Recent progress in the design, synthesis and applications of chiral metal-organic frameworks.

Chiral Metal-Organic Frameworks (CMOFs) are unique crystalline and porous class of materials which is composed of organic linkers and metal ions. CMOFs surpass traditional organic and inorganic porous materials because of their tunable shape, size, functional diversity, and selectivity. Specific applications of CMOFs may be exploited by introducing desired functional groups. CMOFs have chiral recognition abilities, making them unique for chiral compound synthesis and separation. The CMOFs can be synthesized through different approaches. Two main approaches have been discussed, i.e., direct and indirect synthesis. Synthetic strategies play an essential role in getting desired properties in MOFs. CMOFs find potential applications in adsorption, asymmetric catalysis, luminescence, degradation, and enantioselective separation. The MOFs' porosity, stability, and reusability make them an attractive material for these applications. The plethora of applications of CMOFs have motivated chemists to synthesize novel MOFs and number of MOFs have been ever-escalating. Herein, the synthetic methods of CMOFs and their various applications have been discussed.

Direct air capture (DAC) of CO2 using polyethylenimine (PEI) "snow": a scalable strategy.

We have developed a cross-linked polyethyleneimine non-porous material (PEI "snow") for direct air capture (DAC) of CO2. This new hydrogel is green, inexpensive, readily scalable and can be fabricated through simple crosslinking of PEI with triglycidyl trimethylolpropane ether (TTE) in 10 minutes. It demonstrates outstanding DAC performance (overall CO2 uptake efficiency of approximately 50 mg g-1 of sorbent) at lab scale (sorbent weight roughly 60 g, air flow rate 2000 ml min-1) and the CO2 can be desorbed using low-grade waste steam.

Direct infrared spectroscopy for the size-independent identification and quantification of respirable particles relative mass in mine dusts.

Due to the global need for energy and resources, many workers are involved in underground and surface mining operations where they can be exposed to potentially hazardous crystalline dust particles. Besides commonly known alpha quartz, a variety of other materials may be inhaled when a worker is exposed to airborne dust. To date, the challenge of rapid in-field monitoring, identification, differentiation, and quantification of those particles has not been solved satisfactorily, in part because conventional analytical techniques require laboratory environments, complex method handling, and tedious sample preparation procedures and are in part limited by the effects of particle size. Using a set of the three most abundant minerals in limestone mine dust (i.e., calcite, dolomite, and quartz) and real-world dust samples, we demonstrate that Fourier transform infrared (FTIR) spectroscopy in combination with appropriate multivariate data analysis strategies provides a versatile tool for the identification and quantification of the mineral composition in relative complex matrices. An innovative analytical method with the potential of in-field application for quantifying the relative mass of crystalline particles in mine dust has been developed using transmission and diffuse reflection infrared Fourier transform spectroscopy (DRIFTS) within a unified multivariate model. This proof-of-principle study shows how direct on-site quantification of crystalline particles in ambient air may be accomplished based on a direct-on-filter measurement, after mine dust particles are collected directly onto PVC filters by the worker using body-mounted devices. Without any further sample preparation, these loaded filters may be analyzed via transmission infrared (IR) spectroscopy and/or DRIFTS, and the mineral content is immediately quantified via a partial least squares regression (PLSR) algorithm that enables the combining of the spectral data of both methods into a single robust model. Furthermore, it was also demonstrated that the size regime of dust particles may be classified into groups of hazardous and less hazardous size regimes. Thus, this technique may provide additional essential information for controlling air quality in surface and underground mining operations. Graphical Abstract.

Polyethylenimine "Snow": An Emerging Material for Efficient Carbon Removal.

