Preparation of corn stalk-based adsorbents and their specific application in metal ions adsorption

Corn stalk-based adsorbents modified from corn stalk were prepared by Cu(0)-mediated reversible-deactivation radical polymerization (Cu(0)-mediated RDRP). They were applied to remove metal ions and they exhibited good adsorption capacity, especially for Hg(II). Adsorption properties of corn stalk can be enhanced by introducing cyano, amino, amidoxime, and carboxyl groups onto its surface, which results in efficient adsorbents for different metal ions. TGA, SEM, EA, and FTIR analyses were employed to characterize the structures of corn stalk-graft-polyacrylonitrile (CS-g-PAN), corn stalk-graft-polyacrylamide (CS-g-PAM), amidoxime corn stalk-graft-polyacrylonitrile (AO CS-g-PAN) and carboxyl corn stalk-graft-poly(methyl acrylate) (CO CS-g-PMA). The maximum adsorption capacity for Hg(II) was 8.06 mmol g^?1 of AO CS-g-PAN. Kinetics of the Hg(II) adsorption on AO CS-g-PAN was found to follow the pseudo-second-order model and the adsorption isotherms were well fitted with the Freundlich isotherm model.     

Synthesis and characterization of <Emphasis Type="Italic">β</Emphasis>-cyclodextrin–carboxymethyl cellulose–graphene oxide composite materials and its application for removal of basic fuchsin

A novel β-cyclodextrin–carboxymethyl cellulose–graphene oxide composite material (β-CD–CMC–GO) was synthesized, and its application as excellent adsorbents was carried out for removal basic fuchsin (BF) in aqueous solution. The structure and morphology of β-CD–CMC–GO composite material were characterized by using FTIR, SEM, TEM, XRD, TG and DSC methods. The composites could remove basic fuchsin from aqueous solution efficiently. The adsorption experiment was carried out and the optimum experimental conditions were ascertained. The highest adsorption efficiency was obtained 97.3% at 0.015 g/mL dosage of β-CD–CMC–GO, the temperature of 25 °C and time of 2.5 h. Adsorption kinetics, adsorption isotherm and adsorption thermodynamic were used to analyze the adsorption system. The experimental data of adsorption kinetics of system were well followed by pseudo-second-order equation. The adsorption isotherm data were fitted using Langmuir isotherm model and Freundlich isotherm model. The maximum adsorption capacity of basic fuchsin reached 58.65 mg/g. The thermodynamic parameters indicated that the adsorption process was spontaneous and exothermic. The adsorbent has excellent regeneration ability and reproducibility. The proposed method shows that the β-CD–CMC–GO could be applied to removal of basic fuchsin in wastewater with satisfactory result.     

The Role of Temperature in Enantioseparation of Norgestrel with Native Cyclodextrins: A Combined LC and NMR Study

Temperature dependence (10–50 °C) of the chiral LC separation of norgestrel was studied using native CDs added to a methanol–water 1:1 eluent. α- or β-CDs gave no enantiodiscrimination, while baseline LC separation was achieved with γ-CD. ¹H NMR titrations of the racemate with α-CD showed only weak complexation, while β- or γ-CDs caused enantiomeric splitting of the steroid signals. Both the chiral selectivity values and their insignificant temperature dependence measured in the γ-CD-modified LC system were successfully reproduced by NMR titrations. This agreement corroborates the intuitive view for a wider temperature range that the stability difference of the diastereomeric γ-CD/steroid complexes governs this LC enantioseparation.     

Preparation and characterization of the inclusion complexes of equol with sulfobutylether-β-cyclodextrin: their antioxidant activity and dissolution evaluation

The formation of inclusion complexes between S-(?)-equol (SEq) and cyclodextrins (CDs) was investigated. The binding constant (K_c) of the SEq/sulfobutylether-β-cyclodextrin (SBE-β-CD) inclusion complex was determined to be 1600 L/mol based on UV data. The phenyl ring of the SEq molecule was found to be inserted from the secondary hydroxyl face of the SBE-β-CD as evidenced from ¹H–¹H rotating frame nuclear Overhauser effect spectroscopy (ROESY) NMR. The thermal properties of the solid SEq/SBE-β-CD inclusion complexes prepared by physical mixing, kneading and freeze-drying methods were studied by differential scanning calorimetry. For the solid complex obtained by the freeze-drying method, the endothermic peak corresponding to the melting point of SEq disappeared. The solid SEq/SBE-β-CD complexes exhibited a high score in antioxidant activity evaluation tests compared to SEq alone. Dissolution test revealed that the solid complex obtained by freeze-drying method had improved dissolution of SEq.     

