Correction: Diamond nanowires modified with poly[3-(pyrrolyl)carboxylic acid] for the immobilization of histidine-tagged peptides.

Correction for 'Diamond nanowires modified with poly[3-(pyrrolyl)carboxylic acid] for the immobilization of histidine-tagged peptides' by Palaniappan Subramanian et al., Analyst, 2014, 139, 4343-4349, https://doi.org/10.1039/C4AN00146J.

Solar-Driven Ammonia Production through Engineering of the Electronic Structure of a Zr-Based MOF.

As a hydrogen carrier and a vital component in fertilizer production, ammonia (NH3) is set to play a crucial role in the planet's future. While its industrial production feeds half of the global population, it uses fossil fuels and emits greenhouse gases. To tackle this issue, photocatalytic nitrogen fixation using visible light is emerging as an effective alternative method. This strategy avoids carbon dioxide (CO2) emissions and harnesses the largest share of sunlight. In this work, we successfully incorporated a 5-nitro isophthalic acid linker into MOF-808 to introduce structural defects and open metal sites. This has allowed modulation of the electronic structure of the MOF and effectively reduced the band gap energy from 3.8 to 2.6 eV. Combination with g-C3N4 enhanced further NH3 production, as these two materials possess similar band gap energies, and g-C3N4 has shown excellent performance for this reaction. The nitro groups serve as acceptors, and their integration into the MOF structure allowed effective interaction with the free electron pairs on N-(C)3 in the g-C3N4 network nodes. Based on DFT calculations, it was concluded that the adsorption of N2 molecules on open metal sites caused a decrease in their triple bond energy. The modified MOF-808 showed superior performance compared with the other MOFs studied in terms of N2 photoreduction under visible light. This design concept offers valuable information about how to engineer band gap energy in MOF structures and their combination with appropriate semiconductors for solar-powered photocatalytic reactions, such as N2 or CO2 photoreduction.

Graphene-based field-effect transistors for biosensing: where is the field heading to?

Two-dimensional (2D) materials hold great promise for future applications, notably their use as biosensing channels in the field-effect transistor (FET) configuration. On the road to implementing one of the most widely used 2D materials, graphene, in FETs for biosensing, key issues such as operation conditions, sensitivity, selectivity, reportability, and economic viability have to be considered and addressed correctly. As the detection of bioreceptor-analyte binding events using a graphene-based FET (gFET) biosensor transducer is due to either graphene doping and/or electrostatic gating effects with resulting modulation of the electrical transistor characteristics, the gFET configuration as well as the surface ligands to be used have an important influence on the sensor performance. While the use of back-gating still grabs attention among the sensor community, top-gated and liquid-gated versions have started to dominate this area. The latest efforts on gFET designs for the sensing of nucleic acids, proteins and virus particles in different biofluids are presented herewith, highlighting the strategies presently engaged around gFET design and choosing the right bioreceptor for relevant biomarkers.

State of the art and future research directions of materials science applied to electrochemical biosensor developments.

Centralized laboratories in which analytical processes are automated to enable the analysis of large numbers of samples at relatively low cost are used for analytical testing throughout the world. However, healthcare is changing, partly due to the general recognition that care needs to be more patient-centered and putting the patient at the center of action. One way to achieve this goal is to consider point-of-care testing (PoC) devices as alternative analytical concepts. This requires miniaturization of current analytical concepts and the use of cost-effective diagnostic tools with appropriate sensitivity and specificity. Electrochemical sensors are ideally adapted as they provide robust, low-cost, and miniaturized solutions for the detection of variable analytes, yet lack the high sensitivity comparable to more classical diagnosis approaches. Advances in nanotechnology have opened up a plethora of different nanomaterials to be applied as electrode and/or sensing materials in electrochemical biosensors. The choice of materials significantly influences the sensor's sensitivity, selectivity, and overall performance. A critical review of the state of the art with respect to the development of the utilized materials (between 2019 and 2023) and where the field is heading to are the focus of this article.

Nanoparticles and Nanocolloidal Carbon: Will They Be the Next Antidiabetic Class That Targets Fibrillation and Aggregation of Human Islet Amyloid Polypeptide in Type 2 Diabetes?

