A molecularly imprinted polymer as artificial receptor for the detection of indole-3-carbinol is reported

A molecularly imprinted polymer (MIP) for the specific retention of neopterin has been developed. A set of 6 polymers was prepared by radical polymerization under different experimental condition using methacrylic acid as functional monomer and ethylene glycol dimethacrylate as crosslinker, with the aim to understand their influence on the efficiency of the MIP. The performance of each MIP was tested in batch experiments via their binding capacity. The MIP prepared in the presence of nickel ions in dimethylsulfoxide-acetonitrile mixture (P4) exhibited the highest binding capacity for neopterin (260 μmol per gram of polymer). A selectivity study with two other pteridines demonstrated the polymer P4 also to possess the best selectivity.

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).

In the present study, it was defined the complete anthocyanins profile in Myrtus communis berries, a perennial wild shrub typical of the Mediterranean area. To the best of our knowledge, the anthocyanin composition of myrtle berries in above area has never been described. So, because of beneficial effects of these compounds reported during the last decades in the literature, an anthocyanins extraction from berries of Salento area was performed. The pigments were extracted with 0.1% HCl in methanol and purified using a C-18 solid-phase cartridge in about 24 h. High-performance liquid chromatography/electrospray ionization quadrupole time-of-flight mass spectrometry (LC/ESI-Q-TOF) method was developed optimizing chromatographic parameters in order to obtain an unequivocal identification of anthocyanins. Comparing to the conventional technologies employed for anthocyanins identification (HPLC-DAD and triple quadrupole), the Q-TOF used in this work is a last generation mass spectrometry technique that demonstrated to be able to provide accurate data on anthocyanins identification. The results obtained showed that delphinidin 3-O-glucoside represented about 31.5%, petunidin 3-O-glucoside was about 25.8%, and malvidin 3-O-glucoside represented 24.3% of the total pigments. Other anthocyanins found in minor amounts were delphinidin-pentose (4%), delphinidin-pentose (3.8%), cyanidin 3-O-glucoside (6.3%), petunidin-pentose (0.7%), petunidin-pentose (1.6%), and peonidin 3-O-glucoside (2%). The characterization of the anthocyanins profile in Myrtus communis berries of Salento, characteristic shrubs of Mediterranean region, make these fruits an excellent source of natural antioxidants compounds, which can be very useful in new biotechnological applications in food and pharmaceutical fields. © 2017, Springer Science+Business Media New York.

Cardanol is a renewable, low cost natural material, widely available as a by-product of the cashew industry. It is a mixture of 3-n-pentadecylphenol, 3-(pentadeca-8- enyl)phenol, 3-(pentadeca-8,11-dienyl)phenol and 3-(pentadeca-8,11,14-trienyl)phenol. Olefin metathesis (OM) reaction on cardanol is an important class of reactions that allows for the synthesis of new olefins that are sometime impossible to prepare via other methods. The application of this natural and renewable material to both academic and industrial research will be discussed.

This manuscript describes the preparation of green nanovesicles by using cardanol as renewable starting material with embedded minor amounts of phthalazines, a class of heterocyclic bioactive compounds. The nanovesicles were prepared by stirring induced self-assembly in aqueous medium without involvement of any organic solvent. Dynamic light scattering studies and transmission electron microscopy revealed the formation of nanostructure with an average diameter in the range of 227375 nm and a well defined spherical morphology. Potential antioxidant activity of nanovesicles were evaluated for the first time by 2,20-azino-bis-(3ethylbenzothiazoline-6-sulfonic acid) (ABTS) scavenging assay and bleomycin-dependent DNA damage. Moreover, their cytotoxic effects were also investigated by 3-[4,5-dimethylthiazole-2-yl]-2,5diphenyltetrazolium bromide (MTT) assay on different tumour cell lines. Unloaded nanovesicles showed moderate antioxidant and antitumoural activity that was further enhanced particularly by embedding the 2-[4-(4-Hydrazinophthalazin-1-yl)-phenyl]-isoindole1,3-dione compound.

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 4.20X103 M-1) and low-affinity (Ka 0.79X103 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 microg 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 micromg mL-1 of limit of detection, a linear range of 2.5–55 microg mL-1 with a relative standard deviation of 2%.

