Covalent organic frameworks as multifunctional materials for chemical detection

Sensitive and selective detection of chemical and biological analytes is critical in various scientific and technological fields. As an emerging class of multifunctional materials, covalent organic frameworks (COFs) with their unique properties of chemical modularity, large surface area, high stability, low density, and tunable pore sizes and functionalities, which together define their programmable properties, show promise in advancing chemical detection. This review demonstrates the recent progress in chemical detection where COFs constitute an integral component of the achieved function. This review highlights how the unique properties of COFs can be harnessed to develop different types of chemical detection systems based on the principles of chromism, luminescence, electrical transduction, chromatography, spectrometry, and others to achieve highly sensitive and selective detection of various analytes, ranging from gases, volatiles, ions, to biomolecules. The key parameters of detection performance for target analytes are summarized, compared, and analyzed from the perspective of the detection mechanism and structure–property–performance correlations of COFs. Conclusions summarize the current accomplishments and analyze the challenges and limitations that exist for chemical detection under different mechanisms. Perspectives on how future directions of research can advance the COF-based chemical detection through innovation in novel COF design and synthesis, progress in device fabrication, and exploration of novel modes of detection are also discussed

Influence of Fluorocarbon and Hydrocarbon Acyl Groups at the Surface of Bovine Carbonic Anhydrase II on the Kinetics of Denaturation by Sodium Dodecyl Sulfate

This paper examines the influence of acylation of the Lys-ε-NH3+ groups of bovine carbonic anhydrase (BCA, EC 4.2.1.1) to Lys-ε-NHCOR (R = −CH3, −CH2CH3, and −CH(CH3)2, −CF3) on the rate of denaturation of this protein in buffer containing sodium dodecyl sulfate (SDS). Analysis of the rates suggested separate effects due to electrostatic charge and hydrophobic interactions. Rates of denaturation (kAc,n) of each series of acylated derivatives depended on the number of acylations (n). Plots of log kAc,n vs n followed U-shaped curves. Within each series of derivatives, rates of denaturation decreased as n increased to 7; this decrease was compatible with increasingly unfavorable electrostatic interactions between SDS and protein. In this range of n, rates of denaturation also depended on the choice of the acyl group as n increased to 7, in a manner compatible with favorable hydrophobic interactions between SDS and the −NHCOR groups. As n increased in the range 7 < n < 14, however, rates of denaturation stayed approximately constant; analysis suggested that these rates were compatible with an increasingly important contribution to denaturation that depended both on the net negative charge of the protein and on the hydrophobicity of the R group. The mechanism of denaturation thus seems to change with the extent of acylation of the protein. For derivatives with the same net electrostatic charge, rates of denaturation increased with the acyl group (by a factor of 3 for n 14) in the order CH3CONH− < CH3CH2CONH− < (CH3)2CHCONH− < CF3CONH−. These results suggested that the hydrophobicity of CF3CONH− is slightly greater (by a factor of <2) than that of RHCONH− with similar surface area.Chemistry and Chemical Biolog

Templated Self-Assembly in Three Dimensions Using Magnetic Levitation

Although self-assembly (SA) in two dimensions (2D) is highly developed (especially using surfaces as a templates), SA in three dimensions (3D) has been more difficult. This paper describes a strategy for SA in 3D of diamagnetic plastic objects (mm- to cm-sized in this work, but in principle in sizes from [similar]10 μm to m) supported in a paramagnetic fluid by a non-uniform magnetic field. The magnetic field and its gradient levitate the objects, template their self-assembly, and influence the shape of the assembled cluster. The structure of the 3D assembling objects can be further directed using hard mechanical templates—either the walls of the container or co-levitating components—which coincide spatially with the soft template of the magnetic field gradient. Mechanical agitation anneals the levitating clusters; the addition of photocurable adhesive, followed by UV illumination, can permanently fuse components together.Chemistry and Chemical Biolog