Nanotechnology is revolutionizing human medicine. Nanoparticles (NPs) are currently used for treating various cancers, for developing vaccines, and for imaging, and other promises offered by NPs might come true soon. Due to the interplay between NPs and proteins, there is more and more evidence supporting the role of NPs for treating amyloid-based diseases. NPs can induce some conformational changes of the adsorbed protein molecules via various molecular interactions, leading to inhibition of aggregation and fibrillation of several and different amyloid proteins. Though an in depth understanding of such interactions between NPs and amyloid structures is still lacking, the inhibition of protein aggregation by NPs represents a new generation of innovative and effective medicines to combat metabolic diseases such as type 2 diabetes (T2D). Here, we lay out advances made in the field of T2D notably for optimizing protein aggregation inhibition strategies. This Account covers discussions about the current understanding of ß-cells, the insulin producing cells within the pancreas, under diabetic conditions, notably increased glucose and fatty acid levels, and the implication of these conditions on the formation of human islet amyloid polypeptide (hIAPP) amylin oligomers and aggregates. Owing to the great potential of carbon nanostructures to interfere with protein aggregation, an important part of this Account will be devoted to the state of the art of therapeutic options in the form of emerging nanomaterials-based amyloidosis inhibitors. Our group has recently made some substantial progress in this regard by investigating the impact of glucose and fatty acid concentrations on hIAPP aggregation and ß-cell toxicity. Furthermore, the great potential of carbon nanocolloids in reversing hIAPP aggregation under diabetic conditions will be highlighted as the approach has been validated on ß-cell cultures from rats. We hope that this Account will evoke new ideas and concepts in this regard. We give some lead references below on pancreatic ß-cell aspects and carbon quantum dots for managing diabetics and nanomedicine related aspects, a topic of interest in our laboratory.

In Vitro and Ex Vivo Models for Assessing Drug Permeation across the Cornea.

Drug permeation across the cornea remains a major challenge due to its unique and complex anatomy and physiology. Static barriers such as the different layers of the cornea, as well as dynamic aspects such as the constant renewal of the tear film and the presence of the mucin layer together with efflux pumps, all present unique challenges for effective ophthalmic drug delivery. To overcome some of the current ophthalmic drug limitations, the identification and testing of novel drug formulations such as liposomes, nanoemulsions, and nanoparticles began to be considered and widely explored. In the early stages of corneal drug development reliable in vitro and ex vivo alternatives, are required, to be in line with the principles of the 3Rs (Replacement, Reduction, and Refinement), with such methods being in addition faster and more ethical alternatives to in vivo studies. The ocular field remains limited to a handful of predictive models for ophthalmic drug permeation. In vitro cell culture models are increasingly used when it comes to transcorneal permeation studies. Ex vivo models using excised animal tissue such as porcine eyes are the model of choice to study corneal permeation and promising advancements have been reported over the years. Interspecies characteristics must be considered in detail when using such models. This review updates the current knowledge about in vitro and ex vivo corneal permeability models and evaluates their advantages and limitations.

Exhaled breath condensate as bioanalyte: from collection considerations to biomarker sensing.

Since the SARS-CoV-2 pandemic, the potential of exhaled breath (EB) to provide valuable information and insight into the health status of a person has been revisited. Mass spectrometry (MS) has gained increasing attention as a powerful analytical tool for clinical diagnostics of exhaled breath aerosols (EBA) and exhaled breath condensates (EBC) due to its high sensitivity and specificity. Although MS will continue to play an important role in biomarker discovery in EB, its use in clinical setting is rather limited. EB analysis is moving toward online sampling with portable, room temperature operable, and inexpensive point-of-care devices capable of real-time measurements. This transition is happening due to the availability of highly performing biosensors and the use of wearable EB collection tools, mostly in the form of face masks. This feature article will outline the last developments in the field, notably the novel ways of EBA and EBC collection and the analytical aspects of the collected samples. The inherit non-invasive character of the sample collection approach might open new doors for efficient ways for a fast, non-invasive, and better diagnosis.

Enhanced diabetic wound healing using platelet-derived extracellular vesicles and reduced graphene oxide in polymer-coordinated hydrogels.

