Synthesis and application of a thermosensitive tri-block copolymer as an efficient sample treatment technique for preconcentration and ultra-trace detection of lead ions

We have designed and synthesized a thermosensitive tri-block copolymer for selective trace extraction of Pb(II) ions from biological and food samples. The polymer was characterized by Fourier transform IR and NMR spectroscopy, and by gel permeation chromatography. The critical aggregation concentration and lower critical solution temperature were determined via fluorescence and UV spectrophotometry, respectively. The effects of solution pH value, amount of copolymer, of the temperature on extraction and on phase separation, and of the matrix on the extraction of Pb(II) were optimized. Pb(II) ions were then quantified by FAAS. The use of this copolymer resulted in excellent figures of merit including a calibration plot extending from 0.5 to 160 μg L^?1 (with an R² of >0.99), a limit of detection (LOD) as low as 90 pg L^?1, an extraction efficiency of >98 %, and relative standard deviations of <4 % for eight separate extraction experiments.

Biogas Production from N-Methylmorpholine-N-oxide (NMMO) Pretreated Forest Residues

Lignocellulosic biomass represents a great potential for biogas production. However, a suitable pretreatment is needed to improve their digestibility. This study investigates the effects of an organic solvent, N-Methylmorpholine-N-oxide (NMMO) at temperatures of 120 and 90 °C, NMMO concentrations of 75 and 85 % and treatment times of 3 and 15 h on the methane yield. The long-term effects of the treatment were determined by a semicontinuous experiment. The best results were obtained using 75 % NMMO at 120 °C for 15 h, resulting in 141 % increase in the methane production. These conditions led to a decrease by 9 % and an increase by 8 % in the lignin and in the carbohydrate content, respectively. During the continuous digestion experiments, a specific biogas production rate of 92 NmL/gVS/day was achieved while the corresponding rate from the untreated sample was 53 NmL/gVS/day. The operation conditions were set at 4.4 gVS/L/day organic loading rate (OLR) and hydraulic retention time (HRT) of 20 days in both cases. NMMO pretreatment has substantially improved the digestibility of forest residues. The present study shows the possibilities of this pretreatment method; however, an economic and technical assessment of its industrial use needs to be performed in the future.     

Effect of Adenine Sulphate Interaction on Growth and Development of Shoot Regeneration and Inhibition of Shoot Tip Necrosis Under In Vitro Condition in Adult Syzygium cumini L.—a Multipurpose Tree

An efficient method for cloning Syzygium cumini (above 40 years old) through mature nodal segments has been successfully developed and that could be exploited for large-scale production of this valuable multipurpose tree. Nodal segments from mature tree were taken as explants and cultured on MS basal medium with different cytokinins (BA, Kin, AdS). The application of BA proved to be the best responsive cytokinin for the induction of shoot buds and shoots, but the proliferated shoots exhibited slower and stunted growth accompanied with abscission of leaves and shoot tip necrosis (STN). The problem of leaf abscission and STN was considerably reduced by the application of an adjuvant, adenine sulphate (AdS) in the optimal medium which led to the production of a maximum of 14 shoots. Further improvement in shoot bud regeneration and improved growth pattern of the regenerating tissue was obtained on the media comprised of MS?+?BA (10 μM)?+?GA₃ (2.5 μM). A total number of 15 shoots with mean shoot length of 5.9 cm was obtained. The healthy elongated shoots were then rooted on MS basal augmented with NAA (5 μM). The plantlets obtained were healthy and were successfully acclimatized and transferred under field condition with 70 % survival rate.     

Electrochemical synthesis and characterization of solid-phase microextraction fibers using conductive polymers: application in extraction of benzaldehyde from aqueous solution

In this work, polyaniline, polypyrrole, and polyaniline/polypyrrole composite fibers were synthesized in the absence and presence of oxidized multiwalled carbon nanotubes using electrochemical cyclic voltammetry with CF₃COOH as dopant. Thermal stability of these fibers was studied by differential scanning calorimetry. Then, headspace solid-phase microextraction process coupled with gas chromatography and flame ionization detector was used for comparing extraction capability of benzaldehyde from aqueous solution. Since polyaniline fiber showed better extraction efficiency than the other fibers, its preparation conditions including acid concentration, aniline concentration, scan rate, and amount of multiwalled carbon nanotubes were studied by means of the “one-factor-at-a-time method”. The analytical performance of polyaniline fibers were investigated to determine benzaldehyde from the aqueous solution. The morphology and texture of polyaniline fibers were examined by field emission scanning electron microscopy and Fourier transform infrared spectroscopy analyses. The attained results revealed that the perfect conditions for acid concentration, aniline concentration, scan rate, and multiwalled carbon nanotubes content were 0.5 M, 0.2 M, 25 mV s^?1, and 0.02 wt%, respectively. The limit of detection for the proposed polyaniline fiber was 15 ng ml^?1.     