Phenolic compound content in Sorbus americana Marsh and Lonicera oblongifolia(Goldie) Hook berries was determined for the first time. An improved solid-liquid microextraction (SLME) method combining with highperformance liquid chromatography (HPLC)-diode array detector (DAD)-mass spectrometry (MS) has been developed to determine the phenolic compounds present in these berries, reducing the amount of sample, reagents, and time consumed. The major phenolic compound identified and quantified was 3-O-caffeoylquinic acid (3-CQA) in both berries. To a lesser extent, 5-Ocaffeoylquinic acid (5-CQA) and quercetin-3-O-glucoside (QG) were also determined. The existence of these phenolic compounds and the great abundance of these fruits in the northeast of North America make S. americana Marsh andL. oblongifoliaHook berries a new and excellent source of natural phenolic compounds (antioxidants), which can be very useful in biotechnological exploitation.

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.

Nicotinamide (NAM) is often added in fortified infant and various food products to ensure an adequate consumption of vitamin. Thus, a proper monitoring of NAM content in foods can be important. In this study, a selective molecularly imprinted polymer as sorbent for solid phase extraction of NAM in animal sources was successfully developed. The molecularly imprinted polymer was synthesized by bulk polymerization technique. The performances of this polymer as sorbent were investigated in NAM standard solutions. One hundred milligrams of polymer was able to retain up to 244 μg of NAM with recovery >80% when chloroform was used as loading and washing solvent and ethanol as eluting solvent. Other solvent mixtures were also tested. The optimal molecularly imprinted solid phase extraction protocol was defined and used for the clean-up of NAM in pork liver samples. Moreover, the performances of the imprinted polymer were compared with that of nonimprinted polymer and with conventional reversed-phase C18 performances. Pork liver samples spiked with 49 μg mL−1 gave a good percentage of recovery of 87%, with relative standard deviation of 8% for imprinted polymer, whereas only 12% of recovery for nonimprinted polymer and 14% of recovery for reversed-phase C18 sorbent were found

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

The degree of crystallinity of cellulose was used for assessing the degradation level of coated and uncoated samples of pine wood after weathering. X-ray diffraction (XRD) and Fourier Transform Infrared (FT-IR) spectroscopy measured the changes in the surface crystallinity of cellulose resulting from weathering, both natural and artificial. Both techniques revealed an increase in the crystallinity index (CI) of cellulose when wood was subjected to weathering. An increase in the size of crystallites was also observed by XRD measurements. These results were related to the reduction of the amorphous fractions of wood, and, consequently, to the enrichment of the relative crystalline content. Thanks to FT-IR analysis, the degradation of hemicellulose was observed for uncoated samples after exposure to artificial weathering. The effect of weathering was less evident on coated samples because of the protective action of the coating. A good correlation between the crystallinity indexes obtained from FT-IR and XRD was found. The experimental results proved that the proposed method may be a very useful tool for a rapid and accurate estimation of the degradation level of wood exposed to weathering. This methodology can find application in the field of conservation and restoration of wooden objects or in the industry of wood coatings.

The synthesis of fournewcomplexes based ontridentate bispyrazole ligand by coordinationof 4-[bis[(3 dimethyl-1H-pyrazol-1-yl)methyl]-amino]phenol with different transition metals such as Cu(NO3)2 NiCl2, CoCl2 and Cu(BF4)2 was reported. Their characterization by means of IR, UV–visible and mass spectroscopy was investigated. Their optical pollutant gases recognition capabilities as solid state thin layer on quartz were investigated. Different analytes have been studied such as SO2,NO2, CO, CH4 and NH3. The coordinated complex layer presents reversible system sensitivity towards SO2 and NO2 with good sequences in function with time. No influence on the optical properties was shown in the presence of CO, CH4 and NH3.

A new class of porphyrin(Pp)/Fe co-loaded TiO2 composites opportunely prepared by impregnation of [5,10,15,20-tetra(4-tertbutylphenyl)] porphyrin (H2Pp) or Cu(II)[5,10,15,20-tetra(4-tert-butylphenyl)] porphyrin (CuPp) onto Fe-loaded TiO2 particles showed high activities by carrying out the degradation of 4-nitrophenol (4-NP) as probe reaction in aqueous suspension under heterogeneous photo-Fenton-like reactions by using UV-visible light. e combination of porphyrin-Fe-TiO2 in the presence of H2O2 showed to be more efficient than the simple bare TiO2 or Fe-TiO2.