Amine-functionalized solid adsorbents are one of the most promising alternatives to the conventional "amine scrubbing" for carbon capture with a number of prominent examples being reported. However, their widespread application in industry is unfulfilled due to their overall performance and complex fabrication, which relies on a porous support. In this "proof of concept" study, we report an approach for generating a new type of material called polyethylenimine (PEI) 'snow', which can be prepared for use in under 15 min. The material does not require a support, and the resulting CO2 uptake is the highest reported to date for PEI-functionalized materials. This was achieved through a rigorous material program that identified conditions where a material with the requisite properties could be generated. From experimental measurements, the virtual dryness of the PEI snow results in fast CO2 absorption kinetics, which is comparable to conventional solid adsorbents, but its CO2 uptake (451.5 mg CO2/g PEI) is the highest reported so far. Breakthrough curves demonstrate the outstanding CO2 selectivity over N2 and CH4 (above 1000), with the potential for post-combustion capture and natural gas sweeting. This strategy can be applied in affordable and efficient gas treatment for various large point sources.

The Effect of Pressure and Temperature on Mid-Infrared Sensing of Dissolved Hydrocarbons in Water.

Attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy using a polymer coated internal reflection element/waveguide is an established sensor platform for the detection of a range of organic and hydrocarbon molecules dissolved in water. The polymer coating serves two purposes: to concentrate hydrocarbons from the aqueous phase and to exclude water along with other interfering molecules from the surface of the internal reflection element. Crucial to reliable quantification and analytical performance is the calibration of the ATR-FTIR sensor which is commonly performed in water under mild ambient conditions (i.e., 25 °C and 1 atm). However, there is a pressing need to monitor environmental and industrial processes/events that may occur at high pressures and temperatures where this calibration approach is unsuitable. Using a ruggedized optical fiber probe with a diamond-based ATR, we have conducted mid-infrared sensor experiments to understand the influence of high pressure (up to 207 bar) and temperature (up to 80 °C) on the detection of toluene and naphthalene dissolved in water. Using a poly(isobutylene) film, we have shown that the IR spectroscopic response is relatively unaffected by changes in pressure; however, a diminished response was observed with increasing temperature. We reveal that changes in the refractive index of the polymer film with temperature have only a minor effect on sensitivity. A more plausible explanation for the observed significant change in sensor response with temperature is that the partitioning process is exothermic and becomes less favorable with increasing temperature. This Article shows that the sensitivity is relatively invariant to pressure; however, the thermal variations are significant and need to be considered when quantifying the concentration of hydrocarbons in water.

Mid-Infrared Spectroscopic Method for the Identification and Quantification of Dissolved Oil Components in Marine Environments.

The use of mid-infrared sensors based on conventional spectroscopic equipment for oil spill monitoring and fingerprinting in aqueous systems has to date been mainly confined to laboratory environments. This paper presents a portable-based mid-infrared attenuated total reflectance (MIR-ATR) sensor system that was used to quantify a number of environmentally relevant hydrocarbon contaminants in marine water. The sensor comprises a polymer-coated diamond waveguide in combination with a room-temperature operated pyroelectric detector, and the analytical performance was optimized by evaluating the influence of polymer composition, polymer film thickness, and solution flow rate on the sensor response. Uncertainties regarding the analytical performance and instrument specifications for dissolved oil detection were investigated using real-world seawater matrices. The reliability of the sensor was tested by exposition to known volumes of different oils; crude oil and diesel samples were equilibrated with seawater and then analyzed using the developed MIR-ATR sensor system. For validation, gas chromatographic measurements were performed revealing that the MIR-ATR sensor is a promising on-site monitoring tool for determining the concentration of a range of dissolved oil components in seawater at ppb to ppm levels.

Infrared attenuated total reflectance spectroscopy: an innovative strategy for analyzing mineral components in energy relevant systems.

The direct qualitative and quantitative determination of mineral components in shale rocks is a problem that has not been satisfactorily resolved to date. Infrared spectroscopy (IR) is a non-destructive method frequently used in mineral identification, yet challenging due to the similarity of spectral features resulting from quartz, clay, and feldspar minerals. This study reports on a significant improvement of this methodology by combining infrared attenuated total reflection spectroscopy (IR-ATR) with partial least squares (PLS) regression techniques for classifying and quantifying various mineral components present in a number of different shale rocks. The developed multivariate classification model was calibrated using pure component mixtures of the most common shale minerals (i.e., kaolinite, illite, montmorillonite, calcite, and quartz). Using this model, the IR spectra of 11 real-world shale samples were analyzed and evaluated. Finally, the performance of the developed IR-ATR method was compared with results obtained via X-ray diffraction (XRD) analysis.

