Abu Zayed Md. Badruddoza

Carboxymethyl-β-cyclodextrin conjugated magnetic nanoparticles as nano-adsorbents for removal of copper ions: Synthesis and adsorption studies

A novel nano-adsorbent, carboxymethyl-β-cyclodextrin modified Fe(3)O(4) nanoparticles (CMCD-MNPs) is fabricated for removal of copper ions from aqueous solution by grafting CM-β-CD onto the magnetite surface via carbodiimide method. The characteristics results of FTIR, TEM, TGA and XPS show that CM-β-CD is grafted onto Fe(3)O(4) nanoparticles. The grafted CM-β-CD on the Fe(3)O(4) nanoparticles contributes to an enhancement of the adsorption capacity because of the strong abilities of the multiple hydroxyl and carboxyl groups in CM-β-CD to adsorb metal ions. The adsorption of Cu(2+) onto CMCD-MNPs is found to be dependent on pH and temperature. Adsorption equilibrium is achieved in 30 min and the adsorption kinetics of Cu(2+) is found to follow a pseudo-second-order kinetic model. Equilibrium data for Cu(2+) adsorption are fitted well by Langmuir isotherm model. The maximum adsorption capacity for Cu(2+) ions is estimated to be 47.2mg/g at 25 °C. Furthermore, thermodynamic parameters reveal the feasibility, spontaneity and exothermic nature of the adsorption process. FTIR and XPS reveal that Cu(2+) adsorption onto CMCD-MNPs mainly involves the oxygen atoms in CM-β-CD to form surface-complexes. In addition, the copper ions can be desorbed from CMCD-MNPs by citric acid solution with 96.2% desorption efficiency and the CMCD-MNPs exhibit good recyclability.

Fe3O4/cyclodextrin polymer nanocomposites for selective heavy metals removal from industrial wastewater.

In this work, carboxymethyl-β-cyclodextrin (CM-β-CD) polymer modified Fe(3)O(4) nanoparticles (CDpoly-MNPs) was synthesized for selective removal of Pb(2+), Cd(2+), Ni(2+) ions from water. This magnetic adsorbent was characterized by TEM, FTIR, XPS and VSM. The adsorption of all studied metal ions onto CDpoly-MNPs was found to be dependent on pH, ionic strength, and temperature. Batch adsorption equilibrium was reached in 45 min and maximum uptakes for Pb(2+), Cd(2+) and Ni(2+) in non-competitive adsorption mode were 64.5, 27.7 and 13.2 mg g(-1), respectively at 25 °C. Adsorption data were fitted well to Langmuir isotherm and pseudo-second-order models for kinetic study. The polymer grafted on MNPs enhanced the adsorption capacity because of the complexing abilities of the multiple hydroxyl and carboxyl groups in polymer backbone with metal ions. In competitive adsorption experiments, CDpoly-MNPs could preferentially adsorb Pb(2+) ions with an affinity order of Pb(2+)>>Cd(2+)>Ni(2+) which can be explained by hard and soft acids and bases (HASB) theory. Furthermore, we explored the recyclability of CDpoly-MNPs.

Adsorption of chiral aromatic amino acids onto carboxymethyl-β-cyclodextrin bonded Fe3O4/SiO2 core–shell nanoparticles