Phase solubility and FTIR-ATR studies of idebenone/sulfobutyl ether β-cyclodextrin inclusion complex

The favourable accessibility offered by sulfobutyl ether β-cyclodextrin (SBE-β-CD) for the complexation with idebenone (IDE) has been probed, as a function of temperature, in liquid state, by phase solubility study, and, in solid state, by FTIR-ATR technique. The phase solubility results indicated the formation of a IDE/SBE-β-CD inclusion complex with 1:1 molar ratio (A_L type diagram), whose apparent stability constants at T = 300, 310, and 320 K have been estimated according to the Higuchi–Connors method. The formation of the inclusion complex has been confirmed on a freeze-dried and a co-precipitated product by FTIR-ATR spectroscopy, monitoring the changes induced by complexation on some characteristic vibrational bands of IDE. Quantitative studies, performed in a wide T range, from T = 250 K to T = 340 K, allowed us to extract information on the effect of temperature on the different hydrogen-bonded environments involving host, guest, and crystallization water molecules. Again, complexation is proved to enhance the stability of the guest, at least in the explored T range.     

Facile synthesis of 5A zeolite from attapulgite clay for adsorption of <Emphasis Type="Italic">n</Emphasis>-paraffins

5A zeolites were facilely synthesized from attapulgite clay and sodium aluminate precursors. The optimum synthesis condition for 4A zeolite (Na-form) were H₂O/attapulgite ratio of 40:1 volume/mass, NaOH/attapulgite mass ratio of 2.35:1, the crystallization time was 4 h at 80–85 °C. The 4A zeolite was converted to related 5A zeolite (Ca-form) through ionic exchanges using calcium chloride solution with the Si/Al mole ratio of 1.3. SEM images demonstrated that as-synthesized 5A zeolites are ordered cubic crystals, average crystals length dimension is 1–2 μm. And the zeolites product had a specific surface area of 482 m² g^?1 and total pore volume of 0.274 cm³ g^?1. The static adsorption experiments showed that the equilibrium adsorption capacities of n-decane and n-pentadecane on produced 5A zeolite were 0.253 and 0.510 g g^?1, respectively. And the adsorption equilibrium time of n-decane and n-pentadecane on 5A zeolite were 45 and 60 min, respectively. The experimental adsorption data of n-decane and n-pentadecane on three zeolites could be properly fitted by the Langmuir–Freundlich isotherm model.     

Enzymatic Hydrolysis of Black Liquor Xylan by a Novel Xylose-Tolerant,Thermostable β-Xylosidase from a Tropical Strain of <Emphasis Type="Italic">Aureobasidium pullulans</Emphasis> CBS 135684

From three cell-associated β-xylosidases produced by Aureobasidium pullulans CBS 135684, the principal enzyme was enriched to apparent homogeneity and found to be active at high temperatures (60–70 °C) over a pH range of 5–9 with a specific activity of 163.3 units (U) mg^?1. The enzyme was thermostable, retaining over 80% of its initial activity after a 12-h incubation at 60 °C, with half-lives of 38, 22, and 10 h at 60, 65, and 70 °C, respectively. Moreover, it was tolerant to xylose inhibition with a K _i value of 18 mM. The K _m and V _max values against p-nitrophenyl-β-d-xylopyranoside were 5.57 ± 0.27 mM and 137.0 ± 4.8 μmol min^?1 mg^?1 protein, respectively. When combining this β-xylosidase with xylanase from the same A. pullulans strain, the rate of black liquor xylan hydrolysis was significantly improved by up to 1.6-fold. The maximum xylose yield (0.812 ± 0.015 g g^?1 dry weight) was obtained from a reaction mixture containing 10% (w/v) black liquor xylan, 6 U g^?1 β-xylosidase and 16 U g^?1 xylanase after incubation for 4 h at 70 °C and pH 6.0.     