Novel sandwich-type phthalocyanines containing a rare earth metal core (Pr, Nd, Eu–Lu) and macrocycles peripherally substituted by pentadecylphenoxy groups were synthesized using a cardanol-based phthalonitrile precursor and the respective lanthanide acetate. Additionally, the metal free-base analog compound was studied for comparison. The purified reaction products were all found to be thick and viscous substances at room temperature, showing liquid crystalline behavior with a distinct increase in fluidity at ca. 40 °C. The complexes are readily soluble in chloroalkyl solvents and dissolve fairly well in DMF with some tendency to form aggregates. Besides they are strongly hydrophobic and reveal a peculiar affinity for lipophilic media. The compounds have been characterized by UV-Vis (absorption and emission), FTIR, MS and DSC methods. Photochemical activity in the liquid phase (dimethylformamide, dichloromethane, mineral oil) and the degree of photodegradation demonstrated under constant UV-irradiation (λ = 352 nm) have been analyzed and discussed in terms of photostability.

This study describes the preparation of ion-imprinted polymers (IIPs) for the selective removal of Hg(II) ions from aqueous media. Polymeric sorbents were prepared using different synthesis approaches to understand the influence of diphenylcarbazone (DPC), used as non-polymerizable ligand, on absorption performance. In particular, bulk polymerization was first used to prepare two polymers, IIP1 and IIP2, in the absence and presence of DPC. The trapping of the ligand in IIP2, demonstrated by Fourier Transform Infrared Spectroscopy, promotes the formation of ternary complexes with mercury ions, and 4-vinylpyridine induces an increase in binding performance, as indicated by the Kavalues (1.7 × 103±0.4 M−1 and 12.1 × 103±0.5 M−1, respectively) of IIP1 and IIP2 high affinity binding sites. A third polymer (IIP3) was also synthesized using precipitation polymerization to evaluate the contribution of morphological characteristics on absorption performance compared with the addition of DPC. Competitive studies revealed a stronger influence of IIP3 morphology on selectivity performance. Indeed, monodisperse microbeads were obtained only in this case. Finally, the applicability of the polymers to real-world samples was demonstrated through batch experiments using drinking water spiked with 1μgml−1 of Hg(II) ions, and the best removal efficiency of nearly 80% was obtained for IIP2.

Syntheses of series of heterocyclic compounds based on pyrazole units is reported. The possibility of using these compounds, as solid-state thin layers deposited on quartz substrates, for optical recognition of hazardous pollutant gases was investigated. The gases SO2, NO2, CO, CH4, and NH3 were studied. Two of the ligand layers had reversible sensitivity toward SO2, with good reaction time. The presence of CO, CH4 NO2, and NH3 had no effect on the optical properties. Morphological characterization by use of AFM microscopy was also investigated.

ABSTRACT: The meso-tetranaphthylporphyrins (TNP) derivatives, 5-(2-hydroxy-1-naphthaldehyde- 4-naphthyleneimine)-10,15,20-trinaphthylporphyrin 3, 5-(salicylidene-4-naphthyleneamine)-10,15,20- trinaphthylporphyrin 4 and 5-(thiophene-2-carboxaldehyde-4-naphthyleneimine)-10,15,20-trinaphthyl- porphyrin 5, were synthesized by the reaction of 5-(4-aminonaphthyl)-l0,15,20-trinaphthylporphyrin 2 with different aldehydes. Their photodynamic activity against K562 cells were evaluated in vitro. They displayed low levels or no dark toxicity and high phototoxicity to K562 cells, especially for 5, which offers potential application in photodynamic therapy.

Fmoc-3-nitrotyrosine (Fmoc-3-NT) molecularly imprinted polymers (MIPs) were synthesized to understand the influence of several functional monomers on the efficiency of the molecular imprinting process. Acidic, neutral and basic functional monomers, such as acrylic acid (AA), methacrylic acid (MAA), methacrylamide (MAM), 2-vinylpyridine (2-VP), 4-vinylpyridine (4-VP), have been used to synthesize five different polymers. In this study, the MIPs were tested in batch experiments by UV-visible spectroscopy in order to evaluate their binding properties. The MIP prepared with 2-VP exhibited the highest binding affinity for Fmoc-3NT, for which Scatchard analysis the highest association constant (2.49 × 104 M−1) was obtained. Furthermore, titration experiments of Fmoc-3NT into acetonitrile solutions of 2-VP revealed a stronger bond to the template, such that a total interaction is observed. Non-imprinted polymers as control were prepared and showed no binding affinities for Fmoc-3NT. The results are indicative of the importance of ionic bonds formed between the –OH residues of the template molecule and the pyridinyl groups of the polymer matrix. In conclusion, 2-VP assists to create a cavity which allows better access to the analytes.

