Multivariate Silicification-Assisted Single Enzyme Structure Augmentation for Improved Enzymatic Activity-Stability Trade-Off.

The ability to finely tune/balance the structure and rigidity of enzymes to realize both high enzymatic activity and long-term stability is highly desired but highly challenging. In this work, we propose a new concept of silica-enzyme, referred to as "silicazyme", where solid inorganic silica was controlled hybridization with fragile enzyme under moderate condition at single-enzyme level, realizing simultaneous structure augmentation, long-term stability, and high enzymatic activity preservation. A multivariate silicification approach was utilized and occurred around individual enzymes to allow conformal coating. To realize a high activity-stability trade-off the structure flexibility/rigidity of silicazyme was optimized by a component-adjustment-ternary (CAT) plot method. Moreover, the multivariate organosilica frameworks bring great advantages including surface microenvironment adjustability, reversible modification capability, and functional extensibility through the rich chemistry of silica. Overall silicazymes represent a new class of enzymes that promise to broaden their utilization in catalysis, separations, and nanomedicine.

Nanoscience and nanotechnology for water remediation: an earnest hope toward sustainability.

Water pollution and the global freshwater crisis are the most alarming concerns of the 21st century, as they threaten the sustainability and ecological balance of the environment. The growth of global population, climate change, and expansion of industrial processes are the main causes of these issues. Therefore, effective remediation of polluted water by means of detoxification and purification is of paramount importance. To this end, nanoscience and nanotechnology have emerged as viable options that hold tremendous potential toward the advancement of wastewater treatment methods to enhance treatment efficiency along with augmenting water supply via utilization of unconventional water sources. Materials at the nano level have shown great promise toward water treatment applications owing to their unique physicochemical properties. In this focus article, we highlight the role of new fundamental properties at the nano scale and material properties that are drastically increased due to the nano dimension (e.g. volume-surface ratio) and highlight their impact and potential toward water treatment. We identify and discuss how nano-properties could improve the three main domains of water remediation: the identification of pollutants, their adsorption and catalytic degradation. After discussing all the beneficial aspects we further discuss the key challenges associated with nanomaterials for water treatment. Looking at the current state-of-the-art, the potential as well as the challenges of nanomaterials, we believe that in the future we will see a significant impact of these materials on many water remediation strategies.

Structural Design for EMI Shielding: From Underlying Mechanisms to Common Pitfalls.

Modern human civilization deeply relies on the rapid advancement of cutting-edge electronic systems that have revolutionized communication, education, aviation, and entertainment. However, the electromagnetic interference (EMI) generated by digital systems poses a significant threat to the society, potentially leading to a future crisis. While numerous efforts are made to develop nanotechnological shielding systems to mitigate the detrimental effects of EMI, there is limited focus on creating absorption-dominant shielding solutions. Achieving absorption-dominant EMI shields requires careful structural design engineering, starting from the smallest components and considering the most effective electromagnetic wave attenuating factors. This review offers a comprehensive overview of shielding structures, emphasizing the critical elements of absorption-dominant shielding design, shielding mechanisms, limitations of both traditional and nanotechnological EMI shields, and common misconceptions about the foundational principles of EMI shielding science. This systematic review serves as a scientific guide for designing shielding structures that prioritize absorption, highlighting an often-overlooked aspect of shielding science.

Liquid-templated graphene aerogel electromagnetic traps.

For decades, the inherently reflective nature of metallic electromagnetic (EM) shields and their induced secondary EM pollution have posed significant challenges for sensitive electronics. While numerous efforts have been made to develop superior EM shielding systems, the issue of reflection dominancy in metallic substrates remains unresolved. Herein, we addressed this long-lasting obstacle by pairing metallic shields with ultra-lightweight (density of 3.12-3.40 mg cm-3) elastic anti-reflection aerogels, altering their shielding mechanism from dominant reflection (reflectance >0.8) to absorption (absorbance >0.7) by trapping EM waves inside the aerogel. The aerogel EM traps were generated using interfacial complexation, yielding engineerable filamentous liquid structures. These served as templates for aerogel creation through a follow-up process of freezing and lyophilization. The engineerable lossy medium of aerogels benefits from a multi-scale porous construct with the combined action of dielectric and conduction losses, highly dissipating the EM waves and minimizing the reflections. Notably, declining the diameter of aerogel filaments promoted its absorption dominancy, rendering it a potent dissipating medium for EM waves. Pairing a metallic substrate with filamentous aerogel EM traps has resulted in an exceptionally effective absorption-dominant shielding system, achieving absorbance levels between 0.70-0.81. This system offers a shielding effectiveness of 53-89 dB within the X-band frequency range. This innovation addresses a persistent issue in shielding science related to the reflective characteristics of metallic substrates, effectively inhibiting their induced EM reflections.