β-Cyclodextrin derivatives hybrid Fe3O4 magnetic nanoparticles as the drug delivery for ketoprofen

β-Cyclodextrin (β-CD) and its derivatives carboxymethyl-β-CD (CM-β-CD) and 2,6-dimethyl-β-CD (DM-β-CD) modified magnetic nanoparticles (CD-MNPs) were synthesized via layer-by-layer method. CDs grafted onto Fe₃O₄ MNPs were demonstrated by transmission electron microscopy, Fourier transform infrared and Zeta potential. Magnetic properties of CM-β-CD-MNPs, DM-β-CD-MNPs and β-CD-MNPs were characterized by vibrating sample magnetometer and the magnetic saturation values were 47, 46 and 44 emu g^?1, respectively. CD-MNPs as drug carriers were investigated by inclusion behavior and in vitro release using ketoprofen (KP) as a model drug. The maximum adsorption quantities of CM-β-CD-MNPs, DM-β-CD-MNPs and β-CD-MNPs for KP were 37.03, 7.63 and 25.12 mg g^?1, respectively, and the loading behaviors followed the Langmuir adsorption isotherm model with monolayer adsorption. The release profiles of KP released from KP-loaded CD-MNPs were rapid in initial 60 min and then gradually tend to level off, the release efficiency order was CM-β-CD-MNPs > β-CD-MNPs > DM-β-CD-MNPs, which was consistent with the order of inclusion capability. Therefore, the CD-MNPs were promising candidates for drug delivery.     

Power consumption for an agitated vessel equipped with pitched blade turbine and short baffles

Power characteristics for an agitated vessel equipped with planar short baffles of length L and pitched blade turbine of pitch β are presented in the paper. The studies were carried out in the vessel of inner diameter D = 0.6 m, where the baffles were located in the distance p from the vessel bottom (p + L = H). Torque was measured using strain gauge method within the turbulent regime of the flow of Newtonian liquid in the agitated vessel. The effects of the pitch β and geometrical parameter p/H on the power number Ne were determined mathematically. The results showed that, for the assumed value of the angle β, the function Ne = f (L/H) decreases with the decrease in the baffle length L (i.e. with the increase in the parameter p). Moreover, for the assumed value of the baffle length L, the function Ne = f (β) increases with the increase in the angle β of the inclination of the impeller blade.     

Resolution of ketoconazole enantiomers by high-performance liquid chromatography and inclusion complex formation between selector and enantiomerss

The analytical resolution of ketoconazole (KTZ) enantiomers was performed by high-performance liquid chromatography with sulphobutylether-β-cyclodextrin (SBE-β-CD) as a chiral mobile phase additive (chiral selector). Some important factors affecting the resolution of KTZ enantiomers were investigated. In addition, the molecular interaction between KTZ and SBE-β-CD was studied using the UV absorption spectrum and HPLC for an understanding of the resolution process. The results show that the type and concentration of the chiral mobile phase additive, the pH of the mobile phase and the volume fraction of methanol (?_MeOH) in the mobile phase all have a clear influence on the resolution of KTZ enantiomers. Under optimal conditions, namely the use of 0.5 mmol L^?1 SBE-β-CD as the chiral mobile phase additive, pH of 4.0 and ?_MeOH in the mobile phase of 0.6, KTZ enantiomers are resolved with a resolution of 3.74. SBE-β-CD can bind to KTZ with a stability constant of 1157. The chromatographic method can provide the complexation stability constants of (+)-KTZ with SBE-β-CD (K₍₊₎) and (?)-KTZ with SBE-β-CD (K_(?)). The intrinsic enantioselectivity was calculated from the K₍₊₎ to (K_(?)) ratio as 1.34.     

