Advances in Nanomaterials Based on Cashew Nut Shell Liquid.

Cashew nut shell liquid (CNSL), obtained as a byproduct of the cashew industry, represents an important natural source of phenolic compounds, with important environmental benefits due to the large availability and low cost of the unique renewable starting material, that can be used as an alternative to synthetic substances in many industrial applications. The peculiarity of the functional groups of CNSL components, such as phenolic hydroxyl, the aromatic ring, acid functionality, and unsaturation(s) in the C15 alkyl side chain, permitted the design of interesting nanostructures. Cardanol (CA), anacardic acid (AA), and cardol (CD), opportunely isolated from CNSL, served as building blocks for generating an amazing class of nanomaterials with chemical, physical, and morphological properties that can be tuned in view of their applications, particularly focused on their bioactive properties.

A New Ion-Imprinted Chitosan-Based Membrane with an Azo-Derivative Ligand for the Efficient Removal of Pd(II).

Herein, we described the synthesis of a novel ion-imprinted membrane for the detection of palladium(II) prepared through the glutaraldehyde crosslinking of chitosan with a 4-[(4-Hydroxy)phenylazo]benzenesulfonic acid ligand trapped into the membrane. The imprinting technology was used to improve adsorption capacity and adsorption selectivity, and was combined with some advantages of the developed membrane, such as low cost and ease of preparation, water-friendly synthesis, and high biocompatible chitosan material. The membranes were characterized by Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM), and Energy Dispersive X-ray Spectrometry (EDS). The results obtained showed a high swelling ratio with a maximum value of 16.4 (1640%) at pH 4 with a strong pH dependence. Batch rebinding experiments gave a maximum adsorption capacity of 101.6 mg of Pd(II) per gram of imprinted membrane. The Pd(II) adsorption behavior was well-described by a Langmuir model with a theoretical maximum adsorption capacity of 93.48 mg g-1, similar to the experimental one. Finally, a selectivity study versus Ag(I), Pb(II), and Fe(III) ions demonstrated a good selectivity of chitosan-imprinted membrane towards Pd(II).

Molecularly Imprinted Composite Membranes for Selective Detection of 2-Deoxyadenosine in Urine Samples.

An important challenge for scientific research is the production of artificial systems able to mimic the recognition mechanisms occurring at the molecular level in living systems. A valid contribution in this direction resulted from the development of molecular imprinting. In this work, a novel molecularly imprinted polymer composite membrane (MIM) was synthesized and employed for the selective detection in urine samples of 2-deoxyadenosine (2-dA), an important tumoral marker. By thermal polymerization, the 2-dA-MIM was cross-linked on the surface of a polyvinylidene-difluoride (PVDF) membrane. By characterization techniques, the linking of the imprinted polymer on the surface of the membrane was found. Batch-wise guest binding experiments confirmed the absorption capacity of the synthesized membrane towards the template molecule. Subsequently, a time-course of 2-dA retention on membrane was performed and the best minimum time (30 min) to bind the molecule was established. HPLC analysis was also performed to carry out a rapid detection of target molecule in urine sample with a recovery capacity of 85%. The experiments indicated that the MIM was highly selective and can be used for revealing the presence of 2-dA in urine samples.

Developments in the synthesis of a water compatible molecularly imprinted polymer as artificial receptor for detection of 3-nitro-L-tyrosine in neurological diseases.