Hydrolytic Transformation of Microporous Metal–Organic Frameworks to Hierarchical Micro‐ and Mesoporous MOFs

A new approach to the synthesis of hierarchical micro‐ and mesoporous MOFs from microporous MOFs involves a simple hydrolytic post‐synthetic procedure. As a proof of concept, a new microporous MOF, POST‐66(Y), was synthesized and its transformation into a hierarchical micro‐ and mesoporous MOF by water treatment was studied. This method produced mesopores in the range of 3 to 20 nm in the MOF while maintaining the original microporous structure, at least in part. The degree of micro‐ and mesoporosity can be controlled by adjusting the time and temperature of hydrolysis. The resulting hierarchical porous MOF, POST‐66(Y)‐wt, can be utilized to encapsulate nanometer‐sized guests such as proteins, and the enhanced stability and recyclability of an encapsulated enzyme is demonstrated.     

An Eco‐friendly Three Component Manifold for the Synthesis of α‐Aminophosphonates under Catalyst and Solvent‐free Conditions,X‐ray Characterization and Their Evaluation as Anticancer Agents

A series of α‐aminophosphonates were synthesized through one‐pot condensation of aryl aldehydes, aryl amines and diethyl phosphite in the absence of any catalyst and organic solvents. All the synthesized α‐aminophosphonates were characterized by spectral and elemental analysis and in the case of compound 4j by X‐ray crystallography. Some of these new α‐aminophosphonate derivatives were found to have cytotoxic activity on the cancer cell line DU145 in vitro by the MTT method.     

Suitability of dispersive liquid–liquid microextraction for the in situ silylation of chlorophenols in water samples before gas chromatography with mass spectrometry

Trace analysis of chlorophenols in water was performed by simultaneous silylation and dispersive liquid–liquid microextraction followed by gas chromatography with mass spectrometry. Dispersive liquid–liquid microextraction was carried out using an organic solvent lighter than water (n‐hexane). The effect of different silylating reagents on the method efficiency was investigated. The influence of derivatization reagent volume, presence of catalyst and derivatization/extraction time on the yield of the derivatization reaction was studied. Different parameters affecting extraction efficiency such as kind and volume of extraction and disperser solvents, pH of the sample and addition of salt were also investigated and optimized. Under the optimum conditions, the calibration graphs were linear in the range of 0.05–100 ng/mL and the limit of detection was 0.01 ng/mL. The enrichment factors were 242, 351, and 363 for 4‐chlorophenol, 2,4‐dichlorophenol, and 2,4,6‐trichlorophenol, respectively. The values of intra‐ and inter‐day relative standard deviations were in the range of 3.0–6.4 and 6.1–9.9%, respectively. The applicability of the method was investigated by analyzing water and wastewater samples.     

Modified carbon nanotubes as a sorbent for solid-phase extraction of gold,and its determination by graphite furnace atomic absorption spectrometry

A simple, sensitive and accurate method was developed for solid-phase extraction and preconcentration of trace levels of gold in various samples. It is based on the adsorption of gold on modified oxidized multi-walled carbon nanotubes prior to its determination by graphite furnace atomic absorption spectrometry. The type and volume of eluent solution, sample pH value, flow rates of sample and eluent, sorption capacity and breakthrough volume were optimized. Under these conditions, the method showed linearity in the range of 0.2–6.0 ng L⁻¹ with coefficients of determination of >0.99 in the sample. The relative standard deviation for seven replicate determinations of gold (at a level of 0.6 ng L⁻¹) is ±3.8 %, the detection limit is 31 pg L⁻¹ (in the initial solution and at an S/N ratio of 3; for n = 8), and the enrichment factor is 200. The sorption capacity of the modified MWCNTs for gold(III) is 4.15 mg g⁻¹. The procedure was successfully applied to the determination of gold in (spiked) water samples, human hair, human urine and standard reference material with recoveries ranging from 97.0 to 104.2 %.

A sorbent based on modified carbon nanotubes was prepared and used to extract gold ion from various samples prior to its determination by graphite furnace atomic absorption spectrometry