Synthesis of cyclic carbonates from CO2 cycloaddition to bio-based epoxides and glycerol: an overview of recent development.

Anthropogenic carbon dioxide (CO2) emissions contribute significantly to global warming and deplete fossil carbon resources, prompting a shift to bio-based raw materials. The two main technologies for reducing CO2 emissions are capturing and either storing or utilizing it. However, while capture and storage have high reduction potential, they lack economic feasibility. Conversely, by utilizing the CO2 captured from streams and air to produce valuable products, it can become an asset and curb greenhouse gas effects. CO2 is a challenging C1-building block due to its high kinetic inertness and thermodynamic stability, requiring high temperature and pressure conditions and a reactive catalytic system. Nonetheless, cyclic carbonate production by reacting epoxides and CO2 is a promising green and sustainable chemistry reaction, with enormous potential applications as an electrolyte in lithium-ion batteries, a green solvent, and a monomer in polycarbonate production. This review focuses on the most recent developments in the synthesis of cyclic carbonates from glycerol and bio-based epoxides, as well as efficient methods for chemically transforming CO2 using flow chemistry and novel reactor designs.

Free carrier-mediated ferromagnetism in nonmagnetic ion (Bi-Li) codoped ZnO nanowires.

Non-magnetic dopants and p-type materials are attractive choices to explore the mechanism and origin of room-temperature defect-based ferromagnetism in metal oxide-based DMSs. In this study, we performed comprehensive transport, magnetic, structural, optical, and compositional as well as DFT studies of pristine, Li-doped, and Bi-Li codoped vertically aligned ZnO NW films to explore the mechanism and origin of ferromagnetism. We used a simple solution process to synthesize a wurtzite structure and vertically aligned ZnO NWs on a Si substrate. The doping, high crystallinity, and vertical alignment along the 002 planes were evidenced through HRTEM, FESEM, and XRD measurements. The XPS analysis confirmed the +1 and +3 states of Li and Bi, respectively. Moreover, Raman analysis also depicted the characteristic peaks of ZnO NWs at 98.31 cm-1 and 437.71 cm-1. The PL studies of doped NWs showed a typical NBE peak of ZnO at ∼395 nm along with a sub-gap defect-related broad peak at ∼504 nm indicating the presence of defects due to doping. The pure ZnO NW samples showed negligible saturation magnetization (Ms) at room temperature while the saturation magnetization was observed to increase with Li-doping and reduced with Bi-Li codoping. According to the Hall studies the pure ZnO NW film showed n-type conductivity, while all doped and codoped samples showed p-type conductivity. The hole concentration was observed to increase with Li-doping and decrease with Bi-Li codoping showing similar behavior to that of the Ms value, thereby suggesting a direct correlation between Ms and carrier concentration. The I-V properties showed a similar trend to that of carrier concentration and Ms. Our DFT studies showed that magnetization increased by Li doping and reduced by Li-Bi codoping in defective ZnO crystals by replacing Zn with Li and Bi atoms at the Zn site. Overall, our studies highlight the immense potential of hole-mediated Bi-Li codoped ZnO NW devices which are expected to play a pivotal role in developing spintronic devices.

Eco-Friendly Sustainable Synthesis of Graphene Quantum Dots from Biowaste as a Highly Selective Sensor.

Graphene quantum dots (GQDs) have generated a great deal of scientific interest due to their bright fluorescence, good biocompatibility, minimal toxicity and fascinating physicochemical features. However, the ultimate issues regarding the acidic contaminations and high synthesis cost of GQDs remain open challenges for their real-world applications. Herein, we report an eco-friendly, acid-free and sustainable method for the preparation of GQDs using a cost-efficient, and renewable carbon source, 'biomass-waste', which simultaneously solves the risk of contamination from strong acids and high expenditure initiated by expensive precursors. The results demonstrate that GQDs possess a size range of 1-5 nm with an average size of ~3 ± 0.4 nm and a thickness of ~1 nm consisting of 1-3 layers of graphene. As-prepared GQDs demonstrate fascinating size-dependent optical properties and considerable surface grafting. Due to their intriguing optical properties, these GQDs are employed as fluorescence probes to detect ferric ions. A focused and sensitive sensor is developed with a detection limit down to 0.29 µM. This study emphasizes the need for using a reasonably green process and an inexpensive biomass precursor to create high-value GQDs that hold great potential for use in photocatalytic, bioimaging and real-world sensing applications.

