Applications In Analytical Chemistry Research Articles

Droplet evaporation on superhydrophobic surfaces

Over the last decades, a fabulous variety of synthetic superhydrophobic surfaces have been created, offering unique anti-wetting properties. A significant focus for these surfaces has been on their stay-dry and self-cleaning properties. However, unless in a saturated environment, water droplets lose mass through evaporation and this itself is a field of significant interest, which is illustrated by a flood of recent studies on surface contamination and potential surface transmission of infection by evaporating sessile droplets during the Covid-19 pandemic. Superhydrophobic surfaces alter a droplet's contact with a substrate and the surrounding environment, thus changing pinning and heat transfer properties. The droplet shape also alters the space into which vapor can diffuse. Despite the many excellent reviews on superhydrophobic surfaces, there does not appear to have been a focus on the overlap with evaporating sessile droplets. Here, we address this gap by outlining the diffusion-limited sessile droplet evaporation theory, applications on patterned superhydrophobic surfaces, effect of evaporative cooling on drop evaporation rates, and practical applications of drop evaporation on superhydrophobic surfaces, such as nanoparticle assembly, biomedical assay, analytical chemistry, and crystallization applications. Finally, we provide our personal views of possible future directions in these overlapping areas.

Recent Progress of Droplet Microfluidic Emulsification Based Synthesis of Functional Microparticles.

The remarkable control function over the functional material formation process enabled by droplet microfluidic emulsification approaches can lead to the efficient and one-step encapsulation of active substances in microparticles, with the microparticle characteristics well regulated. In comparison to the conventional fabrication methods, droplet microfluidic technology can not only construct microparticles with various shapes, but also provide excellent templates, which enrich and expand the application fields of microparticles. For instance, intersection with disciplines in pharmacy, life sciences, and others, modifying the structure of microspheres and appending functional materials can be completed in the preparation of microparticles. The as-prepared polymer particles have great potential in a wide range of applications for chemical analysis, heavy metal adsorption, and detection. This review systematically introduces the devices and basic principles of particle preparation using droplet microfluidic technology and discusses the research of functional microparticle formation with high monodispersity, involving a plethora of types including spherical, nonspherical, and Janus type, as well as core-shell, hole-shell, and controllable multicompartment particles. Moreover, this review paper also exhibits a critical analysis of the current status and existing challenges, and outlook of the future development in the emerging fields has been discussed.

Leveraging the third dimension in microfluidic devices using 3D printing: no longer just scratching the surface.

3D printers utilize cutting-edge technologies to create three-dimensional objects and are attractive tools for engineering compact microfluidic platforms with complex architectures for chemical and biochemical analyses. 3D printing's popularity is associated with the freedom of creating intricate designs using inexpensive instrumentation, and these tools can produce miniaturized platforms in minutes, facilitating fabrication scaleup. This work discusses key challenges in producing three-dimensional microfluidic structures using currently available 3D printers, addressing considerations about printer capabilities and software limitations encountered in the design and processing of new architectures. This article further communicates the benefits of using three-dimensional structures, including the ability to scalably produce miniaturized analytical systems and the possibility of combining them with multiple processes, such as mixing, pumping, pre-concentration, and detection. Besides increasing analytical applicability, such three-dimensional architectures are important in the eventual design of commercial devices since they can decrease user interferences and reduce the volume of reagents or samples required, making assays more reliable and rapid. Moreover, this manuscript provides insights into research directions involving 3D-printed microfluidic devices. Finally, this work offers an outlook for future developments to provide and take advantage of 3D microfluidic functionality in 3D printing. Graphical abstract Creating three-dimensional microfluidic structures using 3D printing will enable key advances and novel applications in (bio)chemical analysis.

Chemical composition of organic acid digest from a municipal wastewater treatment plant and chemical modeling of nuisance struvite formation and phosphorus recovery as brushite

