Advancements in Gas Separation for Energy Applications: Exploring the Potential of Polymer Membranes with Intrinsic Microporosity (PIM).

Membrane-based Polymers of Intrinsic Microporosity (PIMs) are promising candidates for energy-efficient industrial gas separations, especially for the separation of carbon dioxide over methane (CO2/CH4) and carbon dioxide over nitrogen (CO2/N2) for natural gas/biogas upgrading and carbon capture from flue gases, respectively. Compared to other separation techniques, membrane separations offer potential energy and cost savings. Ultra-permeable PIM-based polymers are currently leading the trade-off between permeability and selectivity for gas separations, particularly in CO2/CH4 and CO2/N2. These membranes show a significant improvement in performance and fall within a linear correlation on benchmark Robeson plots, which are parallel to, but significantly above, the CO2/CH4 and CO2/N2 Robeson upper bounds. This improvement is expected to enhance the credibility of polymer membranes for CO2 separations and stimulate further research in polymer science and applied engineering to develop membrane systems for these CO2 separations, which are critical to energy and environmental sustainability. This review aims to highlight the state-of-the-art strategies employed to enhance gas separation performances in PIM-based membranes while also mitigating aging effects. These strategies include chemical post-modification, crosslinking, UV and thermal treatment of PIM, as well as the incorporation of nanofillers in the polymeric matrix.

Ionic Liquids-Polymer of Intrinsic Microporosity (PIMs) Blend Membranes for CO2 Separation.

Membranes with high CO2 solubility are essential for developing a separation technology with low carbon footprint. To this end, physical blend membranes of [BMIM][Ac] and [BMIM][Succ] as Ionic Liquids (ILs) and PIM-1 as the polymer were prepared trying to combine the high permeability properties of PIM-1 with the high CO2 solubility of the chosen ILs. Membranes with a PIM-1/[BMIM][Ac] 4/1 ratio nearly double their CO2 solubility at 0.8 bar (0.86 cm3 (STP)/cm3 cmHg), while other ratios still maintain similar solubilities to PIM-1 (0.47 cm3 (STP)/cm3 cmHg). Moreover, CO2 permeability of PIM-1/[BMIM][Ac] blended membranes were between 1050 and 2090 Barrer for 2/1 and 10/1 ratio, lower than PIM-1 membrane, but still highly permeable. The here presented self-standing and mechanically resistant blend membranes have yet a lower permeability compared to PIM-1 yet an improved CO2 solubility, which eventually will translate in higher CO2/N2 selectivity. These promising preliminary results will allow us to select and optimize the best performing PIM-1/ILs blends to develop outstanding membranes for an improved gas separation technology.

A green and easy-to-assemble electrochemical biosensor based on thylakoid membranes for photosynthetic herbicides detection.

In this study, we report on an easy-to-assemble amperometric electrochemical biosensor incorporating thylakoid membranes for the detection of photosynthetic herbicides. These molecules interfere with the light-induced photosynthetic electron transport occurring at the level of the photosystems within the thylakoid membranes, thus reducing the current of the associated bioelectrode. Thylakoid membranes isolated from pea plants were adsorbed directly on a bare carbon paper working electrode and placed in the measurement cell in the absence of any electrochemical mediator, obtaining a fully environmental-friendly biodevice capable of photocurrent densities up to 14 µA/cm2. Three photosynthetic herbicides inhibiting Photosystem II and belonging to different chemical classes, namely diuron, terbuthylazine and metribuzin, were detected by measuring the electrode photocurrent, which decreased reproducibly in a concentration-dependent manner in a range between 10-7 - 5 × 10-5 M of each herbicide. The limit of detection for the three herbicides was between 4-6 × 10-7 M. Storage stability tests revealed for the biosensor a half-life longer than 15 days at 4 °C and full stability up to 4 months at -80 °C. This study provides a simple, environmental-friendly and cost-effective procedure for the fabrication of a mediatorless carbon paper-based electrochemical biosensor characterized by high photocurrents, long storage stability, reproducible detections and good sensitivity.

Assessment of the imprinting efficiency of an imide with a "stoichiometric" pyridine-based functional monomer in precipitation polymerisation.

