Preparation and Characterization of Self-Healing PVA-H2SO4 Hydrogel for Flexible Energy Storage.

In the past decade, hydrogels have attracted growing interest for emerging applications in flexible electronic devices, human-machine interactions, energy supply, or energy storage. Developing a multifunctional gel architecture with superior ionic conductivity and good mechanical flexibility is a bottleneck to overcome. Herein, poly(vinyl alcohol)/sulfuric acid (PVA-H2SO4) hydrogels were prepared via a freeze-thaw method. With the aim of tuning the formulation in view of a possible application in energy storage, the effects of different combinations in terms of the molecular weight (MW) of PVA and PVA-H2SO4 weight ratio were investigated. Moreover, exploiting the self-healing properties of these hydrogels and the easy possibility of functionalizing them, i.e., introducing a conducting polymer such as poly(2-acrylamido-2-methyl-1-propane) sulfonic acid doped polyaniline (PANI_PAMPSA), a sandwiched all-in-one double-layer hydrogel (electrode/electrolyte configuration) was prepared (PVA-H2SO4-PANI_PAMPSA/PVA-H2SO4). Results showed that the water content is independent of the PVA amount and MW; the polymer concentration has a significant effect on the formation of crystalline domains and therefore on swelling degree, whereas the cross-linking degree depends on the MW. The PVA MW has the maximum effect on the swelling percentage normalized with respect to the polymer fraction and the tensile properties of the hydrogel. The assembled all-in-one electrode/electrolyte shows promising ionic conductivity (439.7 mS cm-1) and specific capacitance performance (0.297 mF cm-2 at a current density of 0.025 mA cm-2), as well as excellent flexibility and considerable self-healing properties. These results will promote the development of self-healing symmetrical supercapacitors for storage devices in wearable electronics.

Cellulose/Zeolitic Imidazolate Framework (ZIF-8) Composites with Antibacterial Properties for the Management of Wound Infections.

Metal-organic frameworks (MOFs) are a class of crystalline porous materials with outstanding physical and chemical properties that make them suitable candidates in many fields, such as catalysis, sensing, energy production, and drug delivery. By combining MOFs with polymeric substrates, advanced functional materials are devised with excellent potential for biomedical applications. In this research, Zeolitic Imidazolate Framework 8 (ZIF-8), a zinc-based MOF, was selected together with cellulose, an almost inexhaustible polymeric raw material produced by nature, to prepare cellulose/ZIF-8 composite flat sheets via an in-situ growing single-step method in aqueous media. The composite materials were characterized by several techniques (IR, XRD, SEM, TGA, ICP, and BET) and their antibacterial activity as well as their biocompatibility in a mammalian model system were investigated. The cellulose/ZIF-8 samples remarkably inhibited the growth of Gram-positive and Gram-negative reference strains, and, notably, they proved to be effective against clinical isolates of Staphylococcus epidermidis and Pseudomonas aeruginosa presenting different antibiotic resistance profiles. As these pathogens are of primary importance in skin diseases and in the delayed healing of wounds, and the cellulose/ZIF-8 composites met the requirements of biological safety, the herein materials reveal a great potential for use as gauze pads in the management of wound infections.

A resistive sensor for humidity detection based on cellulose/polyaniline.

Ambient humidity is an important parameter that affects the manufacturing and storage of several industrial and agricultural goods. In the view of the Internet of Things (IoT), single sensors could be associated with an object for smart monitoring enabling optimum conditions to be maintained. Nevertheless, the production of cost-effective humidity sensors for indoor and outdoor environmental monitoring currently represents the main bottleneck in the development of this technology. Herein we report the results obtained with sensors exclusively made of cellulose and polyaniline (cell/PANI) under strictly controlled relative humidity (30-50 RH%) and temperature (21 ± 1 °C) achieved with a climatic chamber that simulates the conditions of indoor air humidity, and at different RH% in a lab test chamber set-up. Cell/PANI sensors, prepared with a simple, inexpensive, and easily scalable industrial paper process, show a linear trend with a slope of 1.41 µA RH%-1 and a percentage of sensitivity of 13%. Response time as well as percentage of sensitivity results are similar to those of a commercial digital-output relative humidity and temperature sensor (DHT22) employed in parallel for comparison. The commercial sensor DHT22 has a sensitivity of 14%. This low-cost sensor has potential applications in agriculture, food monitoring, and medical and industrial environments as a disposable sensor for humidity detection.