Surface of magnetic silica nanoparticles is modified by grafting with carboxymethyl-β-cyclodextrin (CM-β-CD) via carbodiimide activation. The functionalized magnetic core-shell nanoparticles (MNPs) are characterized by Transmission Electron Microscopy (TEM), Fourier Transform Infra Red (FTIR) spectroscopy, X-ray Diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS) and Vibrating Sample Magnetometer (VSM). These nano-sized particles are scrutinized for adsorption of certain chiral aromatic amino acid enantiomers namely, d- and l-tryptophan (Trp), d- and l-phenylalanine (Phe) and d- and l-tyrosine (Tyr) from phosphate buffer solutions. Adsorption capacities of the coated magnetic nanoparticles toward amino acid enantiomers are in the order: l-Trp>l-Phe>l-Tyr and under the same condition, adsorption capacities are higher for l-enantiomers than the corresponding d-enantiomers. All the equilibrium adsorption isotherms are fitted well to Freundlich model. FTIR studies depict significant changes after adsorption of amino acids onto nanoparticles. The stretching vibration frequencies of NH bonds of the amino acid molecules are changed with complex formation through host-guest interaction. The structure and hydrophobicity of amino acid molecules emphasize the interactions between amino acid molecules and the nano-adsorbents bearing cyclodextrin, thus play important roles in the difference of their adsorption behaviors.

β-Cyclodextrin conjugated magnetic, fluorescent silica core–shell nanoparticles for biomedical applications

We present synthesis of highly uniform magnetic nanocomposite material possessing an assortment of important functionalities: magnetism, luminescence, cell-targeting, and hydrophobic drug delivery. Magnetic particle Fe3O4 is encapsulated within a shell of SiO2 that ensures biocompatibility of the nanocomposite as well as act as a host for fluorescent dye (FITC), cancer-targeting ligand (folic acid), and a hydrophobic drug storage-delivering vehicle (β-cyclodextrin). Our preliminary results suggest that such core-shell nanocomposite can be a smart theranostic candidate for simultaneous fluorescence imaging, magnetic manipulation, cancer cell-targeting and hydrophobic drug delivery.

Synthesis and characterization of β-cyclodextrin-conjugated magnetic nanoparticles and their uses as solid-phase artificial chaperones in refolding of carbonic anhydrase bovine

Surface-functionalized magnetic nanoparticles are widely used in various fields of biotechnology. In this study, beta-cyclodextrin-conjugated magnetic nanoparticles (CD-APES-MNPs) are synthesized and the use of CD-APES-MNPs as a solid-phase artificial chaperone to assist protein refolding in vitro is demonstrated using carbonic anhydrase bovine (CA) as model protein. CD-APES-MNPs are fabricated by grafting mono-tosyl-beta-cyclodextrin (Ts-beta-CD) onto 3-aminopropyltriethoxysilane (APES)-modified magnetic nanoparticles (APES-MNPs). Results obtained from transmission electron microscopy (TEM) and vibrating sample magnetometery (VSM) show that the synthesized magnetic nanoparticles are superparamagnetic with a mean diameter of 11.5 nm. The beta-CD grafting is confirmed by Fourier transform infrared spectroscopy (FTIR) and elemental analysis. The amount of beta-CD grafted on the APES-MNPs is found to be 0.042 mmol g(-1) from elemental analysis. Our refolding results show that a maximum of 85% CA refolding yield can be achieved using these beta-CD-conjugated magnetic nanoparticles which is at the same level as that using liquid-phase artificial chaperone-assisted refolding. In addition, the secondary and tertiary structures of the refolded CA are the same as those of native protein under optimal conditions. These results indicate that CD-APES-MNPs are suitable and efficient stripping agents for solid-phase artificial chaperone-assisted refolding due to easier and faster separation of these nanoparticles from the refolded samples and also due to recycling of the stripping agents.

Monodisperse polymeric ionic liquid microgel beads with multiple chemically switchable functionalities.

We present simple, inexpensive microfluidics-based fabrication of highly monodisperse poly(ionic liquid) microgel beads with a multitude of functionalities that can be chemically switched in facile fashion by anion exchange and further enhanced by molecular inclusion. Specifically, we show how the exquisite control over bead size and shape enables extremely precise, quantitative measurements of anion- and solvent-induced volume transitions in these materials, a crucial feature driving several important applications. Next, by exchanging diverse anions into the synthesized microgel beads, we demonstrate stimuli responsiveness and a multitude of novel functionalities including redox response, controlled release of chemical payloads, magnetization, toxic metal removal from water, and robust, reversible pH sensing. These chemically switchable stimulus-responsive beads are envisioned to open up a vast array of potential applications in portable and preparative chemical analysis, separations and spatially addressed sensing.