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.

The issue of water contaminants, which affects human and environmental health, is not trivial. It is thus paramount to find new cheap and user friendly ways to detect and remove them from the environment. Here, the synthesis of a green chitosan (CS) based molecularly imprinted membrane for the detection and quantification of 4-nitrophenol (4-NO2Ph) in aqueous media is proposed. The concentration of 4-NO2Ph in a water solution was measured by HPLC analysis. CS as a functional polymer, 4-NO2Ph as template, 4-[(4-hydroxy)phenylazo]benzenesulfonic acid as ligand, and glutaraldehyde as crosslinker in the presence of polyethylene glycol as porogen were used. The membrane was characterized by SEM and Fourier transform IR analyses, which confirmed the CS and polyethylene glycol backbone of the membrane. Kinetic studies of the detection system were performed by using pseudo-first-order and pseudo-second-order models. Then, the binding efficiency between 195.33 µmol L−1 and 9235.55 µmol L−1 of 4-NO2Ph was evaluated, finding a maximum adsorption of 723.25 µmol 4-NO2Ph per gram of membrane consistent with the Qmax calculated from the Langmuir isotherm. The selectivity of the membrane versus three phenolic competitor molecules, sharing very similar molecular structure to 4-NO2Ph, was demonstrated. Finally, the applicability of the membrane to real-world samples was evaluated, by using drinking water spiked with 7.19 µmol L−1 of 4-NO2Ph, obtaining a removal efficiency of 70.6%. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry

This work is aimed to study the suitability of cardanol derivatives as plasticizers for poly(vinyl chloride), (PVC). The plasticizers are obtained by chemical modification of cardanol, a natural, renewable resource, obtained as a by-product of the cashew nut shell industry. Due to the choice of environmentally friendly chemical modification routes, partial conversion of cardanol to the target compounds was obtained. Consequently, the tested plasticizers were composed of a mixture of different cardanol derivatives. Rheological tests on PVC plastisols obtained with neat cardanol showed that cardanol must be subjected to chemical modifications, such as acetylation and epoxidation, in order to perform as an effective plasticizer. In particular, only after epoxidation, does the cardanol derivative become fully soluble in PVC. PVC plastisols obtained with such cardanol derivatives present a similar gelation temperature compared to bis (2-ethylhexyl) phthalate (DEHP) based plastisols. Mechanical properties of the flexible PVC produced by the addition of cardanol derived plasticizer after epoxidation are also comparable to those attained by the use of DEHP. Nevertheless ageing tests showed an accelerated migration of cardanol derived plasticizer, attributed to the loss of unreacted cardanol present in the plasticizer, which was in turn responsible for a significantly faster degradation of the properties, compared to flexible PVC containing DEHP. This highlights the relevance of achieving a high yield of the acetylation and epoxidation reactions, which is a relevant issue of the future research and development activities in this field.

Cardanol, a well known hazardous byproduct of the cashew industry, has been used as starting material for the synthesis of useful differently substituted “cardanol-based” porphyrins and their zinc(II), copper(II), cobalt(II) and Fe(III) complexes. Novel composites prepared by impregnation of polycrystalline TiO2 powder with an opportune amount of “cardanol-based” porphyrins, which act as sensitizers for the improvement of the photo-catalytic activity of the bare TiO2, have been used in the photodegradation in water of 4-nitrophenol (4-NP), which is a toxic and bio-refractory pollutant, dangerous for ecosystems and human health.

L’idea inventiva consiste nel creare un polimero a stampo molecolare (MIPs) capace di estrarre L-chinurenina endogena da fluidi biologici in cui è fisiologicamente presente, quali siero, urine ecc.. Il riconoscimento e l’estrazione selettiva di L-chinurenina da matrici biologiche mediante uno specifico MIPs rappresenta la caratteristica tecnica innovativa che consente di garantire laddove necessario adeguati livelli di L-chinurenina.