Graphene Quantum Dots-Based Electrochemical Biosensing Platform for Early Detection of Acute Myocardial Infarction.

Heart failure resulting from acute myocardial infarction (AMI) is an important global health problem. Treatments of heart failure and AMI have improved significantly over the past two decades; however, the available diagnostic tests only give limited insights into these heterogeneous conditions at a reversible stage and are not precise enough to evaluate the status of the tissue at high risk. Innovative diagnostic tools for more accurate, more reliable, and early diagnosis of AMI are urgently needed. A promising solution is the timely identification of prognostic biomarkers, which is crucial for patients with AMI, as myocardial dysfunction and infarction lead to more severe and irreversible changes in the cardiovascular system over time. The currently available biomarkers for AMI detection include cardiac troponin I (cTnI), cardiac troponin T (cTnT), myoglobin, lactate dehydrogenase, C-reactive protein, and creatine kinase and myoglobin. Most recently, electrochemical biosensing technologies coupled with graphene quantum dots (GQDs) have emerged as a promising platform for the identification of troponin and myoglobin. The results suggest that GQDs-integrated electrochemical biosensors can provide useful prognostic information about AMI at an early, reversible, and potentially curable stage. GQDs offer several advantages over other nanomaterials that are used for the electrochemical detection of AMI such as strong interactions between cTnI and GQDs, low biomarker consumption, and reusability of the electrode; graphene-modified electrodes demonstrate excellent electrochemical responses due to the conductive nature of graphene and other features of GQDs (e.g., high specific surface area, π-π interactions with the analyte, facile electron-transfer mechanisms, size-dependent optical features, interplay between bandgap and photoluminescence, electrochemical luminescence emission capability, biocompatibility, and ease of functionalization). Other advantages include the presence of functional groups such as hydroxyl, carboxyl, carbonyl, and epoxide groups, which enhance the solubility and dispersibility of GQDs in a wide variety of solvents and biological media. In this perspective article, we consider the emerging knowledge regarding the early detection of AMI using GQDs-based electrochemical sensors and address the potential role of this sensing technology which might lead to more efficient care of patients with AMI.

Graphene nanocomposites for transdermal biosensing.

Transdermal biosensors for the real-time and continuous detection and monitoring of target molecules represent an intriguing pathway for enhancing health outcomes in a cost-effective and non-invasive fashion. Many transdermal biosensor devices contain microneedles and other miniaturized components. There remains an unmet clinical need for microneedle transdermal biosensors to obtain a more accurate, rapid, and reliable insight into the real-time monitoring of disease. The ability to monitor biomarkers at an intradermal molecular level in a non-invasive manner remains the next technological gap to solve real-world clinical problems. The emergence of the two-dimensional material graphene with unique material properties and the ability to quantify analytes and physiological status can enable the detection of critical biomarkers indicative of human disease. The development of a user-friendly, affordable, and non-invasive transdermal biosensing device for continuous and personalized monitoring of target molecules could be beneficial for many patients. This focus article considers the use of graphene-based transdermal biosensors for health monitoring, evaluation of these sensors for glucose and hydrogen peroxide detection via in vitro, in vivo, and ex vivo studies, recent technological innovations, and potential challenges. This article is categorized under: Diagnostic Tools > Biosensing.

High yield synthesis of graphene quantum dots from biomass waste as a highly selective probe for Fe3+ sensing.

Graphene quantum dots (GQDs), a novel type of zero-dimensional fluorescent materials, have gained considerable attention owing to their unique optical properties, size and quantum confinement. However, their high cost and low yield remain open challenges for practical applications. In this work, a low cost, green and renewable biomass resource is utilised for the high yield synthesis of GQDs via microwave treatment. The synthesis approach involves oxidative cutting of short range ordered carbon derived from pyrolysis of biomass waste. The GQDs are successfully synthesised with a high yield of over 84%, the highest value reported to date for biomass derived GQDs. As prepared GQDs are highly hydrophilic and exhibit unique excitation independent photoluminescence emission, attributed to their single-emission fluorescence centre. As prepared GQDs are further modified by simple hydrothermal treatment and exhibit pronounced optical properties with a high quantum yield of 0.23. These modified GQDs are used for the highly selective and sensitive sensing of ferric ions (Fe3+). A sensitive sensor is prepared for the selective detection of Fe3+ ions with a detection limit of as low as 2.5 × 10-6 M. The utilisation of renewable resource along with facile microwave treatment paves the way to sustainable, high yield and cost-effective synthesis of GQDs for practical applications.