Dye removal using 4A-zeolite/polyvinyl alcohol mixed matrix membrane adsorbents: preparation,characterization, adsorption,kinetics, and thermodynamics

In pursuit of improving performance of the methylene blue adsorption process, the potential of a novel 4A-zeolite/polyvinyl alcohol (PVA) membrane adsorbent was investigated. Adding 4A-zeolite particles to the PVA membrane adsorbent provided an effective structure for the adsorptive membrane in dye removal processes. Effect of zeolite content was also studied via synthesis of different mixed matrix membrane adsorbents (MMMAs) with 5, 10, 15, and 20 wt% 4A-zeolite content. Morphology of MMMAs was analyzed by scanning electron microscope and the intermolecular interactions were determined by Fourier transform infrared spectroscopy. X-ray diffraction was performed to determine the crystal structure of MMMAs. For the sake of finding optimum condition, the adsorption capacity was examined at various operating parameters, such as contact time, temperature, pH, and initial concentration. The maximum value of the adsorption capacity (q _e) of 41.08 mg g^?1 and the highest removal efficiency of 87.41 % were obtained by applying 20 wt% loading of 4A-zeolite. The experimental data were fitted well with the Freundlich adsorption isotherm model (R ² = 0.9917) compared with the Langmuir (R ² = 0.9489) and the Tempkin (R ² = 0.8886) adsorption isotherm models, and the adsorption kinetic data verified the best fitting with the pseudo-second-order model (R ² = 0.9999). The estimated data for Gibb’s free energy (ΔG°) showed that the adsorption process is spontaneous at lower temperature values and non-spontaneous at higher temperature values. Other evaluated thermodynamic parameters such as changing in enthalpy (ΔH°) and entropy (ΔS°) revealed that the adsorption process is exothermic with an increase in orderliness at the solid/solution interface.     

Poly(<Emphasis Type="Italic">β</Emphasis>-cyclodextrin)-mediated polylactide-cholesterol stereocomplex micelles for controlled drug delivery

A series of host-guest interaction-adjusted polylactide stereocomplex micelles was prepared via the self-assembly of 4-armed poly(ethylene glycol)-block-poly(L-lactide/D-lactide)-cholesterol (4-armed PEG-b-PLLA/PDLA-CHOL) and poly(β-cyclodextrin) (PCD) with the molar ratios of CHOL/β-CD at 1:0.5, 1:1, and 1:2 in an aqueous environment. The hydrodynamic diameters of the micelles ranged from 84.1 nm to 107 nm depending on the molar ratio of CHOL/β-CD. It was shown that the micelle with the largest proportion of PCD possessed excellent abilities in drug release, cell internalization as well as proliferation inhibitory effect toward human A549 lung cancer cells. The results demonstrated that the stereocomplex and host-guest interactions-mediated PLA micelles exhibited great potential in sustained drug delivery.     

Determination of Congo red in food samples by methyl-β-cyclodextrin/Triton X-100 synergistic sensitized fluorescence quenching method of the derivatives of calix[4]arene

A novel fluorescent chemosensor of the derivatives of calix[4]arene (SAX) for Congo red (CR) in methyl-β-cyclodextrin/Triton X-100 synergistic sensitized system was developed. The results showed that the fluorescence intensity of SAX could be quenched by CR, and the fluorescence quenching (?F?=?F_SAX ? F_CR-SAX) was synergistic sensitized by methyl-β-CD and Triton X-100. Under the conditions of λ_ex/em?=?332/468 nm and pH 7.5, the linear range and the detection limit for CR were found to be 0.040–8.0 μg/mL and 8.9 ng/mL, respectively. The mechanism of determination was discussed by quenching type analysis and sensitizing effect. This method has also been applied for the determination of CR in beef samples with satisfactory results.     