Effectiveness of Snail Slime in the Green Synthesis of Silver Nanoparticles.

The development of green, low cost and sustainable synthetic routes to produce metal nanoparticles is of outmost importance, as these materials fulfill large scale applications in a number of different areas. Herein, snail slime extracted from Helix Aspersa snails was successfully employed both as bio-reducing agent of silver nitrate and as bio-stabilizer of the obtained nanoparticles. Several trials were carried out by varying temperature, the volume of snail slime and the silver nitrate concentration to find the best biogenic pathway to produce silver nanoparticles. The best results were obtained when the synthesis was performed at room temperature and neutral pH. UV-Visible Spectroscopy, SEM-TEM and FTIR were used for a detailed characterization of the nanoparticles. The obtained nanoparticles are spherical, with mean diameters measured from TEM images ranging from 15 to 30 nm and stable over time. The role of proteins and glycoproteins in the biogenic production of silver nanoparticles was elucidated. Infrared spectra clearly showed the presence of proteins all around the silver core. The macromolecular shell is also responsible of the effectiveness of the synthesized AgNPs to inhibit Gram positive and Gram negative bacterial growth.

Hydroxyapatite Decorated with Tungsten Oxide Nanoparticles: New Composite Materials against Bacterial Growth.

The availability of biomaterials able to counteract bacterial colonization is one of the main requirements of functional implants and medical devices. Herein, we functionalized hydroxyapatite (HA) with tungsten oxide (WO3) nanoparticles in the aim to obtain composite materials with improved biological performance. To this purpose, we used HA, as well as HA functionalized with polyacrilic acid (HAPAA) or poly(ethylenimine) (HAPEI), as supports and polyvinylpyrrolidone (PVP) as stabilizing agent for WO3 nanoparticles. The number of nanoparticles loaded on the substrates was determined through Molecular Plasma-Atomic Emission Spectroscopy and is quite small, so it cannot be detected through X-ray diffraction analysis. It increases from HAPAA, to HA, to HAPEI, in agreement with the different values of zeta potential of the different substrates. HRTEM and STEM images show the dimensions of the nanoparticles are very small, less than 1 nm. In physiological solution HA support displays a greater tungsten cumulative release than HAPEI, despite its smaller loaded amount. Indeed, WO3 nanoparticles-functionalized HA exhibits a remarkable antibacterial activity against the Gram-positive Staphylococcus aureus in absence of cytotoxicity, which could be usefully exploited in the biomedical field.

A Cu(II)-MOF Based on a Propargyl Carbamate-Functionalized Isophthalate Ligand as Nitrite Electrochemical Sensor.

This paper investigates the electrochemical properties of a new Cu(II)-based metal-organic framework (MOF). Noted as Cu-YBDC, it is built upon a linker containing the propargyl carbamate functionality and immobilized on a glassy carbon electrode by drop-casting (GC/Cu-YBDC). Afterward, GC/Cu-YBDC was treated with HAuCl4 and the direct electro-deposition of Au nanoparticles was carried at 0.05 V for 600 s (GC/Au/Cu-YBDC). The performance of both electrodes towards nitrite oxidation was tested and it was found that GC/Au/Cu-YBDC exhibited a better electrocatalytic behavior toward the oxidation of nitrite than GC/Cu-YBDC with enhanced catalytic currents and a reduced nitrite overpotential from 1.20 to 0.90 V. Additionally GC/Au/Cu-YBDC showed a low limit of detection (5.0 µM), an ultrafast response time (<2 s), and a wide linear range of up to 8 mM in neutral pH.

A Cu(ii)-MOF based on a propargyl carbamate-functionalized isophthalate ligand.

A copper-based metal-organic framework (MOF) was prepared using a new linker, a 5-substituted isophthalic acid bearing a propargyl carbamate group, intended to provide a terminal alkyne function protruding from the material surface to generate supported gold species for potential catalytic applications. The novel material was fully characterized by spectroscopic analyses of different kinds: FTIR, Raman, EDX, and XPS, as well as by thermal and surface area measurements. Synchrotron X-ray diffraction data analysis, in particular, revealed that this MOF, labelled [Cu(1,3-YBDC)]·xH2O (x ∼ 2), where Y stands for the pendant alkYne and BDC for benzene dicarboxylate, contains a complex network of 5-substituted isophthalate anions bound to Cu(ii) centers, arranged in pairs within paddlewheel (or "Chinese lantern") fragments of Cu2(µ-COO)4(D)2 formulation (D being a neutral Lewis base), with a short Cu⋯Cu distance of 2.633(4) Å. Quite unexpectedly, the apical atom in the paddlewheel structure belongs to the carbamate carbonyl oxygen atom. Such extra coordination by the propargyl carbamate groups drastically reduces the MOF porosity, a feature that was also confirmed by BET measurements. However, the MOF functionality is retained at the external crystal surface where 2% of active terminal alkynes is located.

