Chiral Recognition by Supramolecular Porphyrin-Hemicucurbit[8]uril-Functionalized Gravimetric Sensors.

Enantiorecognition of a chiral analyte usually requires the ability to respond with high specificity to one of the two enantiomers of a chiral compound. However, in most cases, chiral sensors have chemical sensitivity toward both enantiomers, showing differences only in the intensity of responses. Furthermore, specific chiral receptors are obtained with high synthetic efforts and have limited structural versatility. These facts hinder the implementation of chiral sensors in many potential applications. Here, we utilize the presence of both enantiomers of each receptor to introduce a novel normalization that allows the enantio-recognition of compounds even when single sensors are not specific for one enantiomer of a target analyte. For this purpose, a novel protocol that permits the fabrication of a large set of enantiomeric receptor pairs with low synthetic efforts by combining metalloporphyrins with (R,R)- and (S,S)-cyclohexanohemicucurbit[8]uril is developed. The potentialities of this approach are investigated by an array of four pairs of enantiomeric sensors fabricated using quartz microbalances since gravimetric sensors are intrinsically non-selective toward the mechanism of interaction of analytes and receptors. Albeit the weak enantioselectivity of single sensors toward limonene and 1-phenylethylamine, the normalization allows the correct identification of these enantiomers in the vapor phase indifferent to their concentration. Remarkably, the achiral metalloporphyrin choice influences the enantioselective properties, opening the way to easily obtain a large library of chiral receptors that can be implemented in actual sensor arrays. These enantioselective electronic noses and tongues may have a potential striking impact in many medical, agrochemical, and environmental fields.

Synthesis and Characterization of Gold Chiral Nanoparticles Functionalized by a Chiral Drug.

Inorganic chiral nanoparticles are attracting more and more attention due to their peculiar optical properties and potential biological applications, such as bioimaging, therapeutics, and diagnostics. Among inorganic chiral nanoparticles, gold chiral nanostructures were demonstrated to be very interesting in this context, with good physical chemical stability and also the possibility to decorate the surface, improving biomedical application as the interaction with the bio-systems. Gold (Au) nanostructures were synthesized according to a seed-mediated procedure which envisages the use of cetyltrimethylammonium bromide (CTAB) as the capping agent and L- and D-cysteine to promote chirality. Au nanostructures have been demonstrated to have opposite circular dichroism signals depending on the amino acid enantiomer used during the synthesis. Then, a procedure to decorate the Au surface with penicillamine, a drug used for the treatment of Wilson's disease, was developed. The composite material of gold nanoparticles/penicillamine was characterized using electron microscopy, and the penicillamine functionalization was monitored by means of UV-Visible, Raman, and infrared spectroscopy, highlighting the formation of the Au-S bond. Furthermore, electron circular dichroism was used to monitor the chirality of the synthesized nanostructures and it was demonstrated that both penicillamine enantiomers can be successfully bonded with both the enantiomers of the gold nanostructures without affecting gold nanoparticles' chirality. The effective modification of nanostructures' surfaces via penicillamine introduction allowed us to address the important issue of controlling chirality and surface properties in the chiral nano-system.

Synthesis, Functionalization and Applications of Nanocarbons.

The Special Issue "Synthesis, Functionalization and Applications of Nanocarbons" starts from the growing interest of the scientific community in carbon-based materials and the various applications of these versatile compounds [...].

Poly(l-lactide-co-caprolactone-co-glycolide)-Based Nanoparticles as Delivery Platform: Effect of the Surfactants on Characteristics and Delivery Efficiency.

Polymeric nanoparticles made of the copolymer Poly(L-lactide-co-caprolactone-co-glycolide) were prepared using the solvent evaporation method. Two different surfactants, polyvinyl alcohol and dextran, and a mixture of the two were employed. The three types of nanoparticles were used as hosting carriers of two chemotherapeutic drugs, the hydrophilic doxorubicin and the hydrophobic SN-38. The morphostructural characterization showed similar features for the three types of nanoparticles, while the drug encapsulation efficiency indicated that the dextran-based systems are the most effective with both drugs. Cellular studies with breast cancer cells were performed to compare the delivery capability and the cytotoxicity profile of the three nanosystems. The results show that the unloaded nanoparticles are highly biocompatible at the administered concentrations and confirmed that dextran-coated nanoparticles are the most efficient vectors to release the two drugs, exerting cytotoxic activity. PVA, on the other hand, shows limited drug release in vitro, probably due to strong interactions with both drugs. Data also show the release is more efficient for doxorubicin than for SN-38; indeed, the doxorubicin IC50 value for the dextran-coated nanoparticles was about 35% lower than the free drug. This indicates that these nanocarriers are suitable candidates to deliver hydrophilic drugs while needing further modification to host hydrophobic molecules.