Impaired wound healing is a significant complication of diabetes. Platelet-derived extracellular vesicles (pEVs), rich in growth factors and cytokines, show promise as a powerful biotherapy to modulate cellular proliferation, angiogenesis, immunomodulation, and inflammation. For practical home-based wound therapy, however, pEVs should be incorporated into wound bandages with careful attention to delivery strategies. In this work, a gelatin-alginate hydrogel (GelAlg) loaded with reduced graphene oxide (rGO) was fabricated, and its potential as a diabetic wound dressing was investigated. The GelAlg@rGO-pEV gel exhibited excellent mechanical stability and biocompatibility in vitro, with promising macrophage polarization and reactive oxygen species (ROS)-scavenging capability. In vitro cell migration experiments were complemented by in vivo investigations using a streptozotocin-induced diabetic rat wound model. When exposed to near-infrared light at 2 W cm- 2, the GelAlg@rGO-pEV hydrogel effectively decreased the expression of inflammatory biomarkers, regulated immune response, promoted angiogenesis, and enhanced diabetic wound healing. Interestingly, the GelAlg@rGO-pEV hydrogel also increased the expression of heat shock proteins involved in cellular protective pathways. These findings suggest that the engineered GelAlg@rGO-pEV hydrogel has the potential to serve as a wound dressing that can modulate immune responses, inflammation, angiogenesis, and follicle regeneration in diabetic wounds, potentially leading to accelerated healing of chronic wounds.

Photocatalytic Performance of Perovskite and Metal-Organic Framework Hybrid Material for the Reduction of N2 to Ammonia.

The orthorhombic phase of KNbO3 perovskite has been applied for nitrogen (N2) photoreduction to ammonia (NH3). However, this material suffers from a low surface area and low ammonia production efficiency under UV light irradiation. To eliminate these barriers, we used a metal-organic framework (MOF), named as TMU-5 ([Zn(OBA)(BPDH)0.5]n·1.5DMF, where H2OBA = 4,4'-oxybis(benzoic acid) and BPDH = 2,5-bis(4-pyridyl)-3,4-diaza-2,4-hexadiene), for the synthesis of the KNbO3@TMU-5 hybrid material. KNbO3@TMU-5 achieved a NH3 production rate of 39.9 µmol·L-1·h-1·g-1 upon UV light irradiation, as compared to 20.5 µmol·L-1·h-1·g-1 recorded for KNbO3 under similar experimental conditions. Using different characterization techniques especially gas adsorption, cyclic voltammetry, X-ray photoelectron spectroscopy, photocurrent measurements, and Fourier transform infrared spectroscopy, it has been found that the higher photoactivity of KNbO3@TMU-5 in ammonia production is due to its higher surface area, higher electron-hole separation efficiency, and higher density of negative charges on Nb sites. This work shows that hybridization of conventional semiconductors (SCs) with photoactive MOFs can improve the photoactivity of the SC@MOF hybrid material in different reactions, especially kinetically complex reactions like photoconversion of nitrogen to ammonia.

The role of the surface ligand on the performance of electrochemical SARS-CoV-2 antigen biosensors.

Point-of-care (POC) technologies and testing programs hold great potential to significantly improve diagnosis and disease surveillance. POC tests have the intrinsic advantage of being able to be performed near the patient or treatment facility, owing to their portable character. With rapid results often in minutes, these diagnostic platforms have a high positive impact on disease management. POC tests are, in addition, advantageous in situations of a shortage of skilled personnel and restricted availability of laboratory-based analytics. While POC testing programs are widely considered in addressing health care challenges in low-income health systems, the ongoing pandemic of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) infections could largely benefit from fast, efficient, accurate, and cost-effective point-of-care testing (POCT) devices for limiting COVID-19 spreading. The unrestrained availability of SARS-CoV-2 POC tests is indeed one of the adequate means of better managing the COVID-19 outbreak. A large number of novel and innovative solutions to address this medical need have emerged over the last months. Here, we critically elaborate the role of the surface ligands in the design of biosensors to cope with the current viral outbreak situation. Their notable effect on electrical and electrochemical sensors' design will be discussed in some given examples. Graphical abstract.

Electrochemical and electronic detection of biomarkers in serum: a systematic comparison using aptamer-functionalized surfaces.