Modern municipal wastewater treatment often includes an anaerobic digestion step with a hydraulic retention time of ~1.5 days before the main anaerobic digestors. This step, often termed the organic acid digester or “acid digester” for short, produces a sludge characterized by lower pH, higher volatile fatty acid (VFA) concentrations, and high soluble phosphorus (P) concentrations, particularly if fed sludge from an enhanced biological phosphorus removal process. Here, the analysis of major ions, organic and inorganic, in the organic acid digest from a wastewater treatment plant (WWTP), Nine Springs, Madison, Wisconsin (USA), is reported for a period of 13 weeks. The bioengineered origin of this organic acid digest makes its composition unlike natural waters of any kind. From the chemical composition, the course of subsequent processes can be predicted by chemical modelling. Methanogenesis using VFAs as substrates is predicted to raise digest pH to the point where struvite is expected to form, and nuisance struvite is routinely observed at Nine Springs. Addition of calcium hydroxide to organic acid digest is expected to precipitate ~90% of soluble P from solution as the calcium phosphate mineral brushite at near neutral pH, confirmed by a pilot plant at Nine Springs. This study demonstrates the possible application of chemical analysis and chemical modelling in wastewater systems to predict and possibly adaptively manage waste streams to curb nuisance struvite formation and predict P recovery, and could be refined through broader testing and application at other wastewater treatment facilities.

Rational Fabrication of Ionic Covalent Organic Frameworks for Chemical Analysis Applications.

The rapid development of advanced material science boosts novel chemical analytical technologies for effective pretreatment and sensitive sensing applications in the fields of environmental monitoring, food security, biomedicines, and human health. Ionic covalent organic frameworks (iCOFs) emerge as a class of covalent organic frameworks (COFs) with electrically charged frames or pores as well as predesigned molecular and topological structures, large specific surface area, high crystallinity, and good stability. Benefiting from the pore size interception effect, electrostatic interaction, ion exchange, and recognizing group load, iCOFs exhibit the promising ability to extract specific analytes and enrich trace substances from samples for accurate analysis. On the other hand, the stimuli response of iCOFs and their composites to electrochemical, electric, or photo-irradiating sources endows them as potential transducers for biosensing, environmental analysis, surroundings monitoring, etc. In this review, we summarized the typical construction of iCOFs and focused on their rational structure design for analytical extraction/enrichment and sensing applications in recent years. The important role of iCOFs in the chemical analysis was fully highlighted. Finally, the opportunities and challenges of iCOF-based analytical technologies were also discussed, which may be beneficial to provide a solid foundation for further design and application of iCOFs.

The application of experimental design and green analytical chemistry in HPLC strategy for the determination of five drugs used in antimicrobial combination therapy

Antimicrobial resistance is a significant global issue that has increased mortality rates over the past 100 years. One of the strategies followed to overcome this problem is to use antimicrobial combination therapy with different action modes that can synergize for successful treatment in emergent situations. Ciprofloxacin, Tinidazole, Dexamethasone Sodium Phosphate, Diloxanide Furoate, Metronidazole, and their different combinations are commonly used as effective combination therapies in critical cases. Hence, it is essential to establish an appropriate technique for their simultaneous analysis. The application of green analytical chemistry concepts was also an important issue that should be considered in the development of analytical methods. Hence, a new green micellar organic solvent-free HPLC methodology has been devised to analyze the specified five drugs simultaneously in both their authentic forms and combined pharmaceutical formulations. Response surface methodology was used to investigate the influence of different variable factors on chromatographic performance. Central composite design was utilized for response optimization. A Symmetry C18 column (3.5 µm, 4.6 × 75 mm), an isocratic mixed–micellar mobile phase composed of (70.76 mM of sodium dodecyl sulphate and 21.38 mM of Brij-35, 2.76 pH, and 40 ± 2 °C at a flow rate of 1 mL/min, were the ideal separation circumstances for analytesʹ separation at 260 nm as a chosen detection wavelength. The described approach was satisfactorily utilized todetermine various pharmaceutical formulations of the specified medications in combination. ICH guidelines were followed during the method's validation. Analytical Greenness Measure (AGREE) and Green Analytical Procedure Index (GAPI) fundamentals were followed to judge the developed methodology's greenness.

Feasibility of An Introductory Chemistry for Cultural Heritage E-course for Museum Professionals in the Philippines

Chemistry knowledge is fundamental in preserving and comprehending the tangible nature of museum collections. Despite chemistry’s importance in cultural heritage, a gap exists between the chemist’s knowledge and the accepted competencies of museum workers. This paper describes an initial study on introducing museum professionals with no formal scientific training in basic chemical thinking and research. A two-hour online session was conceived, comprising two separate lectures emphasizing the concepts, instrumental techniques, and example of a case study of an application of chemical analysis on a local heritage material. An open discussion and exchange of ideas followed the lectures. Feedback from the participants was very positive, and they described the online course as informative and valuable for their museum work. The qualitative evaluations obtained from this paper can serve as baseline information for developing a more extensive e-course in the future.

Recent Applications of Quantum Dots in Pharmaceutical Analysis.