A mid-infrared sensor for the determination of perfluorocarbon-based compounds in aquatic systems for geosequestration purposes.

Perfluorocarbon (PFC) compounds have been used as chemical tracer molecules to understand the movement of supercritical carbon dioxide for geosequestration monitoring and verification purposes. A commonly used method for detecting PFCs involves the collection of a sample from either soil-gas or the atmosphere via carbon-based sorbents which are then analyzed in a laboratory. However, PFC analysis in aquatic environments is neglected and this is an issue that needs to be considered since the PFC is likely to undergo permeation through the overlying water formations. This paper presents for the first time an innovative analytical method for the trace level in situ detection of PFCs in water. It reports on the development of a sensor based on mid-infrared attenuated total reflection (MIR-ATR) spectroscopy for determining the concentration of perfluoromethylcyclohexane (PMCH) and perfluoro-1,3-dimethylcyclohexane (PDCH) in aquatic systems. The sensor comprises a zinc selenide waveguide with the surface modified by a thin polymer film. The sensitivity of this device was investigated as a function of polymer type, coating thickness, and solution flow rates. The limit of detection (LOD) was determined to be 23 ppb and 79 ppb for PMCH and PDCH, respectively when using a 5 µm thick polyisobutylene (PIB) coated waveguide. This study has shown that the MIR-ATR sensor can be used to directly quantify PFC-based chemical tracer compounds in water over the 20-400 ppb concentration range.

Fingerprinting oils in water via their dissolved VOC pattern using mid-infrared sensors.

An infrared attenuated total reflection (IR-ATR) method for detecting, differentiating, and quantifying hydrocarbons dissolved in water relevant for oil spills by evaluating the "fingerprint" of the volatile organic compounds (VOCs) associated with individual oil types in the mid-infrared spectral range (i.e., 800-600 cm(-1)) is presented. In this spectral regime, these hydrocarbons provide distinctive absorption features, which may be used to identify specific hydrocarbon patterns that are characteristic for different crude and refined oils. For analyzing the "VOC fingerprint" resulting from various oil samples, aqueous solutions containing the dissolved hydrocarbons from different crude oils (i.e., types "Barrow", "Goodwyn", and "Saladin") and refined oils (i.e., "Petrol" and "Diesel") were analyzed using a ZnSe ATR waveguide as the optical sensing element. To minimize interferences from the surrounding water matrix and for amplifying the VOC signatures by enrichment, a thin layer of poly(ethylene-co-propylene) was coated onto the ATR waveguide surface, thereby enabling the establishment of suitable calibration functions for the quantification of characteristic concentration patterns of the detected VOCs. Multivariate data analysis was then used for a prelininary classification of various oil-types via their VOC patterns.

Pore size dynamics in interpenetrated metal organic frameworks for selective sensing of aromatic compounds.

The two-fold interpenetrated metal-organic framework, [Zn2(bdc)2(dpNDI)]n (bdc=1,4-benzenedicarboxylate, dpNDI=N'N'-di(4-pyridyl)-1,4,5,8-naphthalenediimide) can undergo structural re-arrangement upon adsorption of chemical species changing its pore structure. For a competitive binding process with multiple analytes of different sizes and geometries, the interpenetrated framework will adopt a conformation to maximize the overall binding interactions. In this study, we show for binary mixtures that there is a high selectivity for the larger methylated aromatic compounds, toluene and p-xylene, over the small non-methylated benzene. The dpNDI moiety within [Zn2(bdc)2(dpNDI)]n forms an exciplex with these aromatic compounds. The emission wavelength is dependent on the strength of the host-guest CT interaction allowing these compounds to be distinguished. We show that the sorption selectivity characteristics can have a significant impact on the fluorescence sensor response of [Zn2(bdc)2(dpNDI)]n towards environmentally important hydrocarbons based contaminants (i.e., BTEX, PAH).