Sensitive and selective detection of biomarkers in serum in a short time has a significant impact on health. The enormous clinical importance of developing reliable methods and devices for testing serum levels of cardiac troponin I (cTnI), which are directly correlated to acute myocardial infarction (AMI), has spurred an unmatched race among researchers for the development of highly sensitive and cost-effective sensing formats to be able to differentiate patients with early onset of cardiac injury from healthy individuals with a mean cTnI level of 26 pg mL-1. Electronic- and electrochemical-based detection schemes allow for fast and quantitative detection not otherwise possible at the point of care. Such approaches rely largely on voltammetric and field-effect-based readouts. Here, we systematically investigate electric and electrochemical point-of-care sensors for the detection of cTnI in serum samples by using the same surface receptors, cTnI aptamer-functionalized CVD graphene-coated interdigated gold electrodes. The analytical performances of both sensors are comparable with a limit of detection (LoD) of 5.7 ± 0.6 pg mL-1(electrochemical) and 3.3 ± 1.2 pg mL-1 (electric). However, both sensors exhibit different equilibrium dissociation constant (KD) values between the aptamer-linked surface receptor and the cTnI analyte, being 160 pg mL-1 for the electrochemical and about three times lower for the electrical approach with KD = 51.4 pg mL-1. This difference is believed to be related to the use of a redox mediator in the electrochemical sensor for readout. The ability of the redox mediator to diffuse from the solution to the surface via the cTnI/aptamer interface is hindered, correlating to higher KD values. In contrast, the electric readout has the advantage of being label-free with a sensing limitation due to ionic strength effects, which can be limited using poly(ethylene) glycol surface ligands.

Effective PDT/PTT dual-modal phototherapeutic killing of bacteria by using poly(N-phenylglycine) nanoparticles.

This study investigated, for the first time, the antimicrobial properties of polyethylene glycol-functionalized poly(N-phenylglycine) nanoparticles (PNPG-PEG NPs). PNPG-PEG NPs exhibit high extinction coefficient in the near-infrared (NIR) region; they can convert light energy into heat energy with high thermal transformation efficiency. Additionally, they can generate cytotoxic reactive oxygen species (ROS) upon light irradiation. Also, PNPG-PEG NPs are not cytotoxic. All these properties make them appropriate for combined dual-modal photothermal and photodynamic therapies. The antibacterial activity of PNPG-PEG NPs was assessed using Escherichia coli (Gram-negative) and Staphylococcus aureus (Gram-positive) pathogenic strains. The results revealed that NIR light (810 nm) irradiation for 10 min could kill effectively the planktonic bacteria and destroy Escherichia coli and Staphylococcus aureus biofilms. The results demonstrated that PNPG-PEG NPs represent a very effective nanoplatform for killing of pathogenic bacteria.

The impact of chemical engineering and technological advances on managing diabetes: present and future concepts.

Monitoring blood glucose levels for diabetic patients is critical to achieve tight glycaemic control. As none of the current antidiabetic treatments restore lost functional ß-cell mass in diabetic patients, insulin injections and the use of insulin pumps are most widely used in the management of glycaemia. The use of advanced and intelligent chemical engineering, together with the incorporation of micro- and nanotechnological-based processes have lately revolutionized diabetic management. The start of this concept goes back to 1974 with the description of an electrode that repeatedly measures the level of blood glucose and triggers insulin release from an infusion pump to enter the blood stream from a small reservoir upon need. Next to the insulin pumps, other drug delivery routes, including nasal, transdermal and buccal, are currently investigated. These processes necessitate competences from chemists, engineers-alike and innovative views of pharmacologists and diabetologists. Engineered micro and nanostructures hold a unique potential when it comes to drug delivery applications required for the treatment of diabetic patients. As the technical aspects of chemistry, biology and informatics on medicine are expanding fast, time has come to step back and to evaluate the impact of technology-driven chemistry on diabetics and how the bridges from research laboratories to market products are established. In this review, the large variety of therapeutic approaches proposed in the last five years for diabetic patients are discussed in an applied context. A survey of the state of the art of closed-loop insulin delivery strategies in response to blood glucose level fluctuation is provided together with insights into the emerging key technologies for diagnosis and drug development. Chemical engineering strategies centered on preserving and regenerating functional pancreatic ß-cell mass are evoked in addition as they represent a permanent solution for diabetic patients.

