Combining Chemometrics and Sensors: Toward New Applications in Monitoring and Environmental Analysis.

For many years, an extensive array of chemometric methods have provided a platform upon which a quantitative description of environmental conditions can be obtained. Applying chemometric methods to environmental data allows us to identify and describe the interrelations between certain environmental drivers. They also provide an insight into the interrelationships between these drivers and afford us a greater understanding of the potential impact that these drivers can place upon the environment. However, an effective marriage of these two systems has not been performed. Therefore, it is the aim of this review to highlight the advantages of using chemometrics and sensors to identify hidden trends in environmental parameters, which allow the state of the environment to be effectively monitored. Despite the combination of chemometrics and sensors, to capture new developments and applications in the field of environmental sciences, these methods have not been extensively used. Importantly, although different parameters and monitoring procedures are required for different environments (e.g., air, water, soil), they are not distinct, separate entities. Contemporary developments in the use of chemometrics afford us the ability to predict changes in different aspects of the environment using instrumental methods. This review also provides an insight into the prevailing trends and the future of environmental sensing, highlighting that chemometrics can be used to enhance our ability to monitor the environment. This enhanced ability to monitor environmental conditions and to predict trends would be beneficial to government and research agencies in their ability to develop environmental policies and analysis procedures.

The Multiomics Analyses of Fecal Matrix and Its Significance to Coeliac Disease Gut Profiling.

Gastrointestinal (GIT) diseases have risen globally in recent years, and early detection of the host's gut microbiota, typically through fecal material, has become a crucial component for rapid diagnosis of such diseases. Human fecal material is a complex substance composed of undigested macromolecules and particles, and the processing of such matter is a challenge due to the unstable nature of its products and the complexity of the matrix. The identification of these products can be used as an indication for present and future diseases; however, many researchers focus on one variable or marker looking for specific biomarkers of disease. Therefore, the combination of genomics, transcriptomics, proteomics and metabonomics can give a detailed and complete insight into the gut environment. The proper sample collection, sample preparation and accurate analytical methods play a crucial role in generating precise microbial data and hypotheses in gut microbiome research, as well as multivariate data analysis in determining the gut microbiome functionality in regard to diseases. This review summarizes fecal sample protocols involved in profiling coeliac disease.

Measuring the mechanical properties of flexible crystals using bi-modal atomic force microscopy.

Flexible crystals are an emerging class of material with unique properties and a range of potential applications. Their relatively recent development means that mechanical characterisation protocols have not yet been widely established. There is a lack of quantitative flexibility measurements, such as the elastic modulus (Young's modulus), reported in the literature. In this work, we investigate amplitude modulated-frequency modulated atomic force microscopy (AM-FM AFM) as a fast, versatile method for measuring the elastic modulus of single flexible crystals. Specifically, the elastic modulus of single crystals of copper(ii) acetylacetonate (Cu(acac)2) was measured. The elastic modulus for Cu(acac)2 was found to be 4.79 ± 0.16 GPa. Importantly, this technique was able to map the variation in mechanical properties over the surface of the material with nanoscale resolution, showing some degree of correlation between surface morphology and elastic modulus. Additionally, the distribution of elastic modulus values can be measured at different locations on the crystal, giving a statistically robust distribution, which cannot be achieved using other methods.

Functional Naphthalene Diimides: Synthesis, Properties, and Applications.

This comprehensive review surveys developments over the past decade in the field of naphthalene diimides (NDIs). It explores their application toward: supramolecular chemistry; sensors; host-guest complexes for molecular switching devices, such as catenanes and rotaxanes; ion-channels by ligand gating; gelators for sensing aromatic systems; catalysis through anion-π interactions; and NDI intercalations with DNA for medicinal applications. We have also explored new designs, synthesis, and progress in the field of core-substituted naphthalene diimides (cNDIs), and their implications in areas such as artificial photosynthesis and solar cell technology. Also presented are some interesting synthetic routes and procedures that can be used toward further development of NDI-bearing compounds for future applications. Finally, we conclude with our views on NDI chemistry for future research endeavors, and we outline what we believe are the key obstacles that need to be overcome for NDIs to see real world applications.