Chemistry in Ukraine.

In this special issue, we highlight recent advances in chemical research by scientists in Ukraine, as well as by their compatriots and collaborators outside the country. Besides spotlighting their contributions, we see our task in fostering global partnerships and multi-, inter-, and trans-disciplinary collaborations, including much-needed co-funded projects and initiatives. The three decades of the renewed Ukraine independence have seen rather limited integration of Ukrainian (chemical) science into global research communities.[1] At the same time, the recent surge of collaborative science initiatives between European Union (EU) and Ukraine echoes the unfolding steps towards Ukraine's full research participation to the Horizon Europe Program. This recently implemented step opens enormous possibilities for Ukrainian researchers to apply for diverse EU research grants. Moreover, a number of journal special issues and collections were launched to highlight Ukrainian chemistry (i. e., by Chemistry of Heterocyclic Compounds[2] and ChemistrySelect[3] ). Other scientific initiatives include 'European Chemistry School for Ukrainians'[4] and 'Kharkiv Chemical Seminar'[5] as voluntary projects aimed at engaging Ukrainian scientists into European and international chemical research.

The Importance of Dean Flow in Microfluidic Nanoparticle Synthesis: A ZIF-8 Case Study.

The Dean Flow, a physics phenomenon that accounts for the impact of channel curvature on fluid dynamics, has great potential to be used in microfluidic synthesis of nanoparticles. This study explores the impact of the Dean Flow on the synthesis of ZIF-8 particles. Several variables that influence the Dean Equation (the mathematical expression of Dean Flow) are tested to validate the applicability of this expression in microfluidic synthesis, including the flow rate, radius of curvature, channel cross sectional area, and reagent concentration. It is demonstrated that the current standard of reporting, providing only the flow rate and crucially not the radius of curvature, is an incomplete description that will invariably lead to irreproducible syntheses across different laboratories. An alternative standard of reporting is presented and it is demonstrated how the sleek and simple math of the Dean Equation can be used to precisely tune the final dimensions of high quality, monodisperse ZIF-8 nanoparticles between 40 and 700 nm.

Synthetic Biohybrids of Red Blood Cells and Cascaded-Enzymes@ Metal-Organic Frameworks for Hyperuricemia Treatment.

Hyperuricemia, caused by an imbalance between the rates of production and excretion of uric acid (UA), may greatly increase the mortality rates in patients with cardiovascular and cerebrovascular diseases. Herein, for fast-acting and long-lasting hyperuricemia treatment, armored red blood cell (RBC) biohybrids, integrated RBCs with proximal, cascaded-enzymes of urate oxidase (UOX) and catalase (CAT) encapsulated within ZIF-8 framework-based nanoparticles, have been fabricated based on a super-assembly approach. Each component is crucial for hyperuricemia treatment: 1) RBCs significantly increase the circulation time of nanoparticles; 2) ZIF-8 nanoparticles-based superstructure greatly enhances RBCs resistance against external stressors while preserving native RBC properties (such as oxygen carrying capability); 3) the ZIF-8 scaffold protects the encapsulated enzymes from enzymatic degradation; 4) no physical barrier exists for urate diffusion, and thus allow fast degradation of UA in blood and neutralizes the toxic by-product H2 O2 . In vivo results demonstrate that the biohybrids can effectively normalize the UA level of an acute hyperuricemia mouse model within 2 h and possess a longer elimination half-life (49.7 ± 4.9 h). They anticipate that their simple and general method that combines functional nanomaterials with living cell carriers will be a starting point for the development of innovative drug delivery systems.

Functional Janus structured liquids and aerogels.

Janus structures have unique properties due to their distinct functionalities on opposing faces, but have yet to be realized with flowing liquids. We demonstrate such Janus liquids with a customizable distribution of nanoparticles (NPs) throughout their structures by joining two aqueous streams of NP dispersions in an apolar liquid. Using this anisotropic integration platform, different magnetic, conductive, or non-responsive NPs can be spatially confined to opposite sides of the original interface using magnetic graphene oxide (mGO)/GO, Ti3C2Tx/GO, or GO suspensions. The resultant Janus liquids can be used as templates for versatile, responsive, and mechanically robust aerogels suitable for piezoresistive sensing, human motion monitoring, and electromagnetic interference (EMI) shielding with a tuned absorption mechanism. The EMI shields outperform their current counterparts in terms of wave absorption, i.e., SET ≈ 51 dB, SER ≈ 0.4 dB, and A = 0.91, due to their high porosity ranging from micro- to macro-scales along with non-interfering magnetic and conductive networks imparted by the Janus architecture.