Non-enzymatic electrochemical cholesterol sensor based on strong host-guest interactions with a polymer of intrinsic microporosity (PIM) with DFT study.

Advances in materials science have accelerated the development of diagnostic tools with the last decade witnessing the development of enzyme-free sensors, owing to the improved stability, low cost and simple fabrication of component materials. However, the specificity of non-enzymatic sensors for certain analytes still represents a challenging task, for example the determination of cholesterol level in blood is vital due to its medical relevance. In this work, a reagent displacement assay for cholesterol sensing in serum samples was developed. It is based on coating of a glassy carbon electrode with a polymer of intrinsic microporosity (PIM) that forms a host-guest complex with methylene blue (MB). In the presence of cholesterol, the MB electroactive probe was displaced due to the stronger association of cholesterol guest to the PIM host. The decrease in the oxidative current was proportional to the cholesterol concentration achieving a detection limit of approximately 0.1 nM. Moreover, to further assist the experimental studies, comprehensive theoretical calculations are also performed by using density functional theory (DFT) calculations.

Reduced graphene oxide-based field effect transistors for the detection of E7 protein of human papillomavirus in saliva.

Several challenging biological sensing concepts have been realized using electrolyte-gated reduced graphene oxide field effect transistors (rGO-FETs). In this work, we demonstrate the interest of rGO-FET for the sensing of human papillomavirus (HPV), one of the most common sexually transmitted viruses and a necessary factor for cervical carcinogenesis. The highly sensitive and selective detection of the HPV-16 E7 protein relies on the attractive semiconducting characteristics of pyrene-modified rGO functionalized with RNA aptamer Sc5-c3. The aptamer-functionalized rGO-FET allows for monitoring the aptamer-HPV-16 E7 protein binding in real time with a detection limit of about 100 pg mL-1 (1.75 nM) for HPV-16 E7 from five blank noise signals (95% confidence level). The feasibility of this method for clinical application in point-of-care technology is evaluated using HPV-16 E7 protein suspended in saliva and demonstrates the successful fabrication of a promising field effect transistor biosensor for HPV diagnosis.Graphical abstract.

SERS characterization of aggregated and isolated bacteria deposited on silver-based substrates.

Surface-enhanced Raman scattering (SERS), based on the enhancement of the Raman signal of molecules positioned within a few nanometres from a structured metal surface, is ideally suited to provide bacterial-specific molecular fingerprints which can be used for analytical purposes. However, for some complex structures such as bacteria, the generation of reproducible SERS spectra is still a challenging task. Among the various factors influencing the SERS variability (such as the nature of SERS-active substrate, Raman parameters and bacterial specificity), we demonstrate in this study that the environment of Gram-positive and Gram-negative bacteria deposited on ultra-thin silver films also impacts the origin of the SERS spectra. In the case of densely packed bacteria, the obtained SERS signatures were either characteristic of the secretion of adenosine triphosphate for Staphylococcus aureus (S. aureus) or the cell wall and the pili/flagella for Escherichia coli (E. coli), allowing for an easy discrimination between the various strains. In the case of isolated bacteria, SERS mapping together with principal component analysis revealed some variabilities of the spectra as a function of the bacteria environment and the bactericidal effect of the silver. However, the variability does not preclude the SERS signatures of various E. coli strains to be discriminated.

Dual Monitoring of Surface Reactions in Real Time by Combined Surface-Plasmon Resonance and Field-Effect Transistor Interrogation.

By combining surface plasmon resonance (SPR) and electrolyte gated field-effect transistor (EG-FET) methods in a single analytical device we introduce a novel tool for surface investigations, enabling simultaneous measurements of the surface mass and charge density changes in real time. This is realized using a gold sensor surface that simultaneously serves as a gate electrode of the EG-FET and as the SPR active interface. This novel platform has the potential to provide new insights into (bio)adsorption processes on planar solid surfaces by directly relating complementary measurement principles based on (i) detuning of SPR as a result of the modification of the interfacial refractive index profile by surface adsorption processes and (ii) change of output current as a result of the emanating effective gate voltage modulations. Furthermore, combination of the two complementary sensing concepts allows for the comparison and respective validation of both analytical techniques. A theoretical model is derived describing the mass uptake and evolution of surface charge density during polyelectrolyte multilayer formation. We demonstrate the potential of this combined platform through the observation of layer-by-layer assembly of PDADMAC and PSS. These simultaneous label-free and real-time measurements allow new insights into complex processes at the solid-liquid interface (like non-Fickian ion diffusion), which are beyond the scope of each individual tool.

