Heteropentanuclear {Ru(II)Cu(II)4} Kuratowski Complexes Assembled from a Ruthenium(II) Precursor Complex to Study Competing Exchange Interactions in M(II)(ta)2 Networks [ta(-) = 1,2,3-Triazolate].

We report a directed two-step synthesis toward pentanuclear Kuratowski complexes. First, six 5,6-dimethylbenzo[1,2,3]triazole ligands (Me2btaH) are coordinated to a single Ru(II) ion, providing a topologically ideal template for the addition of further metal ions. The synthesis and crystal structures of [RuCu4X4(Me2bta)6] [X = acetylacetonate (acac) and tris(3,5-dimethyl-1-pyrazolyl)borate (Tp*)] are described. Both represent new members of the family of so-called Kuratowski (K3,3) complexes. The coordination units feature triazolato-bridged metal-centered {MM4} tetrahedra, which are known for frustrated magnetic interactions in both complexes and metal-organic frameworks. The novel Ru(II)-centered complexes were synthesized in order to investigate the influence of the presence or absence of a paramagnetic central metal ion in the Kuratowski complex. Superconducting quantum interference device and electron spin resonance measurements demonstrate that small deviations in bond lengths and valence angles can lead to the formation of pairs of magnetic exchange-coupled Cu(II) ions. Which Cu(II) ions pair up can be predicted in Jahn-Teller active compounds by the overlap of the respective orbitals. These data are compared with those gleaned for M(II)(ta)2 (ta = 1,2,3-triazolate) lattices, in which structurally similar {MM4} tetrahedra constitute the secondary building units.

Superhydrophobic Metal-Organic Framework-Based Composite Featuring Removal of Hydrophobic Drugs and Pesticides and Antibacterial Activities.

The widespread use and contamination of natural sources by new-generation drugs and pesticides have enhanced concern about environmental pollution. Understanding the above importance, we developed a superhydrophobic metal-organic framework (MOF) (SHMOF': [Zr6O4(OH)4(BDC-NH-CO-R)2.4(BDC-NH2)0.6(CF3COO)6]·2.5H2O·4DMF) for ecological remediation via adsorption-based separation of hydrophobic drugs (flurbiprofen) and pesticides (fluazinam). The newly developed SHMOF' has a high adsorption capacity toward flurbiprofen and fluazinam, i.e., 435 and 575 mg/g, respectively. The adsorption equilibrium time of the MOF is very short (15 and 10 min for flurbiprofen and fluazinam, respectively). The outstanding superhydrophobic nature of the MOF was employed to separate flurbiprofen and fluazinam from highly alkaline and acidic media and environmental water samples. The SHMOF' has excellent selectivity toward the adsorption-based separation of flurbiprofen and fluazinam in the coexistence of common analytes. Again, we developed a polypropylene (PP) fabric-based composite of SHMOF' (SHMOF'@PP) to separate the hydrophobic targeted analytes by using a zero-energy-consuming filtration-based separation method, which made this separation process cost-efficient and user-friendly. Moreover, Ag nanoparticles were doped to the superhydrophobic composite. The Ag-doped reusable SHMOF'@PP@Ag composite exhibited excellent bacterial antiadhesion and antibacterial properties toward Staphylococcus aureus bacteria.

Unveiling the atomistic and electronic structure of NiII-NO adduct in a MOF-based catalyst by EPR spectroscopy and quantum chemical modelling.

The nature of the chemical bonding between NO and open-shell NiII ions docked in a metal-organic framework is fully characterized by EPR spectroscopy and computational methods. High-frequency EPR experiments reveal the presence of unsaturated NiII ions displaying five-fold coordination. Upon NO adsorption, in conjunction with advanced EPR methodologies and DFT/CASSCF modelling, the covalency of the metal-NO and metal-framework bonds is directly quantified. This enables unravelling the complex electronic structure of NiII-NO species and retrieving their microscopic structure.

2H NMR studies on the dynamics of supercooled water in a metal-organic framework.