Magnetic Levitation as a Platform for Competitive Protein–Ligand Binding Assays

This paper describes a method based on magnetic levitation (MagLev) that is capable of indirectly measuring the binding of unlabeled ligands to unlabeled protein. We demonstrate this method by measuring the affinity of unlabeled bovine carbonic anhydrase (BCA) for a variety of ligands (most of which are benzene sulfonamide derivatives). This method utilizes porous gel beads that are functionalized with a common aryl sulfonamide ligand. The beads are incubated with BCA and allowed to reach an equilibrium state in which the majority of the immobilized ligands are bound to BCA. Since the beads are less dense than the protein, protein binding to the bead increases the overall density of the bead. This change in density can be monitored using MagLev. Transferring the beads to a solution containing no protein creates a situation where net protein efflux from the bead is thermodynamically favorable. The rate at which protein leaves the bead for the solution can be calculated from the rate at which the levitation height of the bead changes. If another small molecule ligand of BCA is dissolved in the solution, the rate of protein efflux is accelerated significantly. This paper develops a reaction-diffusion (RD) model to explain both this observation, and the physical-organic chemistry that underlies it. Using this model, we calculate the dissociation constants of several unlabeled ligands from BCA, using plots of levitation height versus time. Notably, although this method requires no electricity, and only a single piece of inexpensive equipment, it can measure accurately the binding of unlabeled proteins to small molecules over a wide range of dissociation constants (Kd values within the range from 10 nM to 100 μM are measured easily). Assays performed using this method generally can be completed within a relatively short time period (20 min–2 h). A deficiency of this system is that it is not, in its present form, applicable to proteins with molecular weight greater than approximately 65 kDa.Chemistry and Chemical Biolog

Bimetallic Two-Dimensional Metal–Organic Frameworks for the Chemiresistive Detection of Carbon Monoxide

This paper describes the demonstration of a series of heterobimetallic, isoreticular 2D conductive metal–organic frameworks (MOFs) with metallophthalocyanine (MPc, M=Co and Ni) units interconnected by Cu nodes towards low-power chemiresistive sensing of ppm levels of carbon monoxide (CO). Devices achieve a sub-part-per-million (ppm) limit of detection (LOD) of 0.53 ppm toward CO at a low driving voltage of 0.1 V. MPc-based Cu-linked MOFs can continuously detect CO at 50 ppm, the permissible exposure limit required by the Occupational Safety and Health Administration (OSHA), for multiple exposures, and realize CO detection in air and in humid environment. Diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), density functional theory (DFT) calculations, and comparison experiments suggest the contribution of Cu nodes to CO binding and the essential role of MPc units in tuning and amplifying the sensing response

Analyzing Forensic Evidence Based on Density with Magnetic Levitation

This paper describes a method for determining the density of contact trace objects with magnetic levitation (MagLev). MagLev measurements accurately determine the density (±0.0002 g/cm3) of a diamagnetic object and are compatible with objects that are nonuniform in shape and size. The MagLev device (composed of two permanent magnets with like poles facing) and the method described provide a means of accurately determining the density of trace objects. This method is inexpensive, rapid, and verifiable and provides numerical values—independent of the specific apparatus or analyst—that correspond to the absolute density of the sample that may be entered into a searchable database. We discuss the feasibility of MagLev as a possible means of characterizing forensic-related evidence and demonstrate the ability of MagLev to (i) determine the density of samples of glitter and gunpowder, (ii) separate glitter particles of different densities, and (iii) determine the density of a glitter sample that was removed from a complex sample matrix.Chemistry and Chemical Biolog

Unraveling the Electrical and Magnetic Properties of Layered Conductive Metal-Organic Framework With Atomic Precision

This paper describes structural elucidation of a layered conductive metal-organic framework (MOF) material Cu3(C6O6)2 by microcrystal electron diffraction with sub-angstrom precision. This insight enables the first identification of an unusual π-stacking interaction in a layered MOF material characterized by an extremely short (2.73 Å) close packing of the ligand arising from pancake bonding and ordered water clusters within pores. Band structure analysis suggests semiconductive properties of the MOF, which are likely related to the localized nature of pancake bonds and the formation of a singlet dimer of the ligand. The spin of CuII within the Kagomé arrangement dominates the paramagnetism of the MOF, leading to strong geometrical magnetic frustration