Magnetic Nanoparticles Coated with (R)-9-Acetoxystearic Acid for Biomedical Applications.

The well-known ability to selectively drive nanomagnetic materials coated with anticancer drugs into tumor cells suggested the synthesis and the characterization of magnetic nanoparticles (MNPs) functionalized with (R)-9-acetoxystearic acid, the acetic ester of (R)-9-hydroxystearic acid (9-HSA), an antiproliferative agent active against different cancer cells. The acyl chloride of (R)-9-acetoxystearic acid, synthesized in two steps from 9-HSA, was reacted with (3-aminopropyl)triethoxysilane, chosen as a linker between MNPs and the stearyl moiety. In the last step, the novel amide was bound to magnetite NPs by reaction with silyl groups. A detailed structural, chemical, and magnetic characterization of the obtained material proved that it possesses properties in agreement with the requirements for drug delivery, opening the possibility to further insights focused on the 9-HSA biomedical applications.

(9R)-9-Hydroxystearate-Functionalized Anticancer Ceramics Promote Loading of Silver Nanoparticles.

Functionalization of calcium phosphates for biomedical applications has been proposed as a strategy to enrich the good osteoinductive properties of these materials with specific therapeutic characteristics. Herein, we prepared and characterized hydroxyapatite nanocrystals functionalized with an anticancer agent, (9R)-9-hydroxystearate (HSA), and loaded with an antimicrobial agent, namely silver nanoparticles (AgNPs). Nanocrystals at two different contents of HSA, about 4 and 9 wt %, were prepared via direct synthesis in aqueous solution. Loading with the antibacterial agent was achieved through interaction with different volumes of AgNPs suspensions. The amount of loaded nanoparticles increases with the volume of the AgNPs suspension and with the hydroxystearate content of the nanocrystals, up to about 3.3 wt %. The structural, morphological, and hydrophobic properties of the composite materials depend on hydroxystearate content, whereas they are not affected by AgNPs loading. At variance, the values of zeta potential slightly increase with the content of AgNPs, which exhibit a sustained release in cell culture medium.

A new multifunctionalized material against multi-drug resistant bacteria and abnormal osteoclast activity.

The development of new biomaterials able to favor bone formation and to inhibit bone abnormal resorption is mandatory to face the increasing number of age-related musculo-skeletal disorders. Moreover, the increasing antibiotic resistance of clinically important bacteria, which is among the main causes of implant failure, requires new antimicrobial systems. In this study, we prepared multifunctional materials consisting of hydroxyapatite-zoledronate composite crystals decorated with Ag Nanoparticles (AgNPs). Zoledronate, a potent bisphosphonate widely applied for the treatment of pathologies associated to abnormal bone loss, was incorporated into hydroxyapatite up to about 8 wt%. Loading of poly(ethylenimine) - stabilized AgNPs onto the crystals was promoted by zoledronate functionalization and provoked a significant variation of the values of zeta potential. The results of in vitro tests demonstrate that the multifunctional materials combine the beneficial actions of zoledronate and AgNPs. In fact, they improve osteoblast differentiation and activity, whereas they inhibit osteoclastogenesis and osteoclast differentiation, and significantly hinder the growth of multi-drug resistant Gram positive and Gram negative bacteria. As a consequence, they can be exploited both as antiresorptive agents and as antimicrobial materials able to prevent the development of bone-associated infections.

Structural and morphological peculiarities of hybrid Au/nanodiamond engineered nanostructures.