Using plasticizers to control the hydrocarbon selectivity of a poly(methyl methacrylate)-coated quartz crystal microbalance sensor.

Chemical sensors based on a polymer coated quartz crystal microbalance (QCM) generally present poor molecular selectivity for compounds that contain similar functional groups and possess the same chemical properties. This paper shows for the first time that the selectivity and sensitivity of a poly(methyl methacrylate) (PMMA) based QCM sensor can be significantly enhanced for aromatic hydrocarbons by incorporating a plasticizer into the polymer film. The sensor was fabricated by spin coating PMMA onto a quartz crystal, and the influence of plasticizer type and amount on the response was evaluated. It was shown that the hydrocarbon sensitivity of plasticizer-free PMMA is negligible, while the sensitivity of plasticized PMMA was similar to or in some cases greater relative to highly responsive rubbery polymers such as polyisobutylene (PIB). Detection limits of 4.0, 1.5, 0.4, 0.6, and 0.1 ppm were obtained on a PMMA film containing 25% w/w di(2-ethylhexyl) phthalate for benzene, toluene, ethylbenzene, p-xylene, and naphthalene, respectively. We found that at low plasticizer levels (∼10% w/w) the PMMA film was more sensitive toward ethylbenzene and p-xylene over naphthalene when compared to a PIB film under similar measurement conditions. Attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) measurements were performed to understand the sensing mechanism, and these studies confirmed a higher hydrocarbon uptake by PMMA in the presence of plasticizer. Positron annihilation lifetime spectroscopy (PALS) studies detected variations in the free volume properties of the polymer films as a function of plasticizer content. The accessible free volume as measured by PALS was significantly less in the PMMA films compared to the PIB, and this result correlates favorably with differences in the QCM response pattern. The QCM results have been rationalized in terms of free volume theory which is responsible for the higher hydrocarbon diffusion/sorption with increased plasticizer content.

The impact of water and hydrocarbon concentration on the sensitivity of a polymer-based quartz crystal microbalance sensor for organic compounds.

Long-term environmental monitoring of organic compounds in natural waters requires sensors that respond reproducibly and linearly over a wide concentration range, and do not degrade with time. Although polymer coated piezoelectric based sensors have been widely used to detect hydrocarbons in aqueous solution, very little information exists regarding their stability and suitability over extended periods in water. In this investigation, the influence of water aging on the response of various polymer membranes [polybutadiene (PB), polyisobutylene (PIB), polystyrene (PS), polystyrene-co-butadiene (PSB)] was studied using the quartz crystal microbalance (QCM). QCM measurements revealed a modest increase in sensitivity towards toluene for PB and PIB membranes at concentrations above 90 ppm after aging in water for 4 days. In contrast, the sensitivity of PS and PSB coated QCM sensors depended significantly on the toluene concentration and increased considerably at concentrations above 90 ppm after aging in water for 4 days. Attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) showed that there is a change in the sorption mechanism at higher toluene levels for PS and PSB. Positron annihilation lifetime spectroscopy (PALS) studies were performed to investigate the free volume properties of all polymers and to monitor any changes in the free volume size and distribution due to water and toluene exposure. The PALS did not detect any considerable variation in the free volume properties of the polymer films as a function of solution composition and soaking time, implying that viscoelastic and/or interfacial processes (i.e. surface area changes) are probably responsible for variations in the QCM sensitivity at high hydrocarbon concentrations. The results suggest that polymer membrane conditioning in water is an issue that needs to be considered when performing QCM measurements in the aqueous phase. In addition, the study shows that the hydrocarbon response is concentration dependant for polymers with a high glass transition temperature, and this feature is often neglected when comparing sensor sensitivity in the literature.

Modifying the response of a polymer-based quartz crystal microbalance hydrocarbon sensor with functionalized carbon nanotubes.