We use 2H nuclear magnetic resonance (NMR) to study water (D2O) reorientation and diffusion in the metal-organic framework MFU-4l, which features a regular three-dimensional network of nearly spherical pores with diameters of 1.2 and 1.9 nm. We observe that the rotational correlation times follow Vogel-Fulcher-Tammann and Arrhenius (Ea = 0.48 eV) relations above ∼225 K and below ∼170 K, respectively, whereas the temperature dependence continuously evolves from one to the other behavior in the broad crossover zone in between. In the common temperature range, the present NMR results are fully consistent with previous broadband dielectric spectroscopy (BDS) data on water (H2O) in a very similar framework. Several of our observations, e.g., rotational-translational coupling, indicate that a bulk-like structural (α) relaxation is observed above the crossover region. When cooling through the crossover zone, a quasi-isotropic reorientation mechanism is retained, while 2H spin-lattice relaxation evolves from exponential to nonexponential, implying that the water dynamics probed at low temperatures does no longer fully restore ergodicity on the time scale of this experiment. We discuss that the latter effect may result from bulk-like and/or confinement-imposed spatially heterogeneous water properties. Comparison with previous NMR and BDS results for water in other confinements reveals that, for confinement sizes around 2 nm, water reorientation depends more on the pore diameter than on the pore chemistry, while water diffusion is strongly affected by the connectivity and topology of the pores.

Acenaphtho[1,2-d][1,2,3]triazole and Its Kuratowski Complex: A π-Extended Tecton for Supramolecular and Coordinative Self-Assembly.

π-Extended acenaphtho[1,2-d][1,2,3]triazoles, the unsubstituted Anta-H and its di-tert-butyl derivative Dibanta-H, as well as 5,6,7,8-tetrahydro-1H-naphtho[2,3-d][1,2,3]triazole Cybta-H were obtained in concise syntheses. In the solid state, Dibanta-H forms an unprecedented hydrogen-bonded cyclic tetrad, stabilized by dispersion interactions of the bulky tBu substituents, whereas a cyclic triad was found in the crystal structure of Anta-H. These cyclic assemblies form infinite slipped stacks in the crystals. Evidence for analogous hydrogen-bonded self-assembly in solution was provided by low-temperature NMR spectroscopy and computational analyses. Kuratowski-type pentanuclear complexes [Zn5 Cl4 (Dibanta)6 ] and [Zn5 Cl4 (Cybta)6 ] were prepared from the respective triazoles. In the Dibanta complexes, the π-aromatic surfaces of the ligands extend from the edges of the tetrahedral Zn5 core, yielding an enlarged structure with significant internal molecular free volume and red-shifted fluorescence.

Inhibition, Binding of Organometallics, and Thermally Induced CO Release in an MFU-4-Type Metal-Organic Framework Scaffold with Open Bidentate Bibenzimidazole Coordination Sites.

Triazolate-based MFU-4-type metal-organic frameworks are promising candidates for various applications, of which heterogeneous catalysis has emerged as a hot topic owing to the facile post-synthetic metal and ligand exchange in Kuratowski secondary building units (SBUs). Herein, we present the largest non-interpenetrated isoreticular MFU-4-type framework CFA-19 ([Co5IICl4(H2-bibt)3]; H4-bibt = 1,1',5,5'-tetrahydro-6,6'-biimidazo[4,5-f]benzotriazole; CFA-19 = Coordination Framework Augsburg University-19) and the CFA-19-Tp derivative featuring trispyrazolylborate inhibited SBUs as a scaffold with open bibenzimidazole coordination sites at the backbone of the H4-bibt linker. The proof-of-principle incorporation of accessible MIBr(CO)3 (M = Re, Mn) sites in CFA-19-Tp was revealed by single-crystal X-ray diffraction, and a thermally induced CO release was observed for MnBr(CO)3. Deprotonation of bibenzimidazole was also achieved by the reaction with ZnEt2.

Tridecacyclene Tetraimide: An Easily Reduced Cyclooctatetraene Derivative.

Tridecacyclene tetraimide, TCTI, an electron-deficient non-benzenoid nanocarbon with a C56 N4 polycyclic framework was obtained in a concise synthesis. TCTI has a non-planar structure and forms π-stacked dimers in the solid state. In solution, it undergoes eight single-electron reductions, yielding a range of negatively charged states up to an octaanion. Except for the latter species, which has a remarkably large electronic gap, the anions feature extended near-infrared absorptions, with a particularly strong band at 1692 nm observed for the dianion. A computational analysis of the TCTI anions shows that their stability originates from the combined effects of electron-deficient imide groups and the local aromaticity of reduced acenaphthylene units. The properties of TCTI make it potentially useful in electrochromic and charge storage applications.