Enantioselective Discrimination of Histidine by Means of an Achiral Cubane-Bridged Bis-Porphyrin.

A Langmuir film of cubane-bridged bisporphyrin (H2por-cubane-H2por) at the air/water interface was developed and characterized. The floating film was successfully employed for the chiral discrimination between l- and d-histidine. The enantioselective behavior persisted after the deposition of the film on a solid support using the Langmuir-Schaefer method. Distinct absorption and reflection spectra were observed in the presence of l- or d-histidine, revealing that conformational switching was governed by the interaction between H2por-cubane-H2por and the histidine enantiomer. The mechanism of chiral selection was investigated using an ad hoc modified nulling ellipsometer, indicating the anti-conformation was dominant in the presence of l-histidine, whereas the presence of d-histidine promoted the formation of tweezer conformation.

Coffee Grounds-Derived CNPs for Efficient Cr(VI) Water Remediation.

Carbon nanomaterials are a group of materials characterized by sp2/sp3 carbon backbone which, combined with surface atoms and/or chemical groups, ensures peculiar physical chemical features for a wide range of applications. Among these materials, carbon dots and carbon nanoparticles belong to carbon nanomaterials with a few nanometer dimensions. In this work, carbon nanoparticles were produced from spent coffee grounds as sustainable carbon source through a simple, cheap and eco-friendly procedure according to an oxidation process (at controlled temperature) driven by hydrogen peroxide. Atomic Force Microscope (AFM) and fluorescence, UV-Vis absorption, FT-IR and Raman spectroscopy were used to assess the formation of carbon nanomaterials of about 10 nm with the typical emission and absorption properties of carbon dots and peculiar surface features. In fact, the presence of heteroatoms, i.e., phosphorus, and the carbonyl/carboxyl surface groups on carbon nanoparticles, was proposed to confer peculiar properties allowing the fast Mn(VII) reduction to Mn(II) at neutral pH and the Cr(VI) reduction to Cr(III) in weak acid aqueous media.

Paramagnetic Functionalization of Biocompatible Scaffolds for Biomedical Applications: A Perspective.

The burst of research papers focused on the tissue engineering and regeneration recorded in the last years is justified by the increased skills in the synthesis of nanostructures able to confer peculiar biological and mechanical features to the matrix where they are dispersed. Inorganic, organic and hybrid nanostructures are proposed in the literature depending on the characteristic that has to be tuned and on the effect that has to be induced. In the field of the inorganic nanoparticles used for decorating the bio-scaffolds, the most recent contributions about the paramagnetic and superparamagnetic nanoparticles use was evaluated in the present contribution. The intrinsic properties of the paramagnetic nanoparticles, the possibility to be triggered by the simple application of an external magnetic field, their biocompatibility and the easiness of the synthetic procedures for obtaining them proposed these nanostructures as ideal candidates for positively enhancing the tissue regeneration. Herein, we divided the discussion into two macro-topics: the use of magnetic nanoparticles in scaffolds used for hard tissue engineering for soft tissue regeneration.

Applications of Photoinduced Phenomena in Supramolecularly Arranged Phthalocyanine Derivatives: A Perspective.

This review focuses on the description of several examples of supramolecular assemblies of phthalocyanine derivatives differently functionalized and interfaced with diverse kinds of chemical species for photo-induced phenomena applications. In fact, the role of different substituents was investigated in order to tune peculiar aggregates formation as well as, with the same aim, the possibility to interface these derivatives with other molecular species, as electron donor and acceptor, carbon allotropes, cyclodextrins, protein cages, drugs. Phthalocyanine photo-physical features are indeed really interesting and appealing but need to be preserved and optimized. Here, we highlight that the supramolecular approach is a versatile method to build up very complex and functional architectures. Further, the possibility to minimize the organization energy and to facilitate the spontaneous assembly of the molecules, in numerous examples, has been demonstrated to be more useful and performing than the covalent approach.

Photocatalytic Degradation of Tetracycline by ZnO/γ-Fe2O3 Paramagnetic Nanocomposite Material.

