oxidation by ultra
violet ray and hydrogen peroxide were investigated. Three different initial
concentrations of perchloroethylene at different pH values, detention periods,
and concentrations of hydrogen peroxide were investigated. Head space gas
chromatography with FID detector was used for analyses of perchloroethylene.
This research was performed in 9 months from April through December 2011.
A marked difference in spin relaxation behavior due to hemoglobin magnetism was found for positive muons (μ+) in deoxyhemoglobin in comparison with that observed in oxyhemoglobin in aqueous solution at room temperature under zero and external longitudinal magnetic fields upto 0.4 Tesla. At the same time, small but significant unique relaxation pattern was observed in nonmagnetic oxyhemoglobin. Combined with our previous measurements on hemoglobin in human blood, application of this type of measurement to the studies of the level of oxygenation in various regions of the human brain is suggested.
Molecular dynamics simulations were carried out on a system of caffeine interacting with the sugar alcohol sorbitol. The system examined had a caffeine concentration 0.083 m and a sugar concentration 1.08 m. The trajectories of all molecules in the system were collected over a period of 80 ns and analyzed to determine whether there is any tendency for sorbitol to bind to caffeine, and if so, by what mechanism. The results show that the sorbitol molecules have an affinity for the caffeine molecules and that the binding occurred by the interaction of the aliphatic hydrophobic protons of the sugar with the caffeine face. This intermolecular association via face-to-face stacking, as suggested by simulation studies, is similar to that found for sucrose and for D-glucose, which overwhelmingly exists in the pyranose ring chair form in aqueous solution, as well as for caffeine-caffeine association. The sorbitol molecules, however, exist as relatively extended chains and are, therefore, topologically quite different from the sugars sucrose and glucose. The comparison of the average conformation of sorbitol molecules bound to caffeine with that of molecules in the free state shows a substantial similarity.
Water enables life and plays a critical role in biology. Considered as a versatile and adaptive component of the cell, water engages a wide range of biomolecular interactions. An organism can exist and function only if its self-assembled molecular structures are hydrated. It was shown recently that switching of AMP/ATP binding to the insulin-independent glucose transporter Human Erythrocyte Glucose Transport Protein (GLUT1) may greatly influence the ratio of bulk and bound water during regulation of glucose uptake by red blood cells. In this paper, we present the results on the hydration properties of AMP/ATP obtained by means of dielectric spectroscopy in aqueous solution and for fully ionized forms in solid amorphous films with the help of gravimetric studies.
The study on biochar derived from plant biomass for environmental applications is attracting more and more attention. Twelve sets of biochar were obtained by treating four phytoremediation plants, Salix rosthornii Seemen, Thalia dealbata, Vetiveria zizanioides, and Phragmites sp., sequentially through pyrolysis at 500 °C in a N2 environment, and under different temperatures (500, 600, and 700 °C) in a CO2 environment. The cation exchange capacity and specific surface area of biochar varied with both plant species and pyrolysis temperature. The magnesium (Mg) content of biochar derived from T. dealbata (TC) was obviously higher than that of the other plant biochars. This biochar also had the highest sorption capacity for phosphate and ammonium. In terms of biomass yields, adsorption capacity, and energy cost, T. dealbata biochar produced at 600 °C (TC600) is the most promising sorbent for removing contaminants (N and P) from aqueous solution. Therefore, T. dealbata appears to be the best candidate for phytoremediation application as its biomass can make a good biochar for environmental cleaning.
Boron removal capacity of multi-walled carbon nanotubes (MWCNTs) modified with tartaric acid was investigated in this study. Modification of MWCNTs with tartaric acid was confirmed by Boehm surface chemistry method and fourier transform infra-red (FT-IR) spectroscopy. Experiments were performed to determine the adsorption isotherm and adsorption thermodynamic parameters of boron adsorption on tartaric acid modified MWCNTs (TA-MWCNTs). The effect of variables including initial pH, dosage of adsorbent, contact time and temperature was investigated. Analysis of data showed that adsorption equilibrium could be better described by Freundlich isotherm and the maximum adsorption capacities obtained at the pH of 6.0 was 1.97 mg/g. The estimated thermodynamic values of free energy (ΔG°), entropy (ΔS°) and enthalpy (ΔH°) indicated a spontaneous and an endothermic process. Furthermore, the TA-MWCNTs was magnetized for separation of boron-contaminated adsorbent from aqueous solution by applying magnetic field. The results showed that magnetic TA-MWCNTs particles were separated effectively after adsorption from contaminated water.