An Anthracene-Based Metal-Organic Framework for Selective Photo-Reduction of Carbon Dioxide to Formic Acid Coupled with Water Oxidation.

A Zr-based metal-organic framework has been synthesized and employed as a catalyst for photochemical carbon dioxide reduction coupled with water oxidation. The catalyst shows significant carbon dioxide reduction property with concomitant water oxidation. The catalyst has broad visible light as well as UV light absorption property, which is further confirmed from electronic absorption spectroscopy. Formic acid was the only reduced product from carbon dioxide with a turn-over frequency (TOF) of 0.69 h-1 in addition to oxygen, which was produced with a TOF of 0.54 h-1 . No external photosensitizer is used and the ligand itself acts as the light harvester. The efficient and selective photochemical carbon dioxide reduction to formic acid with concomitant water oxidation using Zr-based MOF as catalyst is thus demonstrated here.

A Zr-Based Metal-Organic Framework with a DUT-52 Structure Containing a Trifluoroacetamido-Functionalized Linker for Aqueous Phase Fluorescence Sensing of the Cyanide Ion and Aerobic Oxidation of Cyclohexane.

A zirconium (Zr) metal-organic framework having a DUT-52 (DUT stands for Dresden University of Technology) structure with face-centered cubic topology and bearing the rigid 1-(2,2,2-trifluoroacetamido) naphthalene-3,7-dicarboxylic acid (H2NDC-NHCOCF3) ligand was prepared, and its solid structure was characterized with the help of the X-ray powder diffraction (XRPD) technique. Other characterization methods like thermogravimetric analysis (TGA) and Fourier transform infrared (FT-IR) spectroscopy were applied to verify the phase purity of the compound. In order to get the solvent-free compound (1'), 1 was stirred with methanol for overnight and subsequently heated at 100 °C overnight under vacuum. As-synthesized (1) and activated (1') compounds are thermally stable up to 300 °C. The Brunsuer Emmett-Teller (BET) surface area of 1' was found to be 1105 m2 g-1. Fluorescence titration experiments showed that 1' exhibits highly selective and sensitive fluorescence turn-on behavior toward cyanide (CN-) anion. The interference experiments suggested that other anions did not interfere in the detection of CN-. Moreover, a very short response time (2 min) was shown by probe 1' for CN- detection. The detection limit was found to be 0.23 µM. 1' can also be effectively used for CN- detection in real water samples. The mechanism for the selective detection of CN- was investigated systematically. Furthermore, the aerobic oxidation of cyclohexane was performed with 1' under mild reaction conditions, observing higher activity than the analogous DUT-52 solid under identical conditions. These experiments clearly indicate the benefits of hydrophobic cavities of 1' in achieving higher conversion of cyclohexane and cyclohexanol/cyclohexanone selectivity. Catalyst stability was proved by two consecutive reuses and comparing the structural integrity of 1' before and after reuses by the XRPD study.

Cooperative Large-Hysteresis Spin-Crossover Transition in the Iron(II) Triazolate [Fe(ta)2] Metal-Organic Framework.

The metal-organic framework [Fe(ta)2] (Hta = 1H-1,2,3-triazole) containing Fe(II) ions and 1,2,3-triazolate ligands shows a reversible phase transition while retaining the cubic crystal symmetry and space group Fd3m (no. 227). The phase transition between room temperature (RT-[Fe(ta)2]; a = 16.6315(2) Å, V = 4600.39(8) Å3) and high temperature (HT-[Fe(ta)2]; a = 17.7566(4) Å, V = 5598.6(1) Å3) phases occurs at a temperature above 290 °C, whereas the phase transition between HT- and RT-[Fe(ta)2] starts at a temperature below 210 °C. Both [Fe(ta)2] polymorphs have identical bond topologies, but they differ by a large increase of the unit cell's volume of 22% for HT-[Fe(ta)2]. The compounds are characterized by powder X-ray diffraction, differential scanning calorimetry, and thermogravimetric analyses. Additionally, Mössbauer spectroscopy, magnetic studies, and the electronic structure of both phases are discussed in detail with respect to the spin-crossover transition from the low-spin (RT-[Fe(ta)2]) to the high-spin phase (HT-[Fe(ta)2]).