Formation of a Highly Stable and Nontoxic Protein Corona upon Interaction of Human α-1-Acid Glycoprotein (AGP) with Citrate-Stabilized Silver Nanoparticles.

Given the importance of protein corona in determining cellular responses to nanoparticles, numerous studies have been devoted to finding stable, biocompatible, and nontoxic protein corona. In this work, the interaction between human α-1-acid glycoprotein (AGP) and citrate-stabilized silver (Ag-CIT) nanoparticles of about 10 nm was methodically studied using molecular docking simulation approach and various experimental techniques. It could be shown that a stable Ag-CIT/AGP bioconjugate was formed with a high binding constant of 109 M-1, several orders of magnitude larger than that of other highly abundant serum proteins. Formation of AGP corona was accompanied by conserving the native conformation of the protein and further associated with a considerable decrease in the cytotoxicity of the silver nanoparticles.

Flow injection enzymatic biosensor for aldehydes based on a Meldola Blue-Ni complex electrochemical mediator.

Carbon nanofibers (CNF) are efficient electrode modifiers in electrochemical biosensors that enhance the electrochemical active area, induce electrocatalytic effect toward the oxidation of the enzymatic cofactor nicotinamide adenine dinucleotide (reduced form, NADH), and enable the quantitative immobilization of enzymes. Combining CNF with efficient and stable mediators radically augments the speed of electron transfer between NADH and solid electrodes and leads to electrochemical sensors characterized by high sensitivity and stability. The main aim of this work was to investigate the performance of a novel mediator for NADH with advantageously low solubility in an electrochemical detector based on a screen-printed CNF electrode as well as its potential in biosensing. Using a mediator, prepared from Meldola Blue and Ni hexamine chloride, a stable and sensitive electrochemical NADH sensor is provided with a detection limit of 0.5 µmol L-1. Further on, covalent immobilization of a recently described aldehyde dehydrogenase from the Antarctic Flavobacterium PL002 strain on the surface of the mediator-modified electrode produced a stable biosensor for the detection of aldehydes. When integrated in a flow injection analysis (FIA) setup with amperometric detection at 0.1 V vs. Ag/AgCl, the measurement of benzaldehyde with a detection limit of 10 µmol L-1 over a linear range of 30-300 µmol L-1 is possible. Determination of trace benzaldehyde impurities in a pharmaceutical excipient was also demonstrated and results compared with a chromatographic method. Graphical abstract.

Carbon-based quantum particles: an electroanalytical and biomedical perspective.

Carbon-based quantum particles, especially spherical carbon quantum dots (CQDs) and nanosheets like graphene quantum dots (GQDs), are an emerging class of quantum dots with unique properties owing to their quantum confinement effect. Many reviews appeared recently in the literature highlighting their optical properties, structures, and applications. These papers cover a broad spectrum of carbon-based nanoparticles, excluding a more detailed discussion about some important aspects related to the definition of carbon-based particles and the correlation of optical and electrochemical aspects in relation to sensing and biomedical applications. A large part of this review is devoted to these aspects. It aims, in particular, to act as a bridge between optical and electrochemical aspects of carbon-based quantum particles, both of which are associated with the electronic nature of carbon-based quantum particles. A special focus will be on their use in electroanalysis, notably their benefits in redox, and in electrochemical analysis with emphasis on their application as sensors. Electroanalysis is an easy and cost-effective means of providing qualitative and quantitative information of a specific analyte in solution in a time scale of some minutes. The integration of carbon-based quantum particles into these detection schemes as well as their incorporation into composite nanomaterials have largely improved detection limits with possibilities for their integration in aspects ranging from point-of-care devices to personalized medicine. This review will focus on some of these aspects while also covering the nanomedical aspects of carbon-based quantum particles, ultimately correlated for such developments.