The effects of varying operating conditions on metals removal from aqueous solution using a novel platinum nanopartcles/Zeolite-4A adsorbent are reported in this paper. Characterization of the adsorbent showed successful production of platinum nanopartcles on Zeolite-4A using 3 Wt% platinum. The effects of operation conditions on metals removal using this adsorbent were investigated. The optimal metals adsorption was observed at pH 7, 0.1 g/10 mL dosage and 30 min contact time. Sorption data have been interpreted in terms of Langmuir and Freundlich isotherms.
The reaction of 2-(4-methyphenyl)ethyl tosylate (Me-1-OTs) in 50/50 (v/v) trifluoroethanol/water at 25 °C is first-order in the concentration of azide anion nucleophile. A carbon-13 NMR analysis of the products of the reactions of Me-1-[α–13C]OTs in 50/50 (v/v) trifluoroethanol/water at 25 °C shows the formation of Me-1-[β–13C]OH, Me-1-[β–13C]OCH2CF3 and Me-1-[β–13C]N3 from the trapping of a symmetrical 4-methylphenonium ion reaction intermediate Me-2+. The formation of Me-1-[α–13C]N3 by concerted bimolecular displacement of azide ion at Me-1-[α–13C]OTs (kN = 3.8 × 10−6 M−1 s−1) and of Me-1-[α–13C]OH and Me-1-[α–13C]OCH2CF3 by concerted bimolecular displacement of solvent (ksolv = 1.8 × 10−8 s−1) is also observed. An analysis of the rate and product data provides a value of kaz/ks = 32 M−1 for partitioning of Me-2+ between addition of azide ion and solvent that is nearly 3-fold smaller than kaz/ks = 83 M−1 reported in an earlier study on the partitioning of MeO-2+ [J. Org. Chem. 2011, 76, 9568]. This change is attributed to a decrease in nucleophile selectivity with increasing electrophile reactivity for the activation-limited addition of solvent and azide anion to X-2+. These data set a limit of 1/ks ≥ 10−7 s for the lifetime of Me-2+ in aqueous solution.
Polydimethylsiloxane (PDMS) is commonly used as the coated polymer in the solid phase microextraction (SPME) technique. In this study, the partition coefficients of organic compounds between SPME/PDMS and the aqueous solution were compiled from the literature sources. The correlation analysis for partition coefficients was conducted to interpret the effect of their physicochemical properties and descriptors on the partitioning process. The PDMS-water partition coefficients were significantly correlated to the polarizability of organic compounds (r = 0.977, p < 0.05). An empirical model, consisting of the polarizability, the molecular connectivity index, and an indicator variable, was developed to appropriately predict the partition coefficients of 61 organic compounds for the training set. The predictive ability of the empirical model was demonstrated by using it on a test set of 26 chemicals not included in the training set. The empirical model, applying the straightforward calculated molecular descriptors, for estimating the PDMS-water partition coefficient will contribute to the practical applications of the SPME technique.
DNA can be concatenated by hybridization of DNA fragments with protruding single-stranded termini. DNA cleavage occurring at a nucleotide containing a DNA base analogue is a useful method to obtain DNA with designed protruding termini. Here, we report a novel non-enzymatic DNA cleavage reaction for DNA concatenation. We found that DNA is cleaved at a nucleotide containing 5-ethynyluracil in a methylamine aqueous solution to generate 5′-phosphorylated DNA fragment as a cleavage product. We demonstrated that the reaction can be applied to DNA concatenation of PCR-amplified DNA fragments. This novel non-enzymatic DNA cleavage reaction is a simple practical approach for DNA concatenation.
Two new tridentate(NNO)-bidentate(NN) compartmental ligands, HL5 and HL6, are synthesized from pyridine and benzimidazole synthons. They react in aqueous solution under physiological conditions with ZnII, LnIII, or a mixture thereof, to yield complexes of different stoichiometries, 1:3, 2:2, 2:3, 1:1:3, the speciation of which is established by UV-visible titrations and ESI mass spectrometry. Photophysical studies of the EuIII-containing solutions in Tris-HCl 0.1 M (pH = 7.4) show that lanthanide luminescence arises from a unique N6O3 coordination site with pseudo D3 symmetry. Relevant parameters such as crystal field splitting, lifetime, radiative lifetime, and intrinsic quantum yield perfectly match those reported for dinuclear 4f-4f helicates in which the EuIII ion has the same coordination environment.
