Recent progress of metal-organic frameworks as sensors in (bio)analytical fields: towards real-world applications.

The deployment of metal-organic frameworks (MOFs) in a plethora of analytical and bioanalytical applications is a growing research area. Their unique properties such as high but tunable porosity, well-defined channels or pores, and ease of post-synthetic modification to incorporate additional functional units make them ideal candidates for sensing applications. This is possible because the interaction of analytes with a MOF often results in a change in its structure, eventually leading to a modification of the intrinsic physicochemical properties of the MOF which is then transduced into a measurable signal. The high porosity allows for the adsorption of analytes very efficiently, while the tunable pore sizes/nature and/or installation of specific recognition groups allow modulating the affinity towards different classes of compounds, which in turn lead to good sensor sensitivity and selectivity, respectively. Some figures are given to illustrate the potential of MOF-based sensors in the most relevant application fields, and future challenges and opportunities to their possible translation from academia (i.e., laboratory testing of MOF sensing properties) to industry (i.e., real-world analytical sensor devices) are critically discussed.

Sonochemically-Promoted Preparation of Silica-Anchored Cyclodextrin Derivatives for Efficient Copper Catalysis.

Silica-supported metallic species have emerged as valuable green-chemistry catalysts because their high efficiency enables a wide range of applications, even at industrial scales. As a consequence, the preparation of these systems needs to be finely controlled in order to achieve the desired activity. The present work presents a detailed investigation of an ultrasound-promoted synthetic protocol for the grafting of ß-cyclodextrin (ß-CD) onto silica. Truly, ultrasound irradiation has emerged as a fast technique for promoting efficient derivatization of a silica surface with organic moieties at low temperature. Three different ß-CD silica-grafted derivatives have been obtained, and the ability of ß-CD to direct and bind Cu when CD is bonded to silica has been studied. A detailed characterization has been performed using TGA, phenolphthalein titration, FT-IR, diffuse reflectance (DR), DR UV-Vis, as well as the inductively-coupled plasma (ICP) of the ß-CD silica-grafted systems and the relative Cu-supported catalysts. Spectroscopic characterization monitored the different steps of the reaction, highlighting qualitative differences in the properties of amino-derivatized precursors and final products. In order to ensure that the Cu-ß-CD silica catalyst is efficient and robust, its applicability in Cu(II)-catalyzed alkyne azide reactions in the absence of a reducing agent has been explored. The presence of ß-CD and an amino spacer has been shown to be crucial for the reactivity of Cu(II), when supported.

Adsorption kinetics of acetic acid into ZnO/castor oil-derived polyurethanes.

HYPOTHESIS: Materials and colloids science can provide significant contributions to the conservation of Cultural Heritage. Hybrid systems made of a castor oil-derived polymeric network and a disperse phase of zinc oxide particles (ZnO/COPs) can be more effective absorbers of acetic acid (AcOH, a major pollutant harmful to artifacts in museums and art collections) than state-of-the-art materials, provided the acid uptake mechanism by the hybrids is elucidated and optimized. The starting hypothesis was that the polymer matrix might act as transporter, while acid adsorption would take place at the ZnO particles surface. The effect of particles size was expected to play a significant role. EXPERIMENTS: The adsorption kinetics of the hybrids were studied in the 23-45˚C range, in comparison with activated charcoal, the benchmark employed by conservators. Morphological and fractal dimension of ZnO micro- and nano-particles in the hybrid networks were investigated and correlated to the adsorption kinetics. FINDINGS: The presence of a two-steps mechanism for AcOH uptake by the hybrids was demonstrated for the first time: a combination of Fickian diffusion and Case-II transport occurs in the COP matrix, and adsorption dominates acid uptake (followed by neutralization) at the particles surface. This mechanism is likely key to explain the enhanced performances of the hybrids vs activated charcoal and state-of-the-art tools to remove AcOH. The hybrids have high uptake capacity, and lower activation energies for the removal process than materials where the uptake of acid relies solely on adsorption. The size of the ZnO particles contributes to the process, i.e. nanoparticles form smaller and ramified fractal clusters that are able to adsorb AcOH more effectively than microparticles. These insights demonstrated the efficacy of the novel hybrids in art conservation, where the control of minimal concentrations of VOCs is crucial for the preventive conservation of masterpieces, and can be useful to other fields where efficient capture of acetic acid is critical (food industry, textile dyeing/printing, etc.).

Synthesis, Characterization, and Soil Burial Degradation of Biobased Polyurethanes.