Paramagnetic Ionic Liquids for Measurements of Density Using Magnetic Levitation

Paramagnetic ionic liquids (PILs) provide new capabilities to measurements of density using magnetic levitation (MagLev). In a typical measurement, a diamagnetic object of unknown density is placed in a container containing a PIL. The container is placed between two magnets (typically NdFeB, oriented with like poles facing). The density of the diamagnetic object can be determined by measuring its position in the magnetic field along the vertical axis (levitation height, h), either as an absolute value, or relative to internal standards of known density. For density measurements by MagLev, PILs have three advantages over solutions of paramagnetic salts in aqueous or organic solutions: (i) negligible vapor pressures; (ii) low melting points; (iii) high thermal stabilities. In addition, the densities, magnetic susceptibilities, glass transition temperatures, thermal decomposition temperatures, viscosities, and hydrophobicities of PILs can be tuned over broad ranges by choosing the cation–anion pair. The low melting points and high thermal stabilities of PILs provide large liquidus windows for density measurements. This paper demonstrates applications and advantages of PILs in density-based analyses using MagLev.Chemistry and Chemical Biolog

Conductive Stimuli-Responsive Coordination Network Linked with Bismuth for Chemiresistive Gas Sensing

This paper describes the design, synthesis, characterization, and performance of a novel semiconductive crystalline coordination network, synthesized using 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) ligands interconnected with bismuth ions, toward chemiresistive gas sensing. Bi(HHTP) exhibits two distinct structures upon hydration and dehydration of the pores within the network, Bi(HHTP)-α and Bi(HHTP)-β, respectively, both with unprecedented network topology (2,3-c and 3,4,4,5-c nodal net stoichiometry, respectively) and unique corrugated coordination geometries of HHTP molecules held together by bismuth ions, as revealed by a crystal structure resolved via microelectron diffraction (MicroED) (1.00 Å resolution). Good electrical conductivity (5.3 × 10–3 S·cm–1) promotes the utility of this material in the chemical sensing of gases (NH3 and NO) and volatile organic compounds (VOCs: acetone, ethanol, methanol, and isopropanol). The chemiresistive sensing of NO and NH3 using Bi(HHTP) exhibits limits of detection 0.15 and 0.29 parts per million (ppm), respectively, at low driving voltages (0.1–1.0 V) and operation at room temperature. This material is also capable of exhibiting unique and distinct responses to VOCs at ppm concentrations. Spectroscopic assessment via X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopic methods (i.e., attenuated total reflectance-infrared spectroscopy (ATR-IR) and diffuse reflectance infrared Fourier transformed spectroscopy (DRIFTS)), suggests that the sensing mechanisms of Bi(HHTP) to VOCs, NO, and NH3 comprise a complex combination of steric, electronic, and protic properties of the targeted analytes

Selective Precipitation and Purification of Monovalent Proteins Using Oligovalent Ligands and Ammonium Sulfate

This paper describes a method for the selective precipitation and purification of a monovalent protein (carbonic anhydrase is used as a demonstration) from cellular lysate using ammonium sulfate and oligovalent ligands. The oligovalent ligands induce the formation of protein–ligand aggregates, and at an appropriate concentration of dissolved ammonium sulfate, these complexes precipitate. The purification involves three steps: (i) the removal of high-molecular-weight impurities through the addition of ammonium sulfate to the crude cell lysate; (ii) the introduction of an oligovalent ligand and the selective precipitation of the target protein–ligand aggregates from solution; and (iii) the removal of the oligovalent ligand from the precipitate by dialysis to release the target protein. The increase of mass and volume of the proteins upon aggregate formation reduces their solubility, and results in the selective precipitation of these aggregates. We recovered human carbonic anhydrase, from crude cellular lysate, in 82% yield and 95% purity with a trivalent benzene sulfonamide ligand. This method provides a chromatography-free strategy of purifying monovalent proteins—for which appropriate oligovalent ligands can be synthesized—and combines the selectivity of affinity-based purification with the convenience of salt-induced precipitation.Chemistry and Chemical Biolog