In-vitro T1 and T2* relaxivities (r1 and r2*) of Gd-DTPA (GaD) in oxygenated human venous blood (OVB) and aqueous solution (AS) at 3T and 7T were calculated. GaD concentrations ([GaD]) in OVB and AS were prepared in the range 0–5 mM. All measurements were acquired at 37±2 °C. At both 3T and 7T, a linear relationship was observed between [GaD] and R1 in both AS and OVB. At 7T, r1 in AS decreased by 7.5% (p = 0.045) while there was a negligible change in OVB. With respect to R2*, a linear relationship with [GaD] was only observed in AS, while a more complex relationship was observed in OVB; quadratic below and linear above 2 mM at both field strengths. There was a significant increase of over four-fold in r2* with GaD in OVB at 7T (for [GaD] above 2mM, p ≪0.01) as compared to 3T. Furthermore, in comparison to r1, r2* in AS was less than two-fold higher at both field strengths while in OVB it was ~twenty-fold and ~ninety-fold higher at 3T and 7T, respectively. This observation emphasizes the importance of r2* knowledge at high magnetic fields, ≥3T. The comparison between r1 and r2* presented in this work is crucial in the design and optimization of high field MRI studies making use of paramagnetic contrast agents. This is especially true in multiple compartment systems such as blood where r2* dramatically increases while r1 remains relatively constant with increasing magnetic field strength.
The nature of the complexes formed in aqueous solution between either Pd(en)Cl2 or [Pd(en)(H2O)2](NO3)2 and 1,5-naphthyridine (1,5-NAP), where en is ethylenediamine, have been investigated by 1-D and 2-D 1H NMR spectroscopy and potentiometric titration. Above pH 5.0, two major complexes have been identified with the stoichiometries of 2:1 and 1:1 (M:L ratio) as well as small amounts of a 1:2 complex and/or oligomer. The 2:1 complex consisted of a Pd(en)2+ moiety symmetrically bonded to each of the nitrogen atoms of the 1,5-NAP, as indicated by the presence of just three 1H NMR resonances in the aromatic region. The 1:1 complex had six resonances as a result of only one 1,5-NAP nitrogen atom being bonded to a Pd(en)2+ group. At pH <5, the uncomplexed nitrogen of the 1:1 and other singly bonded 1,5-NAP species became protonated and resulted in the formation of a large number of complexes. Job’s method plots at pH 6 showed that the 1:1 complex is stable over a large concentration range. Above pH ~6 the 1:1 complex can dimerize via deprotonation of a water ligand on the Pd(en)2+ to form an hydoxo-bridged or oxo-bridged species. Evidence for this was observed in the upfield shifts of the resonances as the pH increased. The species distribution curve from potentiometric titrations and the NMR data were in good agreement at concentrations of 1–4 mM. NOESY data indicated that free 1...
Vertically aligned ZnO nanorods (NRs) on aluminum-doped zinc oxide (AZO) substrates were fabricated by a single-step aqueous solution method at low temperature. In order to optimize optical quality, the effects of annealing on optical and structural properties were investigated by scanning electron microscopy, X-ray diffraction, photoluminescence (PL), and Raman spectroscopy. We found that the annealing temperature strongly affects both the near-band-edge (NBE) and visible (defect-related) emissions. The best characteristics have been obtained by employing annealing at 400°C in air for 2 h, bringing about a sharp and intense NBE emission. The defect-related recombinations were also suppressed effectively. However, the enhancement decreases with higher annealing temperature and prolonged annealing. PL study indicates that the NBE emission is dominated by radiative recombination associated with hydrogen donors. Thus, the enhancement of NBE is due to the activation of radiative recombinations associated with hydrogen donors. On the other hand, the reduction of visible emission is mainly attributed to the annihilation of OH groups. Our results provide insight to comprehend annealing effects and an effective way to improve optical properties of low-temperature-grown ZnO NRs for future facile device applications.
In situ time-resolved XANES measurements of Au ions in an aqueous solution in the presence of support materials were performed under synchrotron X-ray irradiation. The synchrotron X-ray-induced reduction of Au ions leads to the formation of Au nanoparticles on the carbon particles, acrylic cell or polyimide window. The deposited Au metallic spots were affected by the wettability of carbon particles.
Three new heterogemini sulfobetaines and their chloride salts were synthesised. The interfacial activities of the obtained chlorides in aqueous solution were studied by equilibrium and dynamic surface tension measurements. The critical micelle concentration, surface excess concentration, minimum area per surfactant molecule and standard Gibbs energy of adsorption as well as micelle lifetime and diffusion coefficient were determined. The adsorption properties and micelle lifetime of these compounds significantly depend on the length of alkyl chain. The critical micelle concentration decreases with increasing chain length of the compounds considered. The values of the diffusion coefficient of N-alkyl-N-methyl-N-(3-sulfopropyl)-6-(N-alkyl-N-methylamino)hexylammonium chloride tend to decrease as the concentration is increased.