Origin of surface trap states in CdS quantum dots: relationship between size dependent photoluminescence and sulfur vacancy trap states.

Monodisperse cadmium sulphide (CdS) quantum dots (QDs) with a tunable size from 1.4 to 4.3 nm were synthesized by a non-injection method, and their surface states were characterized by photoluminescence spectroscopy and X-ray Photoelectron Spectroscopy (XPS). The steady state photoluminescence study identified that the proportion of the trap state emission increased with the QD size decrease, while from the photoluminescence decay study, it appeared that the trap state emission results from the emission via a surface deep trap state. The XPS measurements revealed the existence of surface Cd with sulfur vacancy sites which act as electron trap sites, and the population of these sites increases with the QD size decrease. These results are consistent to conclude that the trap state emission mainly originates from the surface deep trapped electrons at the surface Cd with sulfur vacancy sites.

Near-infrared absorbing Cu12Sb4S13 and Cu3SbS4 nanocrystals: synthesis, characterization, and photoelectrochemistry.

Herein, we present the novel synthesis of tetrahedrite copper antimony sulfide (CAS) nanocrystals (Cu12Sb4S13), which display strong absorptions in the visible and NIR. Through ligand tuning, the size of the Cu12Sb4S13 NCs may be increased from 6 to 18 nm. Phase purity is achieved through optimizing the ligand chemistry and maximizing the reactivity of the antimony precursor. We provide a detailed investigation of the optical and photoelectrical properties of both tetrahedrite (Cu12Sb4S13) and famatinite (Cu3SbS4) NCs. These NCs were found to have very high absorption coefficients reaching 10(5) cm(-1) and band gaps of 1.7 and 1 eV for tetrahedrite and famatinite NCs, respectively. Ultraviolet photoelectron spectroscopy was employed to determine the band positions. In each case, the Fermi energies reside close to the valence band, indicative of a p-type semiconductor. Annealing of tetrahedrite CAS NC films in sulfur vapor at 350 °C was found to result in pure famatinite NC films, opening the possibility to tune the crystal structure within thin films of these NCs. Photoelectrochemistry of hydrazine free unannealed films displays a strong p-type photoresponse, with up to 0.1 mA/cm(2) measured under mild illumination. Collectively these optical properties make CAS NCs an excellent new candidate for both thin film and hybrid solar cells and as strong NIR absorbers in general.

Interaction of hydrogen with ZnO nanopowders--evidence of hydroxyl group formation.

There have been many investigations to reveal the nature of the hydrogen gas and ZnO nanopowder interaction at elevated temperatures, while at present no conclusive description of such an interaction has been confidently reported. In this work, we demonstrate that a hydroxyl group is formed during this interaction, depending on size and relative crystallinity of nanopowders. Our in situ Raman spectroscopy investigations show that the interaction directly affects the intensity of the Raman signal at 483 cm(-1), relative to the peak at 519 cm(-1). Ex situ x-ray diffraction (XRD) and infrared spectroscopy also show extra peaks at 44° and 1618 cm(-1), respectively, after hydrogenation. These peaks were all identified as surface hydroxyl groups, which can be related to the formation of water on the ZnO nanopowder surfaces.

Synthetic and structural studies on copper 1 H-[1,10]-phenanthrolin-2-one coordination complexes: isolation of a novel intermediate during 1,10-phenanthroline hydroxylation.