Selective recognition and separation of nucleosides using carboxymethyl-β-cyclodextrin functionalized hybrid magnetic nanoparticles

A novel magnetic nanoadsorbent (CMCD-APTS-MNPs) containing the superparamagnetic and molecular recognition properties was synthesized by grafting carboxymethyl-β-cyclodextrin (CM-β-CD) on 3-aminopropyltriethoxysile (APTS) modified Fe(3)O(4) nanoparticles. The feasibility of using CMCD-APTS-MNPs as magnetic nanoadsorbent for selective adsorption of adenosine (A) and guanosine (G) based on inclusion and molecular recognition was demonstrated. The as-synthesized magnetic nanoparticles were characterized by TEM, FTIR and TGA analyses. The effects of pH and initial nucleoside concentrations on the adsorption behavior were studied. The complexation of CMCD-APTS-MNPs with both nucleosides was found to follow the Langmuir adsorption isotherm. The CMCD-APTS-MNPs showed a higher adsorption ability and selectivity for G than A under identical experimental conditions, which results from the ability of selective binding and recognition of the immobilized CM-β-CD towards G. The driving force of the separation between G and A is through the different weak interaction with grafted CM-β-CD, i.e., hydrogen bond interaction, which is evidenced by different inclusion equilibrium constants and FTIR analyses of inclusion complexes between grafted cyclodextrin and the guest molecules. Our results indicated that this nanoadsorbent would be a promising tool for easy, fast and selective separation, analysis of nucleosides and nucleotides in biological samples.

A General Route for Nanoemulsion Synthesis using Low Energy Methods at Constant Temperature

The central dogma of nanoemulsion formation using low-energy methods at constant temperature-popularly known as the emulsion inversion point (EIP) method-is that to create O/W nanoemulsions, water should be added to a mixture of an oil and surfactant. Here, we demonstrate that the above order of mixing is not universal and a reverse order of mixing could be superior, depending on the choice of surfactant and liquid phases. We propose a more general methodology to make O/W as well as W/O nanoemulsions by studying the variation of droplet size with the surfactant hydrophilic-lypophilic balance for several model systems. Our analysis shows that surfactant migration from the initial phase to the interface is the critical step for successful nanoemulsion synthesis of both O/W and W/O nanoemulsions. On the basis of our understanding and experimental results, we utilize the reverse order of mixing for two applications: (1) crystallization and formulation of pharmaceutical drugs with faster dissolution rates and (2) synthesis of alginate-based nanogels. The general route provides insights into nanoemulsion formation through low-energy methods and also opens up possibilities that were previously overlooked in the field.

Low Energy Nanoemulsions as Templates for the Formulation of Hydrophobic Drugs

Most small molecule active pharmaceutical ingredients (APIs) are hydrophobic which poses formulation challenges due to their poor water solubility. Current approaches are energy intensive and involve presenting the API in a nanoparticle form that is then combined with other additives into a stable formulation. Here, a bottom‐up and scalable method that formulates nanoparticles (crystalline or amorphous) of poorly water‐soluble APIs directly embedded in composite hydrogel beads is presented. Using nanoemulsions prepared from a low energy method as templates, the flexible approach allows to vary the embedded API nanoparticle size from 100 to 500 nm and the hydrogel bead size from 100 to 1200 µm, and subsequently achieve control over the dissolution kinetics. To better understand the dissolution process, a physical model is build that allows to collapse the kinetic data onto a master curve and predict the dependence of release rates on size of both API nanoparticles and hydrogel beads. Lastly, it is demonstrated that the dissolution kinetics of multiple drugs embedded in the same hydrogel matrix can be tuned simultaneously, an attractive property for commercial multi‐drug dosage applications. The new approach not only leads to process intensification, but also improved performance.