A highly selective water compatible molecularly imprinted polymer (MIP) for 3-nitro-L-tyrosine (3NT), an oxidative stress marker associated with neurodegenerative disorders, was prepared and its use as solid-phase extraction (SPE) sorbent material was demonstrated. The MIP was prepared by bulk polymerization using methacrylic acid as functional monomer and acetonitrile as porogen with traces of acetic acid and trifluoroacetic acid. In order to evaluate its binding properties, the MIP was analyzed by batch rebinding experiments and subsequently used as SPE sorbent for the selective clean-up and pre-concentration of 3NT from standard solutions and spiked human urine samples. The results obtained from batch rebinding experiments showed the presence of two association constants corresponding to high-affinity (Ka 4.20×10(3) M(-1)) and low-affinity (Ka 0.79×10(3) M(-1)) binding sites. Standard mixture solution loaded on MIP-SPE cartridge gave a recovery of 95% for 3NT, while the other compounds were totally eluted during washing step. Percentage of recovery higher than 90%, with relative standard deviation of 2%, was also obtained when a maximum of 55 µg of 3NT is used in spiked urine sample and loaded into the cartridge. Validation of the analytical method for 3NT quantification in human urine gave 0.7 µg mL(-1) of limit of detection, a linear range of 2.5-55 µg mL(-1) with a relative standard deviation of 2%.

Molecularly imprinted polymers: present and future prospective.

Molecular Imprinting Technology (MIT) is a technique to design artificial receptors with a predetermined selectivity and specificity for a given analyte, which can be used as ideal materials in various application fields. Molecularly Imprinted Polymers (MIPs), the polymeric matrices obtained using the imprinting technology, are robust molecular recognition elements able to mimic natural recognition entities, such as antibodies and biological receptors, useful to separate and analyze complicated samples such as biological fluids and environmental samples. The scope of this review is to provide a general overview on MIPs field discussing first general aspects in MIP preparation and then dealing with various application aspects. This review aims to outline the molecularly imprinted process and present a summary of principal application fields of molecularly imprinted polymers, focusing on chemical sensing, separation science, drug delivery and catalysis. Some significant aspects about preparation and application of the molecular imprinting polymers with examples taken from the recent literature will be discussed. Theoretical and experimental parameters for MIPs design in terms of the interaction between template and polymer functionalities will be considered and synthesis methods for the improvement of MIP recognition properties will also be presented.

Synthesis of nicotinamide-based molecularly imprinted microspheres and in vitro controlled release studies.

Nicotinamide (NAM), which is one of the two principal forms, together with nicotinic acid, of vitamin B3, is both a food nutrient and a drug. Controlled NAM release systems are useful to extend the duration of the drug's pharmacological activity and to minimize administration frequency. In this paper, molecularly imprinted polymers (MIPs) have been used as unconventional synthetic polymeric carriers, to prepare drug delivery systems for sustained release of NAM molecules. In the present study, various MIPs micro-spheres have been synthesized by using methacrylic acid as a functional monomer and ethylene glycol dimethacrylate (EGDMA) as a cross-linker. Different stoichiometric ratios of the reagents have been used, in order to evaluate their influence on NAM recognition and release properties. Non-imprinted systems have been also been prepared as controls. MIPs binding capacity has been evaluated; NAM loading and in vitro release studies, in buffer solution (pH 7.2), that mimics blood plasma conditions, have been performed. Polymer P4 has given the best results since it enables it to rebind selectively and to prolong the release of NAM with higher performance than the non-imprinted one.

Experimental and computational studies on non-covalent imprinted microspheres as recognition system for nicotinamide molecules.

Molecularly imprinted microspheres obtained by precipitation polymerization using nicotinamide (nia) as template have been prepared and characterised by SEM. How various experimental parameters can affect microsphere morphology, reaction yield and re-binding capacity have been evaluated. Pre-polymerization interactions between template and functional monomer in chloroform and MeCN have been studied by (1)H-NMR. The results suggest that the interaction between nia and methacrylic acid (MAA) is mainly based on hydrogen-bonding between amide protons and MAA. Computational density functional theory (DFT) studies on MAA-nia complexes have been also performed to better understand hydrogen-bonding interactions. The imprinted activity of the microspheres, synthesized in chloroform or acetonitrile (MeCN), has been evaluated by spectrophotometric analysis of nia solutions when chloroform or MeCN are used as incubation solvents. The results suggest that MeCN interferes with hydrogen bonding between template and MAA during either the polymerization step or re-binding process as also observed from theoretical results. Finally, the selectivity towards selected nia analogues has been also confirmed.