The synthesis and crystal structure elucidation of a novel dinuclear heteroleptic copper(II) complex has led to an alternative mechanism in the formation of covalent hydrates. During further studies on the synthesis and properties of [Cu(2)(ophen)(2)] (1), a dinuclear complex of copper(I) with 1 H-[1,10]-phenanthrolin-2-one (Hophen), two intermediates/alternative products 2 and 3 were isolated. The dinuclear, antiferromagnetic complex [Cu(2)(ophen)(2)(phen)(2)](NO(3))(2)9H(2)O (3, phen=1,10-phenanthroline) contains two five-coordinate copper(II) ions, both with trigonal-bipyramidal coordination, which are bridged together through deprotonated hydroxyl groups with a Cu--Cu non-bonding distance of 3.100 A. Complex [Cu(phen)(2)(H(2)O)](NO(3))(2) (2) is a polymorph of a previously reported material. The occurrence of 2 and 3 has led us to propose a variation to the Gillard mechanism for the formation of covalent hydrates in bidentate N-heterocycles in which the attacking nucleophile may be the deprotonated form of 2, [Cu(phen)(2)(OH)](-), rather than free OH(-).

Chemometrics for environmental monitoring: a review.

Environmental monitoring is necessary to ensure the overall health and conservation of an ecosystem. However, ecosystems (e.g. air, water, soil), are complex, involving numerous processes (both native and external), inputs, contaminants, and living organisms. As such, monitoring an environmental system is not a trivial task. The data obtained from natural systems is often multifaceted and convoluted, as a multitude of inputs can be intertwined within the matrix of the information obtained as part of a study. This means that trends and important results can be easily overlooked by conventional and single dimensional data analysis protocols. Recently, chemometric methods have emerged as a powerful method for maximizing the details contained within a chemical data set. Specifically, chemometrics refers to the use of mathematical and statistical analysis methods to evaluate chemical data, beyond univariant analysis. This type of analysis can provide a quantitative description of environmental measurements, while also having the capacity to reveal previously overlooked trends in data sets. Applying chemometrics to environmental data allows us to identify and describe the inter-relationship of environmental drivers, sources of contamination, and their potential impact upon the environment. This review aims to provide a detailed understanding of chemometric techniques, how they are currently used in environmental monitoring, and how these techniques can be used to improve current practices. An enhanced ability to monitor environmental conditions and to predict trends would be greatly beneficial to government and research agencies in their ability to develop environmental policies and analytical procedures.

Nano-plastics and their analytical characterisation and fate in the marine environment: From source to sea.

Polymer contamination is a major pollutant in all waterways and a significant concern of the 21st Century, gaining extensive research, media, and public attention. The polymer pollution problem is so vast; plastics are now observed in some of the Earth's most remote regions such as the Mariana trench. These polymers enter the waterways, migrate, breakdown; albeit slowly, and then interact with the environment and the surrounding biodiversity. It is these biodiversity and ecosystem interactions that are causing the most nervousness, where health researchers have demonstrated that plastics have entered the human food chain, also showing that plastics are damaging organisms, animals, and plants. Many researchers have focused on reviewing the macro and micro-forms of these polymer contaminants, demonstrating a lack of scientific data and also a lack of investigation regarding nano-sized polymers. It is these nano-polymers that have the greatest potential to cause the most harm to our oceans, waterways, and wildlife. This review has been especially ruthless in discussing nano-sized polymers, their ability to interact with organisms, and the potential for these nano-polymers to cause environmental damage in the marine environment. This review details the breakdown of macro-, micro-, and nano-polymer contamination, examining the sources, the interactions, and the fates of all of these polymer sizes in the environment. The main focus of this review is to perform a comprehensive examination of the literature of the interaction of nanoplastics with organisms, soils, and waters; followed by the discussion of toxicological issues. A significant focus of the review is also on current analytical characterisation techniques for nanoplastics, which will enable researchers to develop protocols for nanopolymer analysis and enhance understanding of nanoplastics in the marine environment.

Density functional theory study of hydrogen bonding in ionic molecular materials.

