Trace Adsorptive Removal of PFAS from Water by Optimizing the UiO-66 MOF Interface.

The confluence of pervasiveness, bioaccumulation, and toxicity in freshwater contaminants presents an environmental threat second to none. Exemplifying this trifecta, per- and polyfluoroalkyl substances (PFAS) present an alarming hazard among the emerging contaminants. State-of-the-art PFAS adsorbents used in drinking water treatment, namely, activated carbons and ion-exchange resins, are handicapped by low adsorption capacity, competitive adsorption, and/or slow kinetics.

Tailoring the Coordination Micro-Environment in Nanotraps for Efficient Platinum/Palladium Separation.

Recovering platinum group metals from secondary resources is crucial to meet the growing demand for high-tech applications. Various techniques are explored, and adsorption using porous materials has emerged as a promising technology due to its efficient performance and environmental beingness. However, the challenge lies in effectively recovering and separating individual platinum group metals (PGMs) given their similar chemical properties.

Immobilization of Amino-site into a Pore-Partitioned Metal-Organic Framework for Highly Efficient Separation of Propyne/Propylene.

Adsorptive separation of propyne/propylene (CH/CH) is a crucial yet complex process, however, it remains a great difficulty in developing porous materials that can meet the requirements for practical applications, particularly with an exceptional ability to bind and store trace amounts of CH. Functionalization of pore-partitioned metal-organic frameworks (ppMOFs) is methodically suited for this challenge owing to the possibility of dramatically increasing binding sites on highly porous and confined domains. We here immobilized Lewis-basic (-NH) and Lewis-acidic (-NO) sites on this platform.

Complete separation of benzene-cyclohexene-cyclohexane mixtures via temperature-dependent molecular sieving by a flexible chain-like coordination polymer.

The separation and purification of C6 cyclic hydrocarbons (benzene, cyclohexene, cyclohexane) represent a critically important but energy intensive process. Developing adsorptive separation technique to replace thermally driven distillation processes holds great promise to significantly reduce energy consumption. Here we report a flexible one-dimensional coordination polymer as an efficient adsorbent to discriminate ternary C6 cyclic hydrocarbons via an ideal molecular sieving mechanism.

Creation of Cationic Polymeric Nanotrap Featuring High Anion Density and Exceptional Alkaline Stability for Highly Efficient Pertechnetate Removal from Nuclear Waste Streams.

There is an urgent need for highly efficient sorbents capable of selectively removing TcO from concentrated alkaline nuclear wastes, which has long been a significant challenge. In this study, we present the design and synthesis of a high-performance adsorbent, CPN-3 (CPN denotes cationic polymeric nanotrap), which achieves excellent TcO capture under strong alkaline conditions by incorporating branched alkyl chains on the N3 position of imidazolium units and optimizing the framework anion density within the pores of a cationic polymeric nanotrap. CPN-3 features exceptional stability in harsh alkaline and radioactive environments as well as exhibits fast kinetics, high adsorption capacity, and outstanding selectivity with full reusability and great potential for the cost-effective removal of TcO/ReO from contaminated water.

Metal-Free Heterogeneous Asymmetric Hydrogenation of Olefins Promoted by Chiral Frustrated Lewis Pair Framework.

The development of metal-free and recyclable catalysts for significant yet challenging transformations of naturally abundant feedstocks has long been sought after. In this work, we contribute a general strategy of combining the rationally designed crystalline covalent organic framework (COF) with a newly developed chiral frustrated Lewis pair (CFLP) to afford chiral frustrated Lewis pair framework (CFLPF), which can efficiently promote the asymmetric olefin hydrogenation in a heterogeneous manner, outperforming the homogeneous CFLP counterpart. Notably, the metal-free CFLPF exhibits superior activity/enantioselectivity in addition to excellent stability/recyclability.

Visible-Light-Promoted C(sp)-C(sp) Cross-Coupling of Amino Acids and Aryl Trifluoromethyl Ketones Through Simultaneous Decarboxylation and Defluorination.

A photoredox-catalyzed approach for the difluoroalkylation of amino acids was achieved through simultaneous decarboxylation and defluorination processes. This innovative protocol employs commonly available amino acids and trifluoroacetophenones as the primary starting materials, eliminating the necessity for preactivation. This strategy has enabled the synthesis of several difluoroketone functionalized amines in moderate to impressive yields.

Luminescent Metal-Organic Framework for the Selective Detection of Aldehydes.

The detection of toxic, hazardous chemical species is an important task because they pose serious risks to either the environment or human health. Luminescent metal-organic frameworks (LMOFs) as alternative sensors offer rapid and sensitive detection of chemical species. Interactions between chemical species and LMOFs result in changes in the photoluminescence (PL) profile of the LMOFs which can be readily detected using a simple fluorometer.