Nanotechnology has emerged as one of the most potential areas for pharmaceutical analysis. The need for nanomaterials in pharmaceutical analysis is comprehended in terms of economic challenges, health and safety concerns. Quantum dots (QDs)or colloidal semiconductor nanocrystals are new groups of fluorescent nanoparticles that bind nanotechnology to drug analysis. Because of their special physicochemical characteristics and small size, QDs are thought to be promising candidates for the electrical and luminescent probes development. They were originally developed as luminescent biological labels, but are now discovering new analytical chemistry applications, where their photo-luminescent properties are used in pharmaceutical, clinical analysis, food quality control and environmental monitoring. In this review, we discuss QDs regarding properties and advantages, advances in methods of synthesis and their recent applications in drug analysis in the recent last years.

Quantum sensing of radio-frequency signal with NV centers in SiC.

Silicon carbide is an emerging platform for quantum technologies that provides wafer scale and low-cost industrial fabrication. The material also hosts high-quality defects with long coherence times that can be used for quantum computation and sensing applications. Using an ensemble of nitrogen-vacancy centers and an XY8-2 correlation spectroscopy approach, we demonstrate a room-temperature quantum sensing of an artificial AC field centered at ~900 kHz with a spectral resolution of 10 kHz. Implementing the synchronized readout technique, we further extend the frequency resolution of our sensor to 0.01 kHz. These results pave the first steps for silicon carbide quantum sensors toward low-cost nuclear magnetic resonance spectrometers with a wide range of practical applications in medical, chemical, and biological analysis.

A Facile Dual‐Emission Ratiometric Carbon‐Dot Fluorescent Probe and Its Application in Portable Chemical Sensors and Water Quality Analysis

AbstractBased on the dual signal of double‐emitting carbon quantum dots (G‐CDs), a ratiometric fluorescence sensor is established to realize the analysis and detection of Fe3+in real samples. When the excitation wavelength is 360 nm and 480 nm, the double emission fluorescence peaks are located at the wavelengths of 477 nm and 523 nm. The former is the fluorescence response signal, and the latter is the fluorescence background signal. The semi‐quantitative analysis of Fe3+was achieved based on the linear relationship between the ratio F477/F523of the two signals and the Fe3+concentration. The linear range of this method is 0.015–120 μM, and the limit of detection (LOD, S/N=3) is 5 nM. Meanwhile, the naked‐eye visual detection of Fe3+can be realized according to the fluorescence color of the probe. The probe exhibits excellent anti‐interference, selectivity and repeatability, and this method can be applied to the detection of Fe3+in actual samples.

Advances in single-molecule junctions as tools for chemical and biochemical analysis.

The development of miniaturized electronics has led to the design and construction of powerful experimental platforms capable of measuring electronic properties to the level of single molecules, along with new theoretical concepts to aid in the interpretation of the data. A new area of activity is now emerging concerned with repurposing the tools of molecular electronics for applications in chemical and biological analysis. Single-molecule junction techniques, such as the scanning tunnelling microscope break junction and related single-molecule circuit approaches have a remarkable capacity to transduce chemical information from individual molecules, sampled in real time, to electrical signals. In this Review, we discuss single-molecule junction approaches as emerging analytical tools for the chemical and biological sciences. We demonstrate how these analytical techniques are being extended to systems capable of probing chemical reaction mechanisms. We also examine how molecular junctions enable the detection of RNA, DNA, and traces of proteins in solution with limits of detection at the zeptomole level.

Biosensors For Cancer Diagnosis Based on Quantum Dots

Cancer, one of the most dangerous illnesses threatening people’s lives, caused nearly 2.4 million death last year in China. Effective and timely detection is the key to relieving and even successfully treating this disease. In order to realize the aim of early and sensitive diagnosis, multiple nanomaterials have been used, including the rising materials in recent years, quantum dots. Compared with other materials, quantum dots (QDs) have various advantages, like cheap fabrication expense, great fluorescent behavior, high sensitivity to targeted cells or related markers, versatile recognizing strategies, no toxicity and low detection limits. These properties enable this material to become the popular choice for biosensors. In this review, two main streams were chosen in the quantum dots-based biosensors: graphene quantum dots (GQDs) based biosensors and carbon quantum dots (CQDs) based biosensors. The character of each kind of quantum dot was reported and the recent development of these two nanomaterials was introduced, including their synthesis and application of optical and chemical analysis. Therefore, this report can offer great value to the research in the field of quantum dots-based biosensors, which will be used for cancer diagnosis in the future.