Surfactant-Mediated Highly Conductive Cellulosic Inks for High-Resolution 3D Printing of Robust and Structured Electromagnetic Interference Shielding Aerogels.

Technological fusion of emerging three-dimensional (3D) printing of aerogels with gel processing enables the fabrication of lightweight and functional materials for diverse applications. However, 3D-printed constructs via direct ink writing for fabricating electrically conductive structured biobased aerogels suffer several limitations, including poor electrical conductivity, inferior mechanical strength, and low printing resolution. This work addresses these limitations via molecular engineering of conductive hydrogels. The hydrogel inks, namely, CNC/PEDOT-DBSA, featured a unique formulation containing well-dispersed cellulose nanocrystal decorated by a poly(3,4-ethylene dioxythiophene) (PEDOT) domain combined with dodecylbenzene sulfonic acid (DBSA). The rheological properties were precisely engineered by manipulating the solid content and the intermolecular interactions among the constituents, resulting in 3D-printed structures with excellent resolution. More importantly, the resultant aerogels following freeze-drying exhibited a high electrical conductivity (110 ± 12 S m-1), outstanding mechanical properties (Young's modulus of 6.98 MPa), and fire-resistance properties. These robust aerogels were employed to address pressing global concerns about electromagnetic pollution with a specific shielding effectiveness of 4983.4 dB cm2 g-1. Importantly, it was shown that the shielding mechanism of the 3D printed aerogels could be manipulated by their geometrical features, unraveling the undeniable role of additive manufacturing in materials design.

Uptake and Intracellular Fate of Fluorophore Labeled Metal-Organic-Framework (MOF) Nanoparticles.

The uptake and the fate of Zr-based metal-organic-framework nanoparticles labeled with organic fluorophores in HeLa cells has been monitored with fluorescence detection and elemental analysis. The nanoparticles have been selected as a model system of carrier nanoparticles (here Zr-based metal-organic-framework nanoparticles) with integrated cargo molecules (here organic fluorophores), with aze that does not allow for efficient exocytosis, a material which only partly degrades under acidic conditions as present in endosomes/lysosomes, and with limited colloidal stability. Data show that, for Zr-based metal-organic-framework nanoparticles of 40 nm size as investigated here, the number of nanoparticles per cells decreases faster due to particle redistribution upon proliferation than due to nanoparticle exocytosis and that, thus, also for this system, exocytosis is not an efficient pathway for clearance of the nanoparticles from the cells.

Alignment of Breathing Metal-Organic Framework Particles for Enhanced Water-Driven Actuation.

As the majority of known metal-organic frameworks (MOFs) possess anisotropic crystal lattices and thus anisotropic physicochemical properties, a pressing practical challenge in MOF research is the establishment of robust and simple processing methods to fully harness the anisotropic properties of the MOFs in various applications. We address this challenge by applying an E-field to precisely align MIL-88A microcrystals and generate MIL-88A@polymer films. Thereafter, we demonstrate the impact of MOF crystal alignment on the actuation properties of the films as a proof of concept. We investigate how different anisotropies of the MIL-88A@polymer films, specifically, crystal anisotropy, particle alignment, and film composition, can lead to the synergetic enhancement of the film actuation upon water exposure. Moreover, we explore how the directionality in application of the external stimuli (dry/humid air stream, water/air interface) affects the direction and the extent of the MIL-88A@polymer film movement. Apart from the superior water-driven actuation properties of the developed films, we demonstrate by dynamometer measurements the higher degree of mechanical work performed by the aligned MIL-88A@polymer films with the preserved anisotropies compared to the unaligned films. The insights provided by this work into anisotropic properties displayed by aligned MIL-88A@polymer films promise to translate crystal performance benefits measured in laboratories into real-world applications. We anticipate that our work is a starting point to utilize the full potential of anisotropic properties of MOFs.

Liquid-Templating Aerogels.