Crystal structures are usually described in geometric terms. However, it is the energetics of intermolecular interactions that determine the chemical and physical properties of molecular materials.(1) In this paper, we use density functional theory (DFT) in combination with numerical basis sets to analyze the hydrogen bonding interactions in a family of novel ionic molecular materials. We find that the calculated binding energies are consistent with those of other ionic hydrogen bonded systems. We also examine electron density distributions for the systems of interest to gain insight into the nature of the hydrogen bonding interaction and investigate the effects of different aspects of the crystal field on the geometry of the hydrogen bond.

Ab initio calculations as a quantitative tool in the inelastic neutron scattering study of a single-molecule magnet analogue.

Ab initio calculations carried out on the Tb analogue of the single-molecule magnet family Na9[Ln(W5O18)2] (Ln = Nd, Gd, Ho and Er) have allowed interpretation of the inelastic neutron scattering spectra. The combined experimental and theoretical approach sheds new light on the sensitivity of the electronic structure of the Tb(III) ground and excited states to small structural distortions from axial symmetry, thus revealing the subtle relationship between molecular geometry and magnetic properties of the two isostructural species that comprise the sample.

Exfoliation Solvent Dependent Plasmon Resonances in Two-Dimensional Sub-Stoichiometric Molybdenum Oxide Nanoflakes.

Few-layer two-dimensional (2D) molybdenum oxide nanoflakes are exfoliated using a grinding assisted liquid phase sonication exfoliation method. The sonication process is carried out in five different mixtures of water with both aprotic and protic solvents. We found that surface energy and solubility of mixtures play important roles in changing the thickness, lateral dimension, and synthetic yield of the nanoflakes. We demonstrate an increase in proton intercalation in 2D nanoflakes upon simulated solar light exposure. This results in substoichiometric flakes and a subsequent enhancement in free electron concentrations, producing plasmon resonances. Two plasmon resonance peaks associated with the thickness and the lateral dimension axes are observable in the samples, in which the plasmonic peak positions could be tuned by the choice of the solvent in exfoliating 2D molybdenum oxide. The extinction coefficients of the plasmonic absorption bands of 2D molybdenum oxide nanoflakes in all samples are found to be high (ε > 10(9) L mol(-1) cm(-1)). It is expected that the tunable plasmon resonances of 2D molybdenum oxide nanoflakes presented in this work can be used in future electronic, optical, and sensing devices.

Two-step synthesis of luminescent MoS(2)-ZnS hybrid quantum dots.

A surfactant assisted technique has been used to promote the exfoliation of molybdenum disulphide (MoS2) in a water-ethanol mixture, to avoid the use of harsh organic solvents, whilst still producing sufficient concentration of MoS2 in suspension. The exfoliated flakes are converted into MoS2 quantum dots (QDs), through a hydrothermal procedure. Alternatively, when the flakes are processed with precursors for zinc sulphide (ZnS) synthesis, a simultaneous break-down and composite growth is achieved. The products are separated by centrifugation, into large ZnS spheres (200-300 nm) and small MoS2-ZnS hybrid QD materials (<100 nm), of which, the latter show favorable optical properties. Two concurrent photoluminescent (PL) peaks are seen at 380 and 450 nm, which are assigned to MoS2 and ZnS components of QDs, respectively. The PL emission from MoS2-ZnS QDs is of high energy and is more intense than the bare MoS2 flakes or QDs, with a quantum yield as high as 1.96%. The emission wavelength is independent from the excitation wavelength and does not change over time. Due to such properties, the developed hybrid QDs are potentially suitable for imaging and sensing applications.

A unique in vivo approach for investigating antimicrobial materials utilizing fistulated animals.