Incorporation of Chiral Frustrated Lewis Pair into Metal-Organic Framework with Tailored Microenvironment for Heterogeneous Enantio- and Chemoselective Hydrogenation.

The development of efficient heterogeneous catalysts with multiselectivity (e.g., enantio- and chemoselectivity) has long been sought after but with limited progress being made so far.

Confinement of 1D Chain and 2D Layered CuI Modules in K-INA-R Frameworks via Coordination Assembly: Structure Regulation and Semiconductivity Tuning.

Herein, we present a new series of CuI-based hybrid materials with tunable structures and semiconducting properties. The CuI inorganic modules can be tailored into a one-dimensional (1D) chain and two-dimensional (2D) layer and confined/stabilized in coordination frameworks of potassium isonicotinic acid (HINA) and its derivatives (HINA-R, R = OH, NO, and COOH). The resulting CuI-based hybrid materials exhibit interesting semiconducting behaviors associated with the dimensionality of the inorganic module; for instance, the structures containing the 2D-CuI module demonstrate significantly enhanced photoconductivity with a maximum increase of five orders of magnitude compared to that of the structures containing the 1D-CuI module.

Magnetically Induced Binary Ferrocene with Oxidized Iron.

Ferrocene is perhaps the most popular and well-studied organometallic molecule, but our understanding of its structure and electronic properties has not changed for more than 70 years. In particular, all previous attempts of chemically oxidizing pure ferrocene by binding directly to the iron center have been unsuccessful, and no significant change in structure or magnetism has been reported. Using a metal organic framework host material, we were able to fundamentally change the electronic and magnetic structure of ferrocene to take on a never-before observed physically stretched/bent high-spin Fe(II) state, which readily accepts O from air, chemically oxidizing the iron from Fe(II) to Fe(III).

Neoadjuvant PD-1/PD-L1 axis blockade for patients with head and neck squamous cell carcinoma.

Head and neck squamous cell carcinoma (HNSCC) is a common type of cancer, and approximately 64 % are in a locally advanced stage at diagnosis. Therefore, neoadjuvant therapy is of great importance. However, traditional neoadjuvant strategies for HNSCC have shown limited efficacy and high complications.

One Atom Can Make All the Difference: Gas-Induced Phase Transformations in Bisimidazole-Linked Diamondoid Coordination Networks.

Coordination networks (CNs) that undergo gas-induced transformation from closed (nonporous) to open (porous) structures are of potential utility in gas storage applications, but their development is hindered by limited control over their switching mechanisms and pressures. In this work, we report two CNs, [Co(bimpy)(bdc)] () and [Co(bimbz)(bdc)] () (Hbdc = 1,4-benzendicarboxylic acid; bimpy = 2,5-bis(1H-imidazole-1-yl)pyridine; bimbz = 1,4-bis(1H-imidazole-1-yl)benzene), that both undergo transformation from closed to isostructural open phases involving at least a 27% increase in cell volume. Although and only differ from one another by one atom in their -donor linkers (bimpy = pyridine, and bimbz = benzene), this results in different pore chemistry and switching mechanisms.

Efficacy of Music Intervention for Dental Anxiety Disorders: A Systematic Review and Meta-Analysis.

To evaluate the effectiveness of music therapy for dental anxiety disorders. In order to gather clinical randomized controlled trials comparing the effectiveness of music interventions to traditional oral manipulation in patients with dental anxiety disorders, computer searches of the electronic databases of Wanfang, CNKI, VIP, PubMed, Web of Science, ScienceDirect, Cochrane library, Scopus, and CINAHL were conducted. The search period covered from 23 December 2022, through to the development of the database.

Monitoring the Activation of Open Metal Sites in [FeM(μ-O)] Cluster-Based Metal-Organic Frameworks by Single-Crystal X-ray Diffraction.

While trinuclear [FeM(μ-O)] cluster-based metal-organic frameworks (MOFs) have found wide applications in gas storage and catalysis, it is still challenging to identify the structure of open metal sites obtained through proper activations and understand their influence on the adsorption and catalytic properties. Herein, we use in situ variable-temperature single-crystal X-ray diffraction to monitor the structural evolution of [FeM(μ-O)]-based MOFs (PCN-250, M = Ni, Co, Zn, Mg) upon thermal activation and provide the snapshots of metal sites at different temperatures. The exposure of open Fe sites was observed along with the transformation of Fe coordination geometries from octahedron to square pyramid.

Optimal Binding Affinity for Sieving Separation of Propylene from Propane in an Oxyfluoride Anion-Based Metal-Organic Framework.

Highly efficient adsorptive separation of propylene from propane offers an ideal alternative method to replace the energy-intensive cryogenic distillation technology. Molecular sieving-type separation via high-performance adsorbents is targeted for superior selectivity, but the limit in adsorption capacity remains a great challenge. Here, we report an oxyfluoride-based ultramicroporous metal-organic framework , [Ni(WOF)(pyz)] (pyz = pyrazine), featuring one-dimensional pore channels that can accommodate the propylene molecules with optimal binding affinity while specifically excluding the propane molecules.