Introduction to Light Properties and Basic Principles of Spectroscopy at the High-School Level: A Pilot Study

Spectroscopy is the basis of many applications in chemistry; however, the basic principles of light, light–matter interaction, and the operation of spectrophotometers are rarely present in chemistry curricula at the high-school level, or they are only briefly introduced to students before focusing on analytical chemistry applications. In this work, we report the results of a study conducted over several years, aimed to design, optimise, and put into practice a didactic sequence on light phenomena such as reflection, refraction, interference, diffraction, and light dispersion, as well as the basic principles of ultraviolet–visible spectroscopy and spectroscopic instruments. Difficult concepts of light phenomena and related topics were deeply investigated, focusing on the best ways to teach them to high-school students in the framework of the content-specific components identified in the topic-specific pedagogical content knowledge theoretical model. Inquiry-based learning and interactive STEM laboratory activities were combined with a historical epistemological teaching method. Short introductory videos were also recorded to help students during the remote lessons in the COVID-19 pandemic period. In this paper, we report and discuss the research strategy used in order to design and implement the sequence of educational activities, leading to a final optimised didactic sequence that was tested in a pilot study. The main results were obtained from the experimentation with several classes in two high-school technical institutes with a chemistry and material sciences curriculum, along with a group of undergraduate students during the first part of an introductory course on molecular spectroscopy.

A Review of Quartz Crystal Microbalance for Chemical and Biological Sensing Applications.

Humans are fundamentally interested in monitoring and understanding interactions that occur in and around our bodies. Biological interactions within the body determine our physical condition and can be used to improve medical treatments and develop new drugs. Daily life involves contact with numerous chemicals, ranging from household elements, naturally occurring scents from common plants and animals, and industrial agents. Many chemicals cause adverse health and environmental effects and require regulation to prevent pollution. Chemical detection is critically important for food and environmental quality control efforts, medical diagnostics, and detection of explosives. Thus, sensitive devices are needed for detecting and discriminating chemical and biological samples. Compared to other sensing devices, the Quartz Crystal Microbalance (QCM) is well-established and has been considered and sufficiently sensitive for detecting molecules, chemicals, polymers, and biological assemblies. Due to its simplicity and low cost, the QCM sensor has potential applications in analytical chemistry, surface chemistry, biochemistry, environmental science, and other disciplines. QCM detection measures resonate frequency changes generated by the quartz crystal sensor when covered with a thin film or liquid. The quartz crystal is sandwiched between two metal (typically gold) electrodes. Functionalizing the electrode's surface further enhances frequency change detection through to interactions between the sensor and the targeted material. These sensors are sensitive to high frequencies and can recognize ultrasmall masses. This review will cover advancements in QCM sensor technologies, highlighting in-sensor and real-time analysis. QCM-based sensor function is dictated by the coating material. We present various high-sensitivity coating techniques that use this novel sensor design. Then, we briefly review available measurement parameters and technological interventions that will inform future QCM research. Lastly, we examine QCM's theory and application to enhance our understanding of relevant electrical components and concepts.

Application of Mathematical Modeling and Chemical Analysis for COVID-19 Pandemic in Bangladesh

Application of Mathematical Modeling and Chemical Analysis for COVID-19 Pandemic in Bangladesh

Fish-Kills in the Urban Stretch of the Tiber River After a Flash-Storm: Investigative Monitoring with Effect-Based Methods, Targeted Chemical Analyses, and Fish Assemblage Examinations

In 2020 and 2021, fish-kills events occurred in the Tiber river in the city of Rome. These events, which caused the death of thousands of fish of different species (e.g., Barbus spp., Cyprinus carpio, Squalius spp.), were preceded the days before by severe flash-storms. Heavy rains in urban areas in recent years are linked to climate change and fish-kills events. With the aim to investigate the causes of these events, effect-based methods (EBMs) and targeted chemical analyses have been performed on a specific site of river Tiber in the center of the city. Additionally, examination and classification of the floating dead fishes have been performed. The chemical analysis performed on several groups of contaminants showed the presence of some pharmaceuticals, insecticides, and PFAS at up to ng/L. Results with the Fish Embryo Toxicity (FET) test confirmed lethal and sub-lethal effects, while acute effects were not detected with the Daphnia magna acute test. The fish-kills events probably can be generated by several factors as a consequence of an increasing human anthropization of the area with the contribution of different stressors together with chemical releases and emissions. This study shows that in multiple stressor scenarios characterized by heavy rainfall, droughts, and strong anthropogenic pressures, the application of EBMs, chemical analysis, and fish assemblage examinations can represent a useful support in the investigation of the causes of extensive fish-kills events.