In recent years, the presence of numerous xenobiotic substances, such as antibiotics, has been detected in water environments. They can be considered as environmental contaminants, even if their effect on human health has yet to be totally understood. Several approaches have been studied for the removal of these kinds of pollutants. Among these compounds, tetracycline (TC), a broad-spectrum antibiotic, is one of the most commonly found in water due to its widespread use. In the context of reducing the presence of TC in aqueous solution, in this contribution, a composite catalyst based on zinc oxide (ZnO) and iron oxide (γ-Fe2O3) was developed and its photocatalytic properties were investigated. The catalytic materials were synthesized by a microwave-assisted aqueous solution method and characterized by Field Emission Scanning Electron Microscope (FESEM), X-Ray Fluorescence (XRF) and Brunauer-Emmett-Teller (BET) analysis. The TC concentration was evaluated by spectrophotometer measurements at specific time intervals. The performed photocatalytic experiments clearly demonstrated that the ZnO/γ-Fe2O3 composite catalyst presents significant photocatalytic activity, indeed a TC degradation efficiency of 88.52% was registered after 150 min. The presence of iron oxide in the structure of the catalyst enhances both the surface area and the pore volume, facilitating the adsorption of the analyte on the surface of nanostructures, a fundamental phase to optimize a photodegradation process. Moreover, ZnO was found to play the key role in the photocatalytic process assisted by γ-Fe2O3 which enhanced the TC degradation efficiency by 20%.

Wet Synthesis of Elongated Hexagonal ZnO Microstructures for Applications as Photo-Piezoelectric Catalysts.

It is well known that energetic demand and environmental pollution are strictly connected; the side products of vehicle and industrial exhausts are considered extremely dangerous for both human and environmental health. In the last years, the possibility to simultaneously photo-degrade water dissolved pollutants by means of ZnO nanostructures and to use their piezoelectric features to enhance the photo-degradation process has been investigated. In the present contribution, an easy and low-cost wet approach to synthetize hexagonal elongated ZnO microstructures in the wurtzite phase was developed. ZnO performances as photo-catalysts, under UV-light irradiation, were confirmed on water dissolved methylene blue dye. Piezoelectric responses of the synthetized ZnO microstructures were evaluated, as well, by depositing them into films onto flexible substrates, and a home-made layout was developed, in order to stimulate the ZnO microstructures deposited on solid supports by means of mechanical stress and UV photons, simultaneously. A relevant increment of the photo-degradation efficiency was observed when the piezopotential was applied, proposing the present approach as a completely eco-friendly tool, able to use renewable energy sources to degrade water solved pollutants.

Supramolecular Chiral Discrimination of D-Phenylalanine Amino Acid Based on a Perylene Bisimide Derivative.

The interaction between homochiral substituted perylene bisimide (PBI) molecule and the D enantiomer of phenylalanine amino acid was monitored. Spectroscopic transitions of PBI derivative in aqueous solution in the visible range were used to evaluate the presence of D-phenylalanine. UV-visible, fluorescence, FT-IR, and AFM characterizations showed that D-phenylalanine induces significant variations in the chiral perylene derivative aggregation state and the mechanism is enantioselective as a consequence of the 3D analyte structure. The interaction mechanism was further investigated in presence of interfering amino acid (D-serine and D-histidine) confirming that both chemical structure and its 3D structure play a crucial role for the amino acid discrimination. A D-phenylalanine fluorescence sensor based on perylene was proposed. A limit of detection (LOD) of 64.2 ± 0.38 nM was calculated in the range 10-7-10-5 M and of 1.53 ± 0.89 µM was obtained in the range 10-5 and 10-3 M.

Sub- and Supramolecular X-Ray Characterization of Engineered Tissues from Equine Tendon, Bovine Dermis, and Fish Skin Type-I Collagen.

Collagen represents one of the most widely used biomaterial for scaffolds fabrication in tissue engineering as it represents the mechanical support of natural tissues. It also provides physical scaffolding for cells and it influences their attachment, growth, and tissue regeneration. Among all fibrillary collagens, type I is considered one of the gold standard for scaffolds fabrication, thanks to its high biocompatibility, biodegradability, and hemostatic properties. It can be extracted by chemical and enzymatic protocols from several collagen-rich tissues, such as tendon and skin, of different animal species. Both the extraction processes and the manufacturing protocols for scaffolds fabrication provide structural and mechanical changes that can be tuned in order to deeply impact the properties of the final biomaterial. The aim of this review is to discuss the role of X-rays to study structural changes of type I collagen from fresh collagen-rich tissues (bovine, equine, fish) to the final scaffolds, with the aim to screen across available collagen sources and scaffolds fabrication protocols to be used in tissue regeneration.