Release profiles of indometacin in <Emphasis Type="Italic">β</Emphasis>-cyclodextrin complexes from HPMC capsules

Powders containing indometacin complexed with β-cyclodextrin (1:1 ratio) obtained by two complexation methods (suspension/solution [with water removed by air stream, spray– and freeze–drying] and kneading techniques) were compared between them to observe the increase on the drug solubility and yield of the complexation process. The tests used for this comparison included the determination of the moisture content, true and bulk densities, angle of repose, Carr’s index and in vitro drug release (at pH 1.0) from HPMC capsules. In the dissolution tests the drug release was analyzed considering different parameters (similarity factor (f ₂), dissolution efficiency (DE) and the amounts released (M _t) at certain times (30, 60 and 180 min) by statistic analysis (α = 0.05)). The results obtained showed poor pharmaceutical properties for all mixtures and that the indometacin released from capsules containing inclusion complexes presented an increase on solubility when compared with reference formulation (lactose and microcrystalline cellulose instead of β-cyclodextrin). The release of indometacin showed no dependency on the amount of water used in the formation of the complexes being the differences observed mostly due to the characteristics of the particles, which were dependent on the complexation method. However the low yield of the complexation that occurred can be explained by the difference between the size of the drug molecule, the guest (diameter—7.5 Å, length—14.2 Å) and the size of the β-cyclodextrin cavity, the host (diameter—6.0–6.5 Å).     

Effect of Ag addition on crystallization kinetics and thermal stability of As–Se chalcogenide glasses

Chalcogenide glasses of (As₅₀Se₅₀)_100?xAg_x (0 ≤ x ≤ 25) were prepared using the melt quenching technique under non-isothermal conditions. Differential scanning calorimetry curves measured at different heating rates (5 ≤ β ≤ 40 K min^?1) are used to characterize the as-quenched samples. The thermal stability was monitored through the calculation of the temperature difference T _c ? T _g, stability parameter S and crystallization rate factor K _p. The glass-forming ability (GFA) was investigated on the basis of Hurby parameter H _r which is a strong indicator of GFA. In addition, the activation energy of glass transition E _t, activation energy of crystallization E _c and Avrami exponent n of the studied compositions were determined. The mechanism of crystallization was found to be a combination of two- and three-dimensional crystal growth.     

Saw-sedge <Emphasis Type="Italic">Cladium mariscus</Emphasis> as a functional low-cost adsorbent for effective removal of 2,4-dichlorophenoxyacetic acid from aqueous systems

For the first time in the published literature, a study is described concerning the use of the saw-sedge Cladium mariscus (C. mariscus) for adsorption of 2,4-dichlorophenoxyacetic acid (2,4-D) from aqueous systems. Among the experiments carried out, the elemental composition of C. mariscus was determined (C = 48.0 %, H = 7.1 %, N = 0.95 %, S = 0.4 %), FTIR spectroscopic analysis was performed to confirm the chemical structure of the adsorbent, and porous structure parameters were measured: BET surface area (A _BET  = 0.6 m²/g), total pore volume (V _p  = 0.001 cm³/g) and average pore size (S _p  = 6.6 nm). It was shown that the effectiveness of removal of 2,4-D from aqueous systems using C. mariscus depends on parameters of the process: contact time, system pH, mass of sorbent, and temperature. Maximum adsorption was attained for a solution at pH = 3. Further increase in the alkalinity of the tested systems led to a reduction in the effectiveness of the process. The kinetic of adsorption of 2,4-D by C. mariscus was also determined, and thermodynamic aspects were investigated. The experimental data obtained correspond to a pseudo-second-order kinetic model of type 1. Additionally the negative values obtained for ΔHº indicate that the process is exothermic, and the negative values of ΔGº show it to be spontaneous. As the temperature of the system increases the spontaneity of adsorption is reduced, in accordance with the exothermic nature of the process.     

Synthesis,crystal structure,and hydrogen-bonded displacive-type structural phase transition of guanidine dichloroacetate

Guanidine dichloroacetate was synthesized and separated as crystals. Differential scanning calorimetry (DSC) measurement shows that this compound undergoes a reversible phase transition at about 275 K with a heat hysteresis of 28 K. Step-like dielectric anomaly observed at 274 K further confirms the phase transition. The single-crystal X-ray diffraction data suggested that these was a transition from a room-temperature phase with the space group of P2₁/n (a = 8.030(5), b = 12.014(9), c = 8.124(6) Å, β = 96.089(1)°, V = 779.3(1) Å³, and Z = 4) to a low-temperature one with the space group of P2₁/c (a = 7.941(2), b = 11.828(3), c = 10.614(2) Å, β = 130.985(1)°, V = 752.6(3) Å³, and Z = 4). The displacements of hydrogen bonds induce the structure phase transition.     