Revisiting Competitive Adsorption of Small Molecules in the Metal-Organic Framework Ni-MOF-74.

To precisely evaluate the potential of metal-organic frameworks (MOFs) for gas separation and purification applications, it is crucial to understand how various molecules competitively adsorb inside MOFs. In this paper, we combine in situ infrared spectroscopy with ab initio calculations to investigate the mechanisms associated with coadsorption of several small molecules, including CO, NO, and CO inside the prototypical structure Ni-MOF-74. Surprisingly, we find that the displacement of CO bound inside Ni-MOF-74 (binding energy of 53 kJ/mol) is readily driven by CO exposure, even though CO has a noticeably weaker binding energy of only 41 kJ/mol; meanwhile, the significantly more strongly binding NO molecule (90 kJ/mol) is not able to easily displace bound CO inside Ni-MOF74.

[Application of CD138 Immunomagnetic Bead Sorting Combined with Fluorescence in Situ Hybridization in Multiple Myeloma].

Objective: To compare the effects of direct fluorescence in situ hybridization (D-FISH) detection without sorting and CD138 immunomagnetic bead sorting technology combined with FISH (MACS-FISH) on cytogenetic analysis of patients with multiple myeloma (MM).

Methods: FISH test results of 229 patients with initial MM were retrospectively analyzed. The patients were divided into two groups, 140 patients were tested with D-FISH and 89 patients with MACS-FISH.

Dominant role of OH and Ti defects on the electronic structure of TiO thin films for water splitting.

Anatase/rutile constituting TiO thin films were prepared by sputter deposition, and the influence of the post-annealing step with a narrow window at 200 °C revealed a gaining factor of 5 in H production. An in-depth analysis of the photocatalytic performance revealed the dominant role of intermediate states rather than the heterocrystalline nature and the mesoscale structure. Structural, chemical and optical investigations based on scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, UV-visible spectroscopy and photoluminescence supported by calculation correlated the H production with the dual presence of OH and Ti defects in the form of titanium interstitial atoms.

CO Capture by Hybrid Ultramicroporous TIFSIX-3-Ni under Humid Conditions Using Non-Equilibrium Cycling.

Although pyrazine-linked hybrid ultramicroporous materials (HUMs, pore size <7 Å) are benchmark physisorbents for trace carbon dioxide (CO ) capture under dry conditions, their affinity for water (H O) mitigates their carbon capture performance in humid conditions. Herein, we report on the co-adsorption of H O and CO by TIFSIX-3-Ni-a high CO affinity HUM-and find that slow H O sorption kinetics can enable CO uptake and release using shortened adsorption cycles with retention of ca. 90 % of dry CO uptake.

Insulin oedema in type 2 diabetes mellitus: A case report.

Insulin oedema is a rare condition that may occur after the initiation or rapid intensification of insulin therapy in patients with long-standing hyperglycaemia, commonly with type 1 diabetes mellitus (DM). We reported a case of insulin oedema in a patient with type 2 DM who presented with swelling of the extremities and weight gain of 3 kg 1 week after insulin initiation. A course of furosemide was administered, but no significant immediate improvement was observed; however, the lower limb swelling resolved spontaneously after 3 months of follow-up.

Identifying the Gate-Opening Mechanism in the Flexible Metal-Organic Framework UTSA-300.

Atomic-level understanding of the gate-opening phenomenon in flexible porous materials is an important step toward learning how to control, design, and engineer them for applications such as the separation of gases from complex mixtures. Here, we report such mechanistic insight through an in-depth study of the pressure-induced gate-opening phenomenon in our earlier reported metal-organic framework (MOF) Zn(dps)(SiF) (dps = 4,4'-dipyridylsulfide), also called UTSA-300, using isotherm and calorimetry measurements, infrared spectroscopy, and simulations. UTSA-300 is shown to selectively adsorb acetylene (CH) over ethylene (CH) and ethane (CH) and undergoes an abrupt gate-opening phenomenon, making this framework a highly selective gas separator of this complex mixture.

Metal-Organic Framework Based Hydrogen-Bonding Nanotrap for Efficient Acetylene Storage and Separation.

The removal of carbon dioxide (CO) from acetylene (CH) is a critical industrial process for manufacturing high-purity CH. However, it remains challenging to address the tradeoff between adsorption capacity and selectivity, on account of their similar physical properties and molecular sizes. To overcome this difficulty, here we report a novel strategy involving the regulation of a hydrogen-bonding nanotrap on the pore surface to promote the separation of CH/CO mixtures in three isostructural metal-organic frameworks (MOFs, named MIL-160, CAU-10H, and CAU-23, respectively).