Nanostructured Au nano-platelets have been synthesized from an Au(III) complex by growth process triggered by nanodiamond (ND). An electroless synthetic route has been used to obtain 2D Au/ND architectures, where individual nanodiamond particles are intimately embedded into face-centered cubic Au platelets. The combined use of high resolution transmission electron microscopy (HR-TEM) and selected area electron diffraction (SAED), was able to reveal the unusual organization of these hybrid nanoparticles, ascertaining the existence of preferential crystallographic orientations for both nanocrystalline species and highlighting their mutual locations. Detailed information on the sample microstructure have been gathered by fast Fourier transform (FFT) and inverse fast Fourier transform (IFFT) of HR-TEM images, allowing us to figure out the role of Au defects, able to anchor ND crystallites and to provide specific sites for heteroepitaxial Au growth. Aggregates constituted by coupled ND and Au, represent interesting systems conjugating the best optoelectronics and plasmonics properties of the two different materials. In order to promote realistically the applications of such outstanding Au/ND materials, the cooperative mechanisms at the basis of material synthesis and their influence on the details of the hybrid nanostructures have to be deeply understood.

Speciation of Gold Nanoparticles by Ex Situ Extended X-ray Absorption Fine Structure and X-ray Absorption Near Edge Structure.

A combined X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) methodology is here presented on a series of partially and fully reduced Au(III) samples. This allows monitoring the relative fraction of Au(III) and Au(0) in the studied samples, displaying a consistent and independent outcome. The strategy followed is based, for the first time, on two structural models that can be fitted simultaneously, and it evaluates the correlation among strongly correlated parameters such as coordination number and the Debye-Waller factor. The results of the present EXAFS and XANES approach can be extended to studies based on X-ray absorption spectroscopy experiments for the in situ monitoring of the formation of gold nanoclusters.

Hydrogen Adsorption Properties of Carbon Nanotubes and Platinum Nanoparticles from a New Ammonium-Ethylimidazolium Chloroplatinate Salt.

Self-supporting membranes built entirely of carbon nanotubes have been prepared by wet methods and characterized by Raman spectroscopy. The membranes are used as supports for the electrodeposition of Pt nanoparticles without the use of additional additives and/or stabilizers. The Pt precursor is an ad hoc synthesized ammonium-ethylimidazolium chloroplatinate(IV) salt, [NH3 (CH2 )2 MIM)][PtCl6 ]. The Pt complex was characterized using NMR spectroscopy, XRD, ESI-MS, and FTIR spectroscopy. The interaction between the Pt-carbon nanotubes nanocomposites and hydrogen is analyzed using electrochemical and quartz microbalance measurements under near-ambient conditions. The contribution of the Pt phase to the hydrogen adsorption on nanotube is found and explained by a kinetic model that takes into account a spillover event. Such a phenomenon may be exploited conveniently for catalysis and electrocatalysis applications in which the hybrid systems could act as a hydrogen transfer agent in specific hydrogenation reactions.

(9R)-9-Hydroxystearate-Functionalized Hydroxyapatite as Antiproliferative and Cytotoxic Agent toward Osteosarcoma Cells.

The possibility to functionalize calcium phosphates with bioactive agents is a promising strategy to design innovative biomaterials for bone repair able to couple the bioactive properties of the inorganic compounds with the therapeutic effect of the functionalizing agent. The R enantiomer of the 9-hydroxystearic acid, (9R)-9-HSA, produced from Dimorphotheca sinuata L. seeds, has proven to act as a natural negative regulator of tumor cell proliferation. On this basis, hydroxyapatite was synthesized with increasing contents of (9R)-9-hydroxystearate, up to ∼8.6 wt %. The incorporation of HSA in the composite nanocrystals induces a reduction of the crystal mean dimensions and of the length of the coherently scattering crystalline domains, which suggest a preferential adsorption onto the hydroxyapatite crystal faces parallel to the c-axis direction. The composite nanocrystals were designed so that their cytostatic and cytotoxic effects toward osteosarcoma cells were modulated by hydroxystearate content. In fact, results of in vitro tests show that the presence of HSA in the composite nanocrystals provokes a significant decrease in SaOS2 osteosarcoma cells proliferation and viability as well as an increase in lactate dehydrogenase, tumor necrosis factor α, and caspase 3 levels, with a cytotoxic effect increasing with HSA content in the nanocrystals.

Straightforward synthesis of iron cyclopentadienone N-heterocyclic carbene complexes.

Novel iron complexes bearing both cyclopentadienone and N-heterocyclic carbene ancillary ligands were obtained by a straightforward synthesis from Fe2(CO)9. The preparation represents a rare example of silver transmetallation involving iron. The reaction is general and occurs in the presence of variously functionalized NHC and cyclopentadienones.

Fluoroalkylsilanes with Embedded Functional Groups as Building Blocks for Environmentally Safer Self-Assembled Monolayers.