Electrospinning of cyclodextrin functionalized chitosan/PVA nanofibers as a drug delivery system

A new type of nanofibrous structure from chitosan bearing carboxymethyl-β-cyclodextrin (CS-g-β-CD) as a novel drug delivery system was synthesized by grafting carboxymethyl-β-cyclodextrin (CM β-CD) onto chitosan (CS) in the presence of water soluble 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC) as the condensing agent and N-hydroxysuccinimide (NHS). Defect free mats containing CS-g-β-CD have been fabricated using electrospinning of an aqueous solution of poly(vinyl alcohol) (PVA)/CS-g-β-CD blends. The morphology and diameter of the electrospun nanofibers were examined by scanning electron microscopy (SEM). The average fiber diameter was in the range of 130–210 nm. SEM images showed that the morphology and diameter of the nanofibers were mainly affected by weight ratio of the blend at constant applied voltage. The results revealed that increasing CS-g-β-CD content in the blends decreases the average fiber diameter. It was observed that the PVA/CS-g-β-CD nanofibrous mat provided a slower release of the entrapped drug in compare to PVA/CS nanofibrous mat.     

Structure,bioactivity and theoretical study of 1-cyano-<Emphasis Type="Italic">N</Emphasis>-p-tolylcyclo-propanecarboxamide

A novel cyclopropane derivative, 1-cyano-N-p-tolylcyclopropanecarboxamide (C₁₂H₁₂N₂O, Mr = 200.24) was synthesized and its structure was studied by X-ray diffraction, FTIR, ¹H and ¹³C NMR spectrum and MS. The crystals are monoclinic, space group P2_1/c with a = 7.109 (4), b = 13.758 (7), c = 11.505 (6) Å, α = 90.00, β = 102.731 (8), γ = 90.00 °, V = 1097.6 (9) ų, Z = 4, F(000) = 312, D _c  = 1.212 g/cm³, μ = 0.0800 mm^?1, the final R = 0.0490 and wR = 0.1480 for 1,375 observed reflections with I > 2σ(I). A total of 6,109 reflections were collected, of which 2,290 were independent (R _int = 0.0290). Theoretical calculation of the title compound was carried out with HF/6-31G (d,p), B3LYP/6-31G (d,p), MP2/6-31G (d,p). The full geometry optimization was carried out using 6-31G(d,p) basis set, and the frontier orbital energy. Atomic net charges were discussed, and the structure-activity relationship was also studied. The preliminary biological test showed that the synthesized compound is bioactive against the KARI of Escherichia coli.     

Sol–gel derived ion imprinted thiocyanato-functionalized silica gel as selective adsorbent of cadmium(II)

A Cd(II)-imprinted thiocyanato-functionalized silica gel adsorbent with high adsorption capacity was prepared by surface imprinting technique combined with sol–gel process for the selective adsorption of Cd(II) ion in aqueous solution, and was characterized by Fourier-transform infrared spectroscopy, nitrogen gas sorption and thermogravimetric analysis. The influences of different conditions (such as the pH of solutions, the contact time and the initial concentrations of Cd(II) ions) on the adsorption capacity of Cd(II) were investigated. The optimum pH of adsorption was in the range of 4–8.5. The adsorption equilibrium could be reached in 20 min. The relatively selectivity coefficients of the imprinted silica were higher than those of the non-imprinted adsorbents. Ho’s pseudo-second-order model well described the kinetics of the adsorption reaction. The adsorption process of metals followed Redlich–Peterson isotherm model, and the experimental value of maximum adsorption capacity for Cd(II) was 72.8 mg·g^?1. The positive value of ΔH ^o suggested endothermic nature of Cd(II) adsorption on the imprinted silica adsorbent. Increase in entropy of adsorption reaction was shown by the positive value of ΔS ^o and the negative value of ΔG ^o indicating that the adsorption was spontaneous in nature.