Zeolitic Imidazolate Framework-8 as pH-Sensitive Nanocarrier for "Arsenic Trioxide" Drug Delivery.

Previous results revealed that arsenic trioxide might be used as promising therapeutic agent for the treatment of some solid tumours as atypical teratoid rhabdoid tumours (ATRT). However, in order to become an approved drug for solid tumour treatment, the active formulation has to get more efficient and feasible-but at the same time less toxic. One of the possibilities to achieve this dichotomy is to use nanomedicine tools. Herein, we report on the Zn-based metal-organic framework ZIF-8 (Zeolitic Imidazolate Framework-8) which turned out to be a promising candidate for the delivery of AsIII species. It conjointly features a high drug loading capacity and a prominent pH-triggered release behaviour. AsIII -loaded ZIF-8 nanoparticles coated and non-coated with polyethylene glycol were studied by XRPD, IR, Raman, TGA, TEM, EDX, CHN-elemental analysis, sorption analysis and ICP-OES, and their cytotoxicity was evaluated in vitro.

Dynamic Studies on Kinetic H2 /D2 Quantum Sieving in a Narrow Pore Metal-Organic Framework Grown on a Sensor Chip.

The separation of deuterium from hydrogen still remains a challenging and industrially relevant task. Compared to traditional cryogenic methods for separation, based on different boiling points of H2 and D2 , the use of ultramicroporous materials offers a more efficient alternative method. Due to their rigid structures, permanently high porosity, tunable pore sizes and adjustable internal surface properties, metal-organic frameworks (MOFs), a class of porous materials built through the coordination between organic linkers and metal ions/clusters, are more suitable for this approach than zeolites or carbon-based materials. Herein, dynamic gas flow studies on H2 /D2 quantum sieving in MFU-4, a metal-organic framework with ultra-narrow pores of 2.5 Å, are presented. A specially designed sensor with a very fast response based on surface acoustic waves is used. On-chip measurements of diffusion rates in the temperature range 27-207 K reveal a quantum sieving effect, with D2 diffusing faster than H2 below 64 K and the opposite selectivity above this temperature. The experimental results obtained are confirmed by molecular dynamic simulation regarding quantum sieving of H2 and D2 on MOFs for which a flexible framework approach was used for the first time.

Achieving Large Volumetric Gas Storage Capacity in Metal-Organic Frameworks by Kinetic Trapping: A Case Study of Xenon Loading in MFU-4.

One of the main problems of gas storage in porous materials is that many molecules of interest adsorb too weakly to be retained effectively. To enhance gas storage in metal-organic frameworks (MOFs), we propose the use of kinetic trapping, i.e., a process where the guest gas is captured in the voids at loading conditions and not released immediately at normal conditions. In this approach, the diffusion-limiting pore size and the framework flexibility have to be matched to the gas, requiring flexible pore apertures to be smaller than the van der Waals diameter of the trapped guest. We selected the Metal-Organic Framework Ulm University-4 (MFU-4) with a pore aperture of 2.52 Å as a model coordination framework and used it for storage of xenon (with van der Waals diameter of 4.4 Å). Although xenon atoms are substantially larger than the MOF pore aperture, MFU-4 could be loaded with xenon by applying moderately high gas pressures. This is demonstrated to be due to the pore flexibility as confirmed by computational studies. The xenon loading could be tuned (from 0 wt % to more than 44.5 wt %) by changing the loading parameters such as pressure, temperature, and time, and the xenon atoms remained inside the pores upon exposing the material to air atmosphere at room temperature. To understand the material behavior, TGA, XRPD, and 129Xe NMR spectroscopy and computational studies were carried out.

Single-Crystal to Single-Crystal Transformation of a Nonporous Fe(II) Metal-Organic Framework into a Porous Metal-Organic Framework via a Solid-State Reaction.

We report the synthesis of an air-stable nonporous coordination compound based on iron(II) centers, formate anions, and a 4,4'-bipyrazole (H2BPZ) ligand. Upon thermal treatment, a porous metal-organic framework (MOF) formed due to decomposition of the incorporated formate anions. This decomposition step and the following structural changes constituted a single-crystal to single-crystal transformation. The resulting [Fe(BPZ)] framework contained tetrahedrally coordinated iron(II) metal centers. The framework was sensitive toward oxidation by molecular oxygen even at temperatures of 183 K, as followed by oxygen sorption measurements and a color change from colorless to metallic black. The semiconductor properties of the oxidized material were studied by diffuse reflectance UV/vis/NIR spectroscopy and dielectric spectroscopy.