Unique in vivo tests were conducted through the use of a fistulated ruminant, providing an ideal environment with a diverse and vibrant microbial community. Utilizing such a procedure can be especially invaluable for investigating the performance of antimicrobial materials related to human and animal related infections. In this pilot study, it is shown that the rumen of a fistulated animal provides an excellent live laboratory for assessing the properties of antimicrobial materials. We investigate microbial colonization onto model nanocomposites based on silver (Ag) nanoparticles at different concentrations into polydimethylsiloxane (PDMS). With implantable devices posing a major risk for hospital-acquired infections, the present study provides a viable solution to understand microbial colonization with the potential to reduce the incidence of infection through the introduction of Ag nanoparticles at the optimum concentrations. In vitro measurements were also conducted to show the validity of the approach. An optimal loading of 0.25 wt% Ag is found to show the greatest antimicrobial activity and observed through the in vivo tests to reduce the microbial diversity colonizing the surface.

Substoichiometric two-dimensional molybdenum oxide flakes: a plasmonic gas sensing platform.

Two-dimensional (2D) molybdenum oxides at their various stoichiometries are promising candidates for generating plasmon resonances in visible light range. Herein, we demonstrate plasmonic 2D molybdenum oxide flakes for gas sensing applications, in which hydrogen (H2) is selected as a model gas. The 2D molybdenum oxide flakes are obtained using a grinding-assisted liquid exfoliation method and exposed to simulated sunlight to acquire its substoichiometric quasi-metallic form. After the exposure to H2 gas molecules, the quasi-metallic molybdenum oxide flakes are partially transformed into semiconducting states, thus gradually losing their plasmonic properties. The novel 2D plasmonic sensing platform is tested using different concentrations of H2 gas at various operating temperatures to comprehensively assess its sensing performance. The presented 2D plasmonic system offers great opportunities for future sensing and optical applications.

Reduced impurity-driven defect states in anodized nanoporous Nb2O5: the possibility of improving performance of photoanodes.

Anodized nanoporous Nb2O5 films are synthesized using two different types of electrolyte compositions onto transparent conductive glasses and their impurities induced during the anodization process are assessed. These films are incorporated as photoanodes in dye sensitized solar cells (DSSCs). The one with no traces of impurity-driven defects exhibits higher current density and longer electron lifetimes, and consequently, an improvement in photoconversion efficiencies compared to the one that contains impurities.

Electrochemical control of photoluminescence in two-dimensional MoS(2) nanoflakes.

Two-dimensional (2D) transition metal dichalcogenide semiconductors offer unique electronic and optical properties, which are significantly different from their bulk counterparts. It is known that the electronic structure of 2D MoS2, which is the most popular member of the family, depends on the number of layers. Its electronic structure alters dramatically at near atomically thin morphologies, producing strong photoluminescence (PL). Developing processes for controlling the 2D MoS2 PL is essential to efficiently harness many of its optical capabilities. So far, it has been shown that this PL can be electrically or mechanically gated. Here, we introduce an electrochemical approach to actively control the PL of liquid-phase-exfoliated 2D MoS2 nanoflakes by manipulating the amount of intercalated ions including Li(+), Na(+), and K(+) into and out of the 2D crystal structure. These ions are selected as they are crucial components in many bioprocesses. We show that this controlled intercalation allows for large PL modulations. The introduced electrochemically controlled PL will find significant applications in future chemical and bio-optical sensors as well as optical modulators/switches.

Anodization of Ti thin film deposited on ITO.

We have investigated several key aspects for the self-organization of nanotubes in RF sputtered titanium (Ti) thin films formed by the anodization process in fluoride-ion-containing neutral electrolytes. Ti films were deposited on indium tin oxide (ITO) glass substrates at room temperature and 300 degrees C, and then anodized. The films were studied using scanning electron microscopy (SEM), X-ray diffraction (XRD), and UV-vis spectrometry before and after anodization. It was observed that anodization of high temperature deposited films resulted in nanotube type structures with diameters in the range of 10-45 nm for an applied voltage of 5-20 V. In addition, the anatase form of TiO(2) is formed during the anodization process which is also confirmed using photocurrent measurements. However, the anodization of room temperature deposited Ti films resulted in irregular pores or holes.