The efficiency of the stoichiometric non-covalent imprinting of the imide 2,3,5-tri-O-acetyluridine (TAU) with 2,6-bis(acrylamido)pyridine (BAAPy) as functional monomer due to their strong donor-acceptor-donor/acceptor-donor-acceptor (DAD/ADA) hydrogen bond array interaction has been evaluated by bulk imprinting. This study is the first to investigate the imprinting and template rebinding efficiencies of the TAU/BAAPy molecularly imprinted polymeric (MIP) system prepared by precipitation polymerisation. We found that the stoichiometric 1:1 T:FM ratio has not been maintained in precipitation polymerisation and an optimal TAU:BAAPy ratio of 1:2.5 was obtained in acetonitrile without agitation affording an affinity constant (1.7 × 104 M-1 ) and a binding capacity (3.69 µmol/g) higher than its bulk counterpart. Molecular modelling, NMR studies, and selectivity assays against analogues uridine and 2,3,5-tri-O-acetyl cytidine (TAC) indicate that, aside from the DAD/ADA hydrogen bond interaction, BAAPy also interacts with the acetyl groups of TAU. Template incorporation and rebinding in precipitation MIPs are favoured by a moderate initiator concentration, ie, initiator:total monomer (I:TM) ratio of 1:131, while low I:TM ratio (ie, 1:200) drastically reduced template incorporation and binding capacity. Vigorous agitation by stirring showed higher template incorporation but significantly lower template rebinding compared to that prepared without agitation. While the imprinting efficiencies for the best performing bulk and precipitation TAU MIPs generated in this study were moderate, 41% and 60%, respectively, their rebinding capacities were only between 3 and 4% of the incorporated template. We also present quantitative nuclear magnetic resonance spectroscopy as an efficient method for MIP characterisation.

Tailor-Made Molecularly Imprinted Polymer for Selective Recognition of the Urinary Tumor Marker Pseudouridine.

Pseudouridine (Ψ) is an important urinary cancer biomarker, especially in human colorectal cancer (CRC). Disclosed herein is the first Ψ molecularly imprinted polymer (Ψ-MIP) material obtained from tailor-engineered functional monomers. The resulting MIP imprint exhibits a remarkable imprinting factor greater than 70. It is successfully used for the selective recognition of Ψ in spiked human urine. This selective functionalized material opens the route to the development of inexpensive disposable chemosensors for noninvasive CRC diagnosis and prognosis.

Carbon nano-onions as fluorescent on/off modulated nanoprobes for diagnostics.

Multishell fullerenes, known as carbon nano-onions (CNOs), have emerged as a platform for bioimaging because of their cell-penetration properties and minimal systemic toxicity. Here, we describe the covalent functionalization of CNOs with a π-extended distyryl-substituted boron dipyrromethene (BODIPY) dye with on/off modulated fluorescence emission activated by an acidic environment. The switching properties are linked to the photoinduced electron transfer (PET) characteristics of the dimethylamino functionalities attached to the BODIPY core. The on/off emission of the fluorescent CNOs is fast and reversible both in solution and in vitro, making this nanomaterial suitable as pH-dependent probes for diagnostic applications.

Recent advances in smart biotechnology: Hydrogels and nanocarriers for tailored bioactive molecules depot.

Over the past ten years, the global biopharmaceutical market has remarkably grown, with ten over the top twenty worldwide high performance medical treatment sales being biologics. Thus, biotech R&D (research and development) sector is becoming a key leading branch, with expanding revenues. Biotechnology offers considerable advantages compared to traditional therapeutic approaches, such as reducing side effects, specific treatments, higher patient compliance and therefore more effective treatments leading to lower healthcare costs. Within this sector, smart nanotechnology and colloidal self-assembling systems represent pivotal tools able to modulate the delivery of therapeutics. A comprehensive understanding of the processes involved in the self-assembly of the colloidal structures discussed therein is essential for the development of relevant biomedical applications. In this review we report the most promising and best performing platforms for specific classes of bioactive molecules and related target, spanning from siRNAs, gene/plasmids, proteins/growth factors, small synthetic therapeutics and bioimaging probes.

Evaluation of molecularly imprinted polymers using 2',3',5'-tri-O-acyluridines as templates for pyrimidine nucleoside recognition.

In this paper, we describe the synthesis and evaluation of molecularly imprinted polymers (MIPs), prepared using 2',3',5'-tri-O-acyluridines as 'dummy' templates, for the selective recognition of uridine nucleosides. The MIPs were synthesised using a non-covalent approach with 2,6-bis-acrylamidopyridine (BAAPy) acting as the binding monomer and ethylene glycol dimethacrylate (EGDMA) as the cross-linking agent. The MIPs were evaluated in terms of capacity, selectivity and specificity by analytical and frontal liquid chromatography measurements. The results obtained in organic mobile phases suggest that the nucleosides are specifically bound to the polymer by the complementary hydrogen bonding motifs of the binding monomer and the nucleoside bases. The MIPs exhibited relatively high imprinting factors for 2',3',5'-tri-O-acyluridines, while they did not show any binding capacity for other nucleosides lacking the imide moiety on their base. Moreover, the presence of ester-COO groups in the EGDMA cross-linker may lead to the formation of additional hydrogen bonds with the 2',3' and/or 5'-OH of sugar part, allowing enhancement of the recognition of the uridine nucleosides. In aqueous media, results show that the binding is driven by hydrophobic interactions.