This report compares the performance of polymer and carbon nanotube-polymer composite membranes on a quartz crystal microbalance (QCM) sensor for the detection of aromatic hydrocarbons (benzene, toluene, ethylbenzene, p-xylene and naphthalene) in aqueous solutions. Several different polymers (polystyrene, polystyrene-co-butadiene, polyisobutylene and polybutadiene) and types of functionalized carbon nanotubes (multi-walled and single-walled carbon nanotubes) were investigated at varying carbon nanotube (CNT) loading levels and film thicknesses. In a majority of instances, the difference in response between membranes comprising pure polymer and membranes containing 10% (w/w) carbon nanotubes were not statistically significant. However, a notable exception is the decreasing sensitivity towards p-xylene with increasing carbon nanotube content in a polybutadiene film. This variation in sensitivity can be attributed to a change in the sorption mechanism from absorption into the polymer phase to adsorption onto the carbon nanotube sidewalls. With much thicker coatings of 10% (w/w) carbon nanotube in polybutadiene, the sensitivity towards toluene was higher compared to the pure polymer. The increased toluene sensitivity may be partially attributed to an increase in the sorption capacity of a carbon nanotube polymer composite film relative to its corresponding pure polymer film. Attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) measurements were performed to understand the mechanism of sorption and these studies showed that the addition of functionalized CNT to the polymer increases the absorption of certain types of hydrocarbons. This study demonstrates that carbon nanotubes can be incorporated into a polymer-coated QCM sensor and that composite films may be used to modify the QCM response and selectivity during the analysis of complex hydrocarbon mixtures.

Mid-infrared sensing of organic pollutants in aqueous environments.

The development of chemical sensors for monitoring the levels of organic pollutants in the aquatic environment has received a great deal of attention in recent decades. In particular, the mid-infrared (MIR) sensor based on attenuated total reflectance (ATR) is a promising analytical tool that has been used to detect a variety of hydrocarbon compounds (i.e., aromatics, alkyl halides, phenols, etc.) dissolved in water. It has been shown that under certain conditions the MIR-ATR sensor is capable of achieving detection limits in the 10-100 ppb concentration range. Since the infrared spectral features of every single organic molecule are unique, the sensor is highly selective, making it possible to distinguish between many different analytes simultaneously. This review paper discusses some of the parameters (i.e., membrane type, film thickness, conditioning) that dictate MIR-ATR sensor response. The performance of various chemoselective membranes which are used in the fabrication of the sensor will be evaluated. Some of the challenges associated with long-term environmental monitoring are also discussed.

Environmental monitoring of hydrocarbons: a chemical sensor perspective.

Assessing the environmental impact of organic pollutants requires reliable analytical tools that can rapidly screen them with minimal sample handling. Chemical sensors are expected to play an increasing role in environmental monitoring, and recent technological advances are certain to facilitate the application of chemical sensing devices. The search for highly selective, sensitive, low cost, stable, and robust sensors for hydrocarbons is an area of interest that is reflected by many publications on this topic. This report surveys some of the work that has been undertaken using sensors to detect hydrocarbons in the gas and liquid phase. The analytical capabilities of various sensors are compared and discussed in terms of their selectivity, sensitivity, and detection limit. It was found that the sensitivity is highly dependent on the experimental conditions used in the preparation of the sensing surface. Many sensors display acceptable sensitivity under controlled laboratory conditions; however, very few are selective enough to distinguish among several hydrocarbons in complex mixtures. Selectivity is still a challenge that is hindering the widespread application of chemical sensors for environmental monitoring of hydrocarbons and a number of strategies have been proposed to help overcome some of these problems.

The role of biosensors in the detection of emerging infectious diseases.

Global biosecurity threats such as the spread of emerging infectious diseases (i.e., avian influenza, SARS, Hendra, Nipah, etc.) and bioterrorism have generated significant interest in recent years. There is considerable effort directed towards understanding and negating the proliferation of infectious diseases. Biosensors are an attractive tool which have the potential to detect the outbreak of a virus and/or disease. Although there is a host of technologies available, either commercially or in the scientific literature, the development of biosensors for the detection of emerging infectious diseases (EIDs) is still in its infancy. There is no doubt that the glucose biosensor, the gene chip, the protein chip, etc. have all played and are still playing a significant role in monitoring various biomolecules. Can biosensors play an important role for the detection of emerging infectious diseases? What does the future hold and which biosensor technology platform is suitable for the real-time detection of infectious diseases? These and many other questions will be addressed in this review. The purpose of this review is to present an overview of biosensors particularly in relation to EIDs. It provides a synopsis of the various types of biosensor technologies that have been used to detect EIDs, and describes some of the technologies behind them in terms of transduction and bioreceptor principles.