The fabrication of silane-based fluorinated self-assembled monolayers (FSAMs) on indium tin oxide (ITO, a transparent electrode) was carried out making use of the following fluoroalkylsilanes (FAS): 2,2,3,3,4,4,5,5,6,6,6-undecafluoro-N-[3-(trimethoxysilyl)propyl]hexanamide (1; R(F) = C5F11) and 1,1,2,2,3,3,4,4,4-nonafluoro-N-[3-(trimethoxysilyl)propyl]butane-1-sulfonamide (2; R(F) = C4F9), containing an embedded amide and a sulfonamide group, respectively, between the short perfluoroalkyl chain (R(F) with C < 6) and the syloxanic moiety. The obtained FSAM-modified/ITO systems were characterized by X-ray photoelectron spectroscopy (XPS), contact angle (CA), surface energy measurements, and electrochemical impedance spectroscopy (EIS) and compared to ITO modified with a 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyltriethoxysilane (3; R(F) = C6F13), with the perfluoroalkyl group linked to the syloxanic moiety through a simple hydrocarbon chain. The results obtained show that the presence of the -NHCO- and -NHSO2- groups have a different mode of action and, with the former, despite the short perfluoroalkyl chain, the ITO-1 system presents a CA (Θ(water )= 113.5°) and surface energy (γl = 14.0 mJ m(-2)) typical of amphiphobic materials. These properties can be exploited in a variety of applications, such as self-cleaning, anti-fouling, and anti-fingerprint coatings, and in advanced microelectronic components.

Primary amino-functionalized N-heterocyclic carbene ligands as support for Au(I)···Au(I) interactions: structural, electrochemical, spectroscopic and computational studies of the dinuclear [Au2(NH2(CH2)2imMe)2][NO3]2.

The N-heterocyclic carbene (NHC) precursor, 1-(2-aminoethyl)-3-methylimidazolium nitrate, [NH(2)(CH(2))(2)imMe)]NO(3) ([3][NO(3)]) reacted with Ag(2)CO(3) in dimethyl sulfoxide readily yielding a Ag(I)-(NHC-NH(2)) complex presenting limited stability in solution. The in situ carbene transfer reaction of the latter with [Au(tht)Cl] afforded the first example of a dinuclear gold(I) complex [Au(2)(NH(2)(CH(2))(2)imMe)(2)][NO(3)](2) ([5][NO(3)](2)) bearing a primary amino-functionalized NHC ligand. The complex has been characterized by NMR, mass spectrometry, X-ray crystallography and cyclic voltammetry; the electrochemical behaviour and photophysical properties of [5][NO(3)](2) have been also investigated and the experimental data have been compared with density functional theory (DFT) and Time Dependent (TDDFT) calculations. Single-crystal structural studies showed that the Au(I)-carbene compound contains dinuclear (AuL)(2) cations in which pairs of gold(I) centres are linked by a pair of bridging ligands, with a Au···Au aurophilic contact of 3.2332(17) Å that is maintained in solution as documented by the DFT calculations. Complex [5][NO(3)](2) is photoluminescent in solution at room temperature and the high energy emission peak at 410 nm is remarkably shifted with respect to the absorption band centered at 260 nm.

Enzyme electrodes based on sono-gel containing ferrocenyl compounds.

An amperometric-mediated glucose sensor has been developed by employing a silica sono-gel carbon composite electrode (SCC). The chosen mediators, ferrocene (Fc) and 1,2-diferrocenylethane (1), have been immobilized in the sono-gel composite matrix. The complex 1 has been employed for the first time as an electron transfer mediator for signal transduction from the active centre of the enzyme to the electrode conductive surface. After the optimisation of the construction procedure the best operative conditions for the analytical performance of the biosensor have been investigated in terms of pH, temperature and applied potential. Cyclic voltammetric and amperometric measurements have been used to study the response of both the glucose sensors, which exhibit a fast response and good reproducibility. The sensitivity to glucose is quite similar (6.7+/-0.1 microA/mM versus 5.3+/-0.1 microA/mM) when either Fc or 1 are used as mediators as are the detection limit ca. 1.0 mM (S/N=3) and the range of linear response (up to 13.0 mM). However, the dynamic range for glucose determination results wider when using 1 (up to 25.0 mM). The apparent Michaelis-Menten constants, calculated from the reciprocal plot under steady state conditions, are 27.7 and 31.6 mM for SCC-Fc/GOx and SCC-1/GOx electrodes, respectively, in agreement with a slightly higher electrocatalytic efficiency for the mediator 1.