[Co5Tp*4(Me2bta)6]: A Highly Symmetrical Pentanuclear Kuratowski Complex Featuring Tris(pyrazolyl)borate and Benzotriazolate Ligands.

The pentanuclear Co(II) complex [Co5Tp*4(Me2bta)6] containing N-donor ligands (5,6-dimethyl benzotriazolate; Me2bta6) and N-donor capping ligands (tris(3,5-dimethyl-1-pyrazolyl)borate; Tp*) was prepared by a simple and efficient ligand exchange reaction from [Co5Cl4(Me2bta)6] and tetra-n-butyl ammonium tris(3,5-dimethyl-1-pyrazolyl)borate. Compared to the precursor complex [Co5Cl4(Me2bta)6], which contains one Co(II) ion in octahedral and four Co(II) ions in tetrahedral coordination geometry, the title compound features all five Co(II) ions in an octahedral coordination environment while keeping a high complex symmetry. This results in modified properties including improved solubility and distinct magnetic behavior as compared to the precursor complex. The molecular structure and phase purity of the compound was verified by XRPD, UV-vis, ESI-MS, IR, and NMR measurements. Thermal stability of the compound was determined via TGA. The magnetic properties of here reported novel complex [Co5Tp*4(Me2bta)6] as well as its precursor [Co5Cl4(Me2bta)6] were examined in detail via ESR and SQUID measurements, which indicated weak anti-ferromagnetic exchange interactions between high-spin Co(II) centers at T < 20 and 50 K, respectively.

Postsynthetic Metal and Ligand Exchange in MFU-4l: A Screening Approach toward Functional Metal-Organic Frameworks Comprising Single-Site Active Centers.

The isomorphous partial substitution of Zn(2+) ions in the secondary building unit (SBU) of MFU-4l leads to frameworks with the general formula [M(x)Zn(5-x)Cl4(BTDD)3], in which x≈2, M = Mn(II), Fe(II), Co(II), Ni(II), or Cu(II), and BTDD = bis(1,2,3-triazolato-[4,5-b],[4',5'-i])dibenzo-[1,4]-dioxin. Subsequent exchange of chloride ligands by nitrite, nitrate, triflate, azide, isocyanate, formate, acetate, or fluoride leads to a variety of MFU-4l derivatives, which have been characterized by using XRPD, EDX, IR, UV/Vis-NIR, TGA, and gas sorption measurements. Several MFU-4l derivatives show high catalytic activity in a liquid-phase oxidation of ethylbenzene to acetophenone with air under mild conditions, among which Co- and Cu derivatives with chloride side-ligands are the most active catalysts. Upon thermal treatment, several side-ligands can be transformed selectively into reactive intermediates without destroying the framework. Thus, at 300 °C, Co(II)-azide units in the SBU of Co-MFU-4l are converted into Co(II)-isocyanate under continuous CO gas flow, involving the formation of a nitrene intermediate. The reaction of Cu(II)-fluoride units with H2 at 240 °C leads to Cu(I) and proceeds through the heterolytic cleavage of the H2 molecule.

Tribenzotriquinacene receptors for C60 †fullerene rotors: towards C3 symmetrical chiral stators for unidirectionally operating nanoratchets.