A small angle neutron scattering and electrochemical impedance spectroscopy study of the nanostructure of the iron chalcogenide glass ion-selective electrode.

This paper presents a preliminary structural and interfacial study of the iron chalcogenide glass [i.e., Fe(x)(Ge(28)Sb(12)Se(60))(100-x)] ion-selective electrode (ISE) using small angle neutron scattering (SANS) and electrochemical impedance spectroscopy (EIS). SANS detected variations in the neutron scattering as a function of iron content in the chalcogenide glass. Furthermore, a change in the chalcogenide glass structure was observed at elevated iron dopant levels. Conversely, EIS was used to show that the iron chalcogenide membrane comprises various time constants, and the interfacial charge transfer reaction depends on the membrane iron content. Equivalent circuit modeling revealed that the charge transfer resistance decreases at elevated iron levels, and this may be related to the presence of iron defects in the glass. It is proposed that the iron chalcogenide membrane comprises an iron nanostructural network embedded in the amorphous matrix, and this directly influences the electrical conductivity and concomitant electrochemical reactivity of the glass.

A multi-technique surface study of the mercury(II) chalcogenide ion-selective electrode in saline media.

X-ray photoelectron spectroscopy (XPS), secondary ion mass spectrometry (SIMS), rotating disc electrode-electrochemical impedance spectroscopy (RDE-EIS) and synchrotron radiation-grazing incidence X-ray diffraction (SR-GIXRD) have been used to study the response mechanism of the mercury(II) chalcogenide ion-selective electrode (ISE) in saline media. XPS and SIMS have shown that the chalcogenide surface is poisoned by silver chloride, or a mixture of silver halides, on continuous exposure to synthetic and real seawater. Significantly, the in-situ SR-GIXRD study demonstrated that electrode fouling in synthetic seawater is linked to the formation of poorly crystalline or amorphous silver chloride, and that the low level of free mercury(II) in a calibration buffer (i.e., 10(-14) M) is able to undergo metathesis with silver(II) sulfide in the membrane generating mercury(II) sulfide. Significantly, the results of this detailed surface study have shown that silver chloride fouling of the electrode is ameliorated in real seawater comprising natural organic ligands, and this has been attributed to the peptization of silver chloride by the surfactant-like nature of seawater ligands at pH 8. RDE-EIS aging studies have revealed that the chalcogenide membrane experiences a sluggish charge transfer reaction in seawater, and contrary to a previous report for a static electrode, the seawater matrix does not passivate the RDE. The results of this XPS, SIMS, RDE-EIS and SR-GIXRD study have elucidated the response mechanism of the mercury(II) ISE in saline media.

Continuous flow analysis of iron in zinc electrowinning electrolyte using an iron chalcogenide glass ion-selective electrode Part I. Synthetic media.

It is shown that the iron(III) chalcogenide glass membrane ion-selective electrode (ISE) can be calibrated in continuous flow analysis (CFA) using acidified iron(III) nitrate standards, yielding a 60+/-3 mV per decade change in activity of Fe(3+) response in the range 10(-7)-10(-2) M total iron(III). Extended ageing of the iron(III) ISE in 2 M zinc(II) sulphate did not alter the potentiometric response characteristics of the electrode. Furthermore, electrochemical impedance spectroscopy and X-ray photoelectron spectroscopy in the presence and absence of zinc(II) sulphate failed to detect a zinc(II) interference on the iron(III) ISE. CFA/ISE determined activities of Fe(3+) in synthetic zinc electrolyte containing 2x10(-3)-2x10(-1) M total iron(III) yielded results falling within +/-0.2logaFe(3+) unit of the corresponding iron speciation data calculated using the minteqa2 program.