An insight on type I collagen from horse tendon for the manufacture of implantable devices.

Type I collagen is the most abundant protein of the human body. Due to its favourable properties, collagen extracted from animal tissues is adopted to manufacture a wide range of devices for biomedical applications. Compared to bovine and porcine collagens, which are the most largely used, equine collagen is free from the risk of zoonosis, has no reported immune reactions, and has not religious constraints. In this work, a recently available type I collagen extracted from horse tendon was evaluated and compared with a commercially available collagen isoform derived from the same species and tissue. Detailed physical, chemical and biological investigations were performed, in agreement with the requirements of the current standard for the characterization of type I collagen to be used for the manufacture of Tissue Engineering Medical Products. To the best of our knowledge, this is the first report on the complete primary structure of the investigated collagen.

Investigations of Processing-Induced Structural Changes in Horse Type-I Collagen at Sub and Supramolecular Levels.

The aim of this work is to evaluate the effects of different extraction and material processing protocols on the collagen structure and hierarchical organization of equine tendons. Wide and Small Angle X-ray Scattering investigations on raw powders and thin films revealed that not only the extraction and purification treatments, but also the processing conditions may affect the extent of the protein crystalline domain and induce a nanoscale "shield effect." This is due to the supramolecular fiber organization, which protects the atomic scale structure from the modifications that occur during fabrication protocols. Moreover, X-ray analyses and Fourier Transform Infrared spectroscopy performed on the biomaterial sheds light on the relationship between processing conditions, triple helical content and the organization in atomic and nanoscale domains. It was found that the mechanical homogenization of the slurry in acidic solution is a treatment that ensures a high content of super-organization of collagen into triple helices and a lower crystalline domain in the material. Finally, mechanical tensile tests were carried out, proving that the acidic solution is the condition which most enhances both mechanical stiffness and supramolecular fiber organization of the films.

SiO2 -Coated ZnO Nanoflakes Decorated with Ag Nanoparticles for Photocatalytic Water Oxidation.

Many strategies have been adopted to improve the photoinduced features of zinc oxide nanostructures for different application fields. In this work, zinc oxide has been synthesised and decorated by plasmonic metal nanoparticles to enhance its photocatalytic activity in the visible range. Furthermore, an insulating layer of SiO2 has been grown between the surface of zinc oxide nanoflakes and silver nanoparticles. A synthetic procedure that allows the accurate modulation of the insulating layer thickness in the range 5-40 nm has been developed. Evidences highlight the crucial role of the SiO2 layer in dramatically increasing photocatalytic water oxidation promoted by the nanostructure under both UV and visible illumination. An ideal thickness value of about 10 nm has been demonstrated to guarantee the plasmon-induced resonance energy-transfer process and to quench the Förster resonance energy-transfer mechanism; thus, optimising the local surface plasmon resonance effect and water oxidation properties.

Singlet oxygen photo-production by perylene bisimide derivative Langmuir-Schaefer films for photodynamic therapy applications.

A perylene bisimide (PBI) derivative was utilized as photosensitizer for photodynamic therapy (PDT) applications, due to its high efficiency in singlet oxygen generation upon photoexcitation. It was immobilized onto a hydrophobized solid support, by means of the Langmuir-Schaefer (LS) technique, to achieve a preliminary medical device able to induce death of cancer cells in vitro. First, PBI derivative solutions, at two different concentrations (4.2 × 10-5 and 1.5 × 10-4 M) were chosen, based on the different PBI aggregation state, to be spread onto a water subphase in a Langmuir trough. Physico-chemical and morphological characterizations of the floating films were performed. Then the floating layers were transferred onto quartz substrates. The resulting multilayer LS films were characterized by spectroscopic measurements showing that the photochemical properties of the PBI derivative were well preserved even when immobilized. The LS film that exhibited the highest efficiency in the singlet oxygen production under light excitation was assessed in in vitro tests on human cervical carcinoma C13 cell line and the photo-toxicity was measured. This study revealed absence of cytotoxicity in dark conditions and a high photo-cytotoxicity toward cancer cells, making it a promising photoactive device.