Raman spectroscopy of optical-trapped single particle using bull's eye nanostructure.

Surface-enhanced Raman spectroscopy (SERS) has enabled single nanoparticle Raman sensing with abundant applications in analytical chemistry, biomaterials, and environmental monitoring. Genuine single particle Raman sensing requires a cumbersome technique, such as atomic force microscopy (AFM) based tip-enhanced Raman spectroscopy; SERS-based single particle Raman sensing still collects an ensemble signal that samples, in principle, a number of particles. Here, we develop in situ Raman-coupled optical tweezers, based on a hybrid nanostructure consisting of a single bowtie aperture surrounded by bull's eye rings, to trap and excite a rhodamine-6G-dye-doped polystyrene sphere. We simulated a platform to ensure sufficient enhancement capability for both optical trapping and SERS of a single nanoparticle. Experiments with well-designed controls clearly attribute the Raman signal origin to a single 15-nm particle trapped at the center of a nanohole, and they also clarified the trapping and Raman enhancement role of the bull's eye rings. We claim Raman sensing of a smallest optically trapped particle.

Recent developments in digital light processing 3D-printing techniques for microfluidic analytical devices

Digital light processing (DLP) 3D printing is rapidly advancing and has emerged as a powerful additive manufacturing approach to fabricate analytical microdevices. DLP 3D-printing utilizes a digital micromirror device to direct the projected light and photopolymerize a liquid resin, in a layer-by-layer approach. Advances in vat and lift design, projector technology, and resin composition, allow accurate fabrication of microchannel structures as small as 18 × 20 µm. This review describes the latest advances in DLP 3D-printing technology with respect to instrument set-up and resin formulation and highlights key efforts to fabricate microdevices targeting emerging (bio-)analytical chemistry applications, including colorimetric assays, extraction, and separation.

High Sensitivity Refractometer Based on Tapering Two-Mode Fiber Embedded Long-Period Fiber Grating

A novel tapered two-mode fiber embedded long-period fiber grating (TTMF-LPFG) sensor is proposed. The long-period fiber grating (LPFG) is fabricated by periodically splicing the two-mode fiber (TMF) and single-mode fiber (SMF), and then the LPFG is tapered to make a refractive index (RI) sensor. By comparing the sensors with different waist diameters, we found that the smaller the diameter of the sensor is, the higher the sensitivity is. When the taper waist diameter is 36 <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$\mu \text{m}$ </tex-math></inline-formula> , the maximum sensitivity reaches 1360.43 nm/RIU. TTMF-LPFG shows low sensitivity to the temperature, avoiding the influence of temperature. For the traditional taper fiber, a very thin taper waist is required to excite strong evanescent field (EF) in order to obtain a large RI sensitivity. This situation creates a sensor fragile. For our structure, through the taper, LPFG can be formed and the sensitivity can be improved at the same time. The sensor has great potential in chemical composition analysis and biomedical applications.

Relaxed-tolerance subwavelength grating coupler

Short-wavelength mid-infrared (MIR) silicon photonics at 2–2.5 μm wavelengths has a wide range of applications in optical communications, chemical analysis, and environmental monitoring. In this spectral region, subwavelength grating (SWG) couplers can be fabricated by using commercial multi-project wafer (MPW) services, due to their larger device feature sizes compared with those in the telecommunication band. However, conventional SWG couplers are still sensitive to variations in dimensions produced by errors in fabrication processes, restricting the fabrication reproducibility of the devices. Here, we demonstrated a relaxed-tolerance SWG coupler that has relaxed fabrication tolerance to overcome this limitation. The approach is based on the design of the SWG coupler with dual-hole structures to reduce the influence of random fabrication variations on the grating effective refractive index. Theoretically, the slope of the center wavelength shift of the relaxed-tolerance SWG coupler to the variation of the subwavelength hole size is 0.58, while that is 0.63 for the conventional SWG coupler. We demonstrated the relaxed-tolerance SWG coupler with a peak coupling efficiency of −6.2 dB at a wavelength of 2.038 μm with a 1-dB bandwidth of about 30 nm. Additionally, fabrication reproducibility and optical fiber coupling tolerance are also presented. The study paves a promising way toward developing short-wavelength MIR grating couplers with high performance, excellent repeatability, and cost-efficiency.