The synthesis of a stereochemically pure concave tribenzotriquinacene receptor (7) for C60 fullerene, possessing C3 point group symmetry, by threefold condensation of C2 -symmetric 1,2-diketone synthons (5) and a hexaaminotribenzotriquinacene core (6) is described. The chiral diketone was synthesized in a five-step reaction sequence starting from C2h -symmetric 2,6-di-tert-butylanthracene. The highly diastereo-discriminating Diels-Alder reaction of 2,6-di-tert-butylanthracene with fumaric acid di(-)menthyl ester, catalyzed by aluminium chloride, is the relevant stereochemistry introducing step. The structure of the fullerene receptor was verified by (1)H and (13)C NMR spectroscopy, mass spectrometry and single crystal X-ray diffraction. VCD and ECD spectra were recorded, which were corroborated by ab initio DFT calculations, establishing the chiral nature of 7 with about 99.7 % ee, based on the ee (99.9 %) of the chiral synthon (1). The absolute configuration of 7 could thus be established as all-S [(2S,7S,16S,21S,30S,35S)-(7)]. Spectroscopic titration experiments reveal that the host forms 1:1 complexes with either pure fullerene (C60) or fullerene derivatives, such as rotor 1'-(4-nitrophenyl)-3'-(4-N,N-dimethylaminophenyl)-pyrazolino[4',5':1,2][60]fullerene (R). The complex stability constants of the complexes dissolved in CHCl3/CS2 (1:1 vol. %) are K([C60 ⊂7]) = 319(±156) M(-1) and K([R⊂7]) = 110(±50) M(-1). With molecular dynamics simulations using a first-principles parameterized force field the asymmetry of the rotational potential for [R⊂7] was shown, demonstrating the potential suitability of receptor 7 to act as a stator in a unidirectionally operating nanoratchet.

Almost enclosed buckyball joints: synthesis, complex formation, and computational simulations of pentypticene-extended tribenzotriquinacene.

We report the synthesis of a tribenzotriquinacene-based (TBTQ) receptor (3) for C60 fullerene, which is extended by pentiptycene moieties to provide an almost enclosed concave ball bearing. The system serves as a model for a self-assembling molecular rotor with a flexible and adapting stator. Unexpectedly, nuclear magnetic resonance spectroscopic investigations reveal a surprisingly low complex stability constant of K1 =213±37 M(-1) for [C60 ⊂3], seemingly inconsistent with the previously reported TBTQ systems. Molecular dynamics (MD) simulations have been conducted for three different [C60 ⊂TBTQ] complexes to resolve this. Because of the dominating dispersive interactions, the binding energies increase with the contact area between guest and host, however, only for rigid host structures. By means of free-energy calculations with an explicit solvent model it can be shown that the novel flexible TBTQ receptor 3 binds weakly because of hampering entropic contributions.

Scorpionate-type coordination in MFU-4l metal-organic frameworks: small-molecule binding and activation upon the thermally activated formation of open metal sites.

Postsynthetic metal and ligand exchange is a versatile approach towards functionalized MFU-4l frameworks. Upon thermal treatment of MFU-4l formates, coordinatively strongly unsaturated metal centers, such as zinc(II) hydride or copper(I) species, are generated selectively. Cu(I)-MFU-4l prepared in this way was stable under ambient conditions and showed fully reversible chemisorption of small molecules, such as O2, N2, and H2, with corresponding isosteric heats of adsorption of 53, 42, and 32 kJ mol(-1), respectively, as determined by gas-sorption measurements and confirmed by DFT calculations. Moreover, Cu(I)-MFU-4l formed stable complexes with C2H4 and CO. These complexes were characterized by FTIR spectroscopy. The demonstrated hydride transfer to electrophiles and strong binding of small gas molecules suggests these novel, yet robust, metal-organic frameworks with open metal sites as promising catalytic materials comprising earth-abundant metal elements.

Naphthalimide functionalized metal-organic framework for rapid and nanomolar level detection of hydrazine and anti-hypertensive drug nicardipine.

The increasing utilization of hydrazine and its derivatives across diverse sectors highlights the pressing need for efficient detection methods to safeguard human health and the environment. Likewise, nicardipine, a widely used medication for heart diseases, necessitates accurate sensing techniques for clinical research and therapeutic monitoring. Here, we propose a novel approach using a naphthalimide-functionalized Zr-MOF as a fluorometric probe capable of detecting both hydrazine and nicardipine in aqueous medium. Our designed probe exhibited a significant 31-fold increase in fluorescence intensity upon interaction with hydrazine. At the same time, nicardipine induced 86% fluorescence quenching with an exceptionally rapid response time (100 s for hydrazine and 5 s for nicardipine). The designed probe has the ability to detect both analytes at nanomolar concentrations (LOD for hydrazine is 1.11 nM while that for nicardipine is 9.6 nM). Investigation across various wastewater samples and pH conditions further validated its practical utility. The mechanism behind fluorometric sensing of nicardipine was thoroughly investigated using modern instrumentation. Our study presents a versatile and effective approach for detecting hydrazine and nicardipine, addressing crucial needs in both industrial and biomedical contexts.