Perylene Bisimide Aggregates as Probes for Subnanomolar Discrimination of Aromatic Biogenic Amines.

Perylene bisimide derivatives show peculiar physical chemical features, such as a highly conjugated system, high extinction coefficients and elevated fluorescence quantum yields, making them suitable for the development of optical sensors of compounds of interest. In particular, they are characterized by the tendency to aggregate into π-π stacked supramolecular structures. In this contribution, the behavior of the PBI derivative N, N'-bis(2-(trimethylammonium)ethylene)perylene bisimide dichloride was investigated both in aqueous solution and on solid support. The electronic communication between PBI aggregates and biogenic amines was exploited in order to discriminate aromatic amines down to subnanomolar concentrations by observing PBI fluorescence variations in the presence of various amines and at different concentrations. The experimental findings were corroborated by density functional theory calculations. In particular, phenylethylamine and tyramine were demonstrated to be selectively detected down to 10-10 M concentration. Then, in order to develop a surface plasmon resonance (SPR) device, PBI was deposited onto a SPR support by means of the layer-by-layer method. PBI was deposited in the aggregated form and was demonstrated to preserve the capability to discriminate, selectively and with an outstanding analytical sensitivity, tyramine in the vapor phase and even if mixed with other aromatic amines.

Carbon nanodot-based heterostructures for improving the charge separation and the photocurrent generation.

The possibility to employ carbon nanodots (CNDs) in solar devices was exploited by combining them with a fulleropyrrolidine derivative (FP2). The interaction between the two species was promoted by the presence of opposite electrostatic charges on CNDs (negatively charged) and FP2 (positively charged). The supramolecular dyad CNDs/FP2 generation was induced at the air/water interface of a Langmuir trough: water soluble CNDs were dissolved in the subphase and FP2 chloroform solution was spread on the subphase; the electrostatic interaction promoted the formation of the supramolecular adduct FP2/CNDs, which was then transferred onto solid substrates. Photo-induced charge transfer was promoted in the FP2/CNDs dyad and we demonstrated that the presence of CNDs increased the short-circuit current density, under light illumination, of a porphyrin-FP2/CNDs thin film by about 300% when compared with a more traditional porphyrin-FP2 solar device.

The role of the central metal ion of ethane-bridged bis-porphyrins in histidine sensing.

Ethane-bridged bis-porphyrin derivatives are reported for the selective detection of various analytes in sensing applications. The central metal ion is able to rule specific molecular arrangements upon analyte binding. Three bis-porphyrin compounds: a free base (metal free), Ni complex, and Cu complex, have been tested for histidine detection in aqueous media. Histidine is involved in various biological processes, including such deadly disease as lung cancer. The conformational changes of bis-porphyrins, induced by histidine binding, can be detected by monitoring the Soret band position. The spectroscopic characterization, at the air-water subphase interface, indicates that, in the presence of histidine, the Ni and Cu metallated derivatives undergo conformational changes. This behaviour was confirmed when these two derivatives were deposited onto the solid support by Langmuir-Schaefer (LS) technique. A prototypal Surface Plasmon Resonance (SPR) detection system for histidine based on these two porphyrin LS films was developed. The Cu substituted compound based SPR system allows the histidine sensing down to nanomolar concentration. Furthermore, a SPR response of the Ni bis-porphyrin shows a semilogarithmic dependence on the histidine concentration up to 10-6 M proposing the use of these two porphyrins in a sensor array for the monitoring of histidine levels in plasma.

Atypical Film-Forming Behavior of Soluble Tetra-3-Nitro-Substituted Copper Phthalocyanine.

Thin films of metal phthalocyanines (MPc) are known to exhibit excellent physical properties but poorly controlled morphologies. Therefore, the present work seeks to understand the film growth mechanism of a model compound for potentially usable MPc, specifically, copper tetra(3-nitro-5-tert-butyl)phthalocyanine (CuPc*). The Langmuir-Schaefer (LS) technique was applied to prepare a series of CuPc* films under different processing conditions. The film growth was examined by Brewster angle microscopy (BAM) on the water surface and small-angle X-ray scattering (SAXS) from the solid films. Neutron reflectometry (NR) measurements of the water uptake into the films and computer simulation of hydrated CuPc* were performed to substantiate an idea of colloidal MPc-water aggregates as nanoscale precursors of smooth solid films. This idea appears fruitful in terms of materials chemistry.