Modern materials science has witnessed the era of advanced fabrication methods to engineer functionality from the nano- to macroscales. Versatile fabrication and additive manufacturing methods are developed, but the ability to design a material for a given application is still limited. Here, a novel strategy that enables target-oriented manufacturing of ultra-lightweight aerogels with on-demand characteristics is introduced. The process relies on controllable liquid templating through interfacial complexation to generate tunable, stimuli-responsive 3D-structured (multiphase) filamentous liquid templates. The methodology involves nanoscale chemistry and microscale assembly of nanoparticles (NPs) at liquid-liquid interfaces to produce hierarchical macroscopic aerogels featuring multiscale porosity, ultralow density (3.05-3.41 mg cm-3 ), and high compressibility (90%) combined with elastic resilience and instant shape recovery. The challenges are overcome facing ultra-lightweight aerogels, including poor mechanical integrity and the inability to form predefined 3D constructs with on-demand functionality, for a multitude of applications. The controllable nature of the coined methodology enables tunable electromagnetic interference shielding with high specific shielding effectiveness (39 893 dB cm2 g-1 ), and one of the highest-ever reported oil-absorption capacities (487 times the initial weight of aerogel for chloroform), to be obtained. These properties originate from the engineerable nature of liquid templating, pushing the boundaries of lightweight materials to systematic function design and applications.

Peptide nucleic acid-zirconium coordination nanoparticles.

Ideal drug carriers feature a high loading capacity to minimize the exposure of patients with excessive, inactive carrier materials. The highest imaginable loading capacity could be achieved by nanocarriers, which are assembled from the therapeutic cargo molecules themselves. Here, we describe peptide nucleic acid (PNA)-based zirconium (Zr) coordination nanoparticles which exhibit very high PNA loading of [Formula: see text] w/w. This metal-organic hybrid nanomaterial class extends the enormous compound space of coordination polymers towards bioactive oligonucleotide linkers. The architecture of single- or double-stranded PNAs was systematically varied to identify design criteria for the coordination driven self-assembly with Zr(IV) nodes at room temperature. Aromatic carboxylic acid functions, serving as Lewis bases, and a two-step synthesis process with preformation of [Formula: see text] turned out to be decisive for successful nanoparticle assembly. Confocal laser scanning microscopy confirmed that the PNA-Zr nanoparticles are readily internalized by cells. PNA-Zr nanoparticles, coated with a cationic lipopeptide, successfully delivered an antisense PNA sequence for splicing correction of the [Formula: see text]-globin intron mutation IVS2-705 into a functional reporter cell line and mediated splice-switching via interaction with the endogenous mRNA splicing machinery. The presented PNA-Zr nanoparticles represent a bioactive platform with high design flexibility and extraordinary PNA loading capacity, where the nucleic acid constitutes an integral part of the material, instead of being loaded into passive delivery systems.

Water Harvesting at the Single-Crystal Level.

Metal-organic frameworks (MOFs) have emerged as a class of porous materials with facile uptake and release of water, turning them into excellent substrates for real-world atmospheric water harvesting applications. The performance of different MOF systems was experimentally characterized at the bulk level by assessing the total amount of water taken up and the release kinetics, leaving the question behind of what the upper limit of the pristine materials actually is. Moreover, recent devices rely on fluidized bed reactors that exploit the harvesting capacities of MOFs at the single-crystal (SC) level. In this publication, we present a novel methodology based on Raman spectroscopy, for acquiring water adsorption isotherms and kinetic curves with a sub-micrometer resolution that provides valuable insights into the material behavior probing the pristine MOF at the SC level. We investigated isolated MOF-801 particles in situ and could dissect contributions of intra- and inter-particle effects on the water harvesting performance of MOF-801 via adsorption-desorption isotherms and kinetic curves. Using spontaneous Raman spectroscopy, we found an almost 20-fold faster uptake for the undisturbed crystalline material. Correlative imaging based on four-wave mixing and coherent anti-Stokes Raman scattering further localized the uptaken water inside MOF-801 and identified inter-particle condensation as the main source for the discrepancies between the performance at the bulk and SC level. Our studies determined an upper limit of around 91.9 L/kgMOF/day for MOF-801.

Dimensional Reduction of Metal-Organic Frameworks for Enhanced Cryopreservation of Red Blood Cells.