There is an urgent need for developing degradable polymeric systems based on bio-derived and sustainable materials. In recent years, polyurethanes derived from castor oil have emerged due to the large availability and sustainable characteristics of castor oil. However, these polymers are normally prepared through tedious and/or energy-intensive procedures or using high volatile and/or toxic reagents such as volatile isocyanates or epoxides. Furthermore, poor investigation has been carried out to design castor oil derived polyurethanes with degradable characteristics or thorough specifically sustainable synthetic procedures. Herein, castor oil-derived polyurethane with more than 90% biomass-derived carbon content and enhanced degradable features was prepared through a simple, eco-friendly (E-factor: 0.2), and scalable procedure, employing a recently developed commercially available biomass-derived (61% bio-based carbon content) low-volatile polymeric isocyanate. The novel material was compared with a castor oil derived-polyurethane prepared with a commercially available fossil-based isocyanate counterpart. The different castor oil-derived polyurethanes were investigated by means of water uptake, soil burial degradation, and disintegration tests in compost. Characterization analyses, including thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and scanning electron microscopy (SEM), were carried out both prior to and after degradation tests. The results suggest potential applications of the degradable castor oil-derived polyurethane in different fields, such as mulch films for agricultural purposes.

Paving the Way for a Green Transition in the Design of Sensors and Biosensors for the Detection of Volatile Organic Compounds (VOCs).

The efficient and selective detection of volatile organic compounds (VOCs) provides key information for various purposes ranging from the toxicological analysis of indoor/outdoor environments to the diagnosis of diseases or to the investigation of biological processes. In the last decade, different sensors and biosensors providing reliable, rapid, and economic responses in the detection of VOCs have been successfully conceived and applied in numerous practical cases; however, the global necessity of a sustainable development, has driven the design of devices for the detection of VOCs to greener methods. In this review, the most recent and innovative VOC sensors and biosensors with sustainable features are presented. The sensors are grouped into three of the main industrial sectors of daily life, including environmental analysis, highly important for toxicity issues, food packaging tools, especially aimed at avoiding the spoilage of meat and fish, and the diagnosis of diseases, crucial for the early detection of relevant pathological conditions such as cancer and diabetes. The research outcomes presented in the review underly the necessity of preparing sensors with higher efficiency, lower detection limits, improved selectivity, and enhanced sustainable characteristics to fully address the sustainable manufacturing of VOC sensors and biosensors.

Environmentally friendly ZnO/Castor oil polyurethane composites for the gas-phase adsorption of acetic acid.

HYPOTHESIS: Acetic acid, a common pollutant present in museums and art galleries, can irreversibly damage works of art. Herein, a sustainable and scalable synthesis of zinc oxide-castor oil polyurethane hybrids (ZnO/COPs), to be used as acetic acid removers in the preventive conservation of Cultural Heritage, is reported. EXPERIMENTS: The adsorption capacities of ZnO/COPs were studied in saturated acetic acid atmosphere, at low acetic acid gas concentration, and inside a wooden crate (naturally emitting acetic acid) representative of those used in the storage deposits of museums and art collections. FINDINGS: Upon exposure, acetic acid interacts with the castor oil polyurethane and diffuses to the surface of ZnO particles where is stably fixed as zinc acetate crystals. Zinc acetate domains form homogeneously on the surface and are distributed evenly within the ZnO/COPs, thanks to weak interactions between the polyurethane matrix and acetic acid that favour the transport of the acid up to reach the zinc oxide surfaces, resulting in a synergistic effect. The ZnO/COPs composites showed significantly enhanced adsorption capacities of acetic acid surpassing those of the activated carbon benchmark, with the advantage of being easily handled and movable, without the health issues and risks associated to the use of non-confined micro/nano-powders.

Sustainable Protocol for the Reduction of Nitroarenes by Heterogeneous Au@SBA-15 with NaBH4 under Flow Conditions.

A gold-incorporated SBA-15 catalyst was prepared by a solvent-free ball-milling approach. The catalyst showed high reactivity and selectivity in the reduction of a variety of nitroarenes to anilines operating in absolute EtOH with NaBH4 as reducing agent. The catalyst was reused in batch conditions over five consecutive runs without any losses of activity or selectivity. Considering the high chemical stability and reusability of the catalytic system, a continuous-flow protocol was also investigated and defined to minimize the generation of waste and optimize the continuous reuse of the catalyst. Benefits of flow conditions were proven by turnover numbers that increased from 47.5 to 1902 and also by the minimization of both leaching (9.5 vs. 1 ppm) and E-factor values (8 vs. 23 in batch).