To increase the red blood cell (RBC) cryopreservation efficiency by metal-organic frameworks (MOFs), a dimensional reduction approach has been proposed. Namely, 3D MOF nanoparticles are progressively reduced to 2D ultra-thin metal-organic layers (MOLs). We found that 2D MOLs are beneficial for enhanced interactions of the interfacial hydrogen-bonded water network and increased utilization of inner ordered structures, due to the higher surface-to-volume ratio. Specifically, a series of hafnium (Hf)-based 2D MOLs with different thicknesses (monolayer to stacked multilayers) and densities of hydrogen bonding sites have been synthesized. Both ice recrystallization inhibition activity (IRI) and RBCs cryopreservation assay confirm the pronounced better IRI activity and excellent cell recovery efficiency (up to ≈63 % at a very low concentration of 0.7 mg mL-1 ) of thin-layered Hf-MOLs compared to their 3D counterparts, thereby verifying the dimensional reduction strategy to improved cryoprotectant behaviors.

Correction: Toxicity of metal-organic framework nanoparticles: from essential analyses to potential applications.

Correction for 'Toxicity of metal-organic framework nanoparticles: from essential analyses to potential applications' by Romy Ettlinger et al., Chem. Soc. Rev., 2022, 51, 464-484, https://doi.org/10.1039/D1CS00918D.

Magnetic sustentation as an adsorption characterization technique for paramagnetic metal-organic frameworks.

Nowadays, there are many reliable characterization techniques for the study of adsorption properties in gas phase. However, the techniques available for the study of adsorption processes in solution, rely on indirect characterization techniques that measure the adsorbate concentration remaining in solution. In this work, we present a sensing method based on the magnetic properties of metal-organic frameworks (MOFs) containing paramagnetic metal centres, which stands out for the rapidity, low cost and in situ direct measurement of the incorporated adsorbate within the porous material. To illustrate this sensing technique, the adsorption in solution of four MOFs have been characterized: MIL-88A(Fe), MOF-74(Cu, Co) and ZIF-67(Co). Our simple and efficient method allows the direct determination of the adsorbed mass, as well as the measurement of adsorption isotherm curves, which we hope will greatly advance the study of adsorption processes in solution, since this method is independent of the chemical nature of the adsorbate that often makes its quantification difficult.

Conformationally Restricted ß-Sheet Breaker Peptides Incorporating Cyclic α-Methylisoserine Sulfamidates.

Peptides containing variations of the ß-amyloid hydrophobic core and five-membered sulfamidates derived from ß-amino acid α-methylisoserine have been synthesized and fully characterized in the gas phase, solid state and in aqueous solution by a combination of experimental and computational techniques. The cyclic sulfamidate group effectively locks the secondary structure at the N-terminus of such hybrid peptides imposing a conformational restriction and stabilizing non-extended structures. This conformational bias, which is maintained in the gas phase, solid state and aqueous solution, is shown to be resistant to structure templating through assays of in vitro ß-amyloid aggregation, acting as ß-sheet breaker peptides with moderate activity.

A State-of-the-Art of Metal-Organic Frameworks for Chromium Photoreduction vs. Photocatalytic Water Remediation.

Hexavalent chromium (Cr(VI)) is a highly mobile cancerogenic and teratogenic heavy metal ion. Among the varied technologies applied today to address chromium water pollution, photocatalysis offers a rapid reduction of Cr(VI) to the less toxic Cr(III). In contrast to classic photocatalysts, Metal-Organic frameworks (MOFs) are porous semiconductors that can couple the Cr(VI) to Cr(III) photoreduction to the chromium species immobilization. In this minireview, we wish to discuss and analyze the state-of-the-art of MOFs for Cr(VI) detoxification and contextualizing it to the most recent advances and strategies of MOFs for photocatalysis purposes. The minireview has been structured in three sections: (i) a detailed discussion of the specific experimental techniques employed to characterize MOF photocatalysts, (ii) a description and identification of the key characteristics of MOFs for Cr(VI) photoreduction, and (iii) an outlook and perspective section in order to identify future trends.

Long-term whole blood DNA preservation by cost-efficient cryosilicification.

Deoxyribonucleic acid (DNA) is the blueprint of life, and cost-effective methods for its long-term storage could have many potential benefits to society. Here we present the method of in situ cryosilicification of whole blood cells, which allows long-term preservation of DNA. Importantly, our straightforward approach is inexpensive, reliable, and yields cryosilicified samples that fulfill the essential criteria for safe, long-term DNA preservation, namely robustness against external stressors, such as radical oxygen species or ultraviolet radiation, and long-term stability in humid conditions at elevated temperatures. Our approach could enable the room temperature storage of genomic information in book-size format for more than one thousand years (thermally equivalent), costing only 0.5 $/person. Additionally, our demonstration of 3D-printed DNA banking artefacts, could potentially allow 'artificial fossilization'.