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Stroke is the second result for death and ischemic stroke constitutes most of all stroke cases. Ischemic stroke takes place when blood clot or embolus blocks cerebral vessel and interrupts blood flow, which often leads to brain damage, permanent disability, or death. There is a 4.5-h (golden hour) treatment window to restore blood flow prior to permanent neurological impairment results. Current stroke treatments consist mechanical system or thrombolytic drug therapy to disrupt or dissolve thrombus. Promising method for stroke treatment is mechanical retrieving of thrombi employing device deployed endovascularly. Advent of smart materials has led to research fabrication of several minimally invasive endovascular devices that take advantage of new materials capabilities. One of these capabilities is shape memory, is capability of material to store temporary form, then activate to primary shape as subjected to stimuli. Shape memory polymers (SMPs) are employed as good materials for thrombectomy device fabrication. Therefore, current review presents thrombectomy device development and fabrication with SMPs. Design, performance, limitations, and in vitro or in vivo clinical results of SMP-based thrombectomy devices are identified. Review also sheds light on SMP's future outlook and recommendations for thrombectomy device application, opening a new era for advanced materials in materials science., (© 2024 The Authors. Macromolecular Rapid Communications published by Wiley‐VCH GmbH.)

Current electric storage systems eagerly focus on high-power and energy-dense Lithium-ion batteries to cope with increasing energy storage demands. Since cathode materials are one of the bottlenecks of these batteries, there is much interest in layered lithium-rich manganese oxide-based (LLMO) cathodes which can develop this technology. However, Initial Coulombic Efficiency (ICE) loss, poor rate performance and cycling instability issues are still persistent as problems to be solved for these materials. Recent research shows that water-soluble binders are effective in improving the performance of LLMO materials. Herein, we describe the synthesis, characterisation, and application of a series of water-soluble composites as a binder for LLMO cathodes. The PPy is introduced as part of the binder to improve the electronic conductivity and two different oxidants and various PPy to PSAP ratios were used to optimise the final properties. The electrochemical performance and morphology of the cathodes before and after cycling were investigated and compared with the conventional PVDF binder. The LLMO-2c electrode showed excellent charge-discharge performance, especially at 5 C and 10 C rates, and high cycling stability at 0.2 C whilst maintaining a final capacity of 184 mAh/g after 200 cycles, which is equal to 89.3 % capacity retention., (© 2024 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

HLA-B*39:06, HLA-B*39:01, and HLA-B*38:01 are closely related HLA allotypes differentially associated with type 1 diabetes (T1D) risk and progression. B*39:06 is highly predisposing, while B*39:01 and B*38:01 are weakly predisposing and protective allotypes, respectively. Here, we aimed to decipher molecular mechanisms underlying the differential association of these allotypes with T1D pathogenesis. We addressed peptide binding and conformational stability of HLA-B allotypes using computational and experimental approaches. Computationally, we found that B*39:06 and B*39:01 allotypes had more rigid peptide-binding grooves and were more promiscuous in binding peptides than B*38:01. Peptidomes of B*39:06 and B*39:01 contained fewer strong binders and were of lower affinity than that of B*38:01. Experimentally, we demonstrated that B*39:06 and B*39:01 had a higher capacity to bind peptides and exit to the cell surface but lower surface levels and were degraded faster than B*38:01. In summary, we propose that promiscuous B*39:06 and B*39:01 may bind suboptimal peptides and transport them the cell surface, where such unstable complexes may contribute to the pathogenesis of T1D., (© 2024 The Authors. European Journal of Immunology published by Wiley‐VCH GmbH.)

Intracranial aneurysm is the abnormal focal dilation in brain arteries. When untreated, it can enlarge to rupture points and account for subarachnoid hemorrhage cases. Intracranial aneurysms can be treated by blocking the flow of blood to the aneurysm sac with clipping of the aneurysm neck or endovascular embolization with embolics to promote the formation of the thrombus. Coils or an embolic device are inserted endovascularly into the aneurysm via a micro-catheter to fill the aneurysm. Many embolization materials have been developed. An embolization coil made of soft and thin platinum wire called the "Guglielmi detachable coil" (GDC) enables safer treatment for brain aneurysms. However, patients may experience aneurysm recurrence because of incomplete coil filling or compaction over time. Unsatisfactory recanalization rates and incomplete occlusion are the drawbacks of endovascular embolization. So, the fabrication of new medical devices with less invasive surgical techniques is mandatory to enhance the long-term therapeutic performance of existing endovascular procedures. For this aim, the current article reviews polymeric materials including blends and composites employed for embolization of intracranial aneurysms. Polymeric materials used in embolic agents, their advantages and challenges, results of the strategies used to overcome treatment, and results of clinical experiences are summarized and discussed., (© 2023 The Authors. Macromolecular Bioscience published by Wiley‐VCH GmbH.)

The use of mass spectrometry and antibody-based sequencing technologies at the single-cell level has led to an increase in single-cell proteomic datasets. Integrating these datasets is crucial to eliminate the batch effect that often arises due to their limited sequencing molecules. Although methods for horizontally integrating high-dimensional single-cell transcriptomic datasets can also be applied to single-cell proteomic datasets, a specialized approach explicitly tailored for low-dimensional proteomic datasets may enhance the integration process. Here, we introduce SCPRO-HI, an algorithm for the horizontal integration of antibody-based single-cell proteomic datasets. It utilizes a hierarchical cell anchoring technique to match cells based on the similarity of distinctive proteins for constituting cell clusters. A novel variational auto-encoder model is employed for correcting batch effects on the protein abundances, eliminating the need for mapping them into a new domain. Moreover, we propose a technique for extending the algorithm to high-dimensional datasets. The performance of the SCPRO-HI algorithm is evaluated using simulated and real-world single-cell proteomic datasets. The findings demonstrate our algorithm outperforms state-of-the-art methods, achieving a 75% higher silhouette score while preserving HVPs 13% better. Furthermore, the algorithm shows competitive performance in transcriptomic datasets, suggesting potential for integrating high-dimensional mass-spectrometry-based proteomic datasets., (© 2023 The Authors. PROTEOMICS published by Wiley‐VCH GmbH.)

This study focuses on creating a specialized nanogel for targeted drug delivery in cancer treatment, specifically targeting prostate cancer. This nanogel (referred to as SGK 636/Peptide 563/PEtOx nanogel) is created using hydrophilic poly(2-ethyl-2-oxazoline) (PEtOx) through a combination of living/cationic ring-opening polymerization (CROP) and alkyne-azide cycloaddition (CuAAC) "click" chemical reactions. A fluorescent probe (BODIPY) is also conjugated with the nanogel to monitor drug delivery. The characterizations through 1 H-NMR, and FT-IR, SEM, TEM, and DLS confirm the successful production of uniform, and spherical nanogels with controllable sizes (100 to 296 nm) and stability in physiological conditions. The biocompatibility of nanogels is evaluated using MTT cytotoxicity assays, revealing dose-dependent cytotoxicity. Drug-loaded nanogels exhibited significantly higher cytotoxicity against cancer cells in vitro compared to drug-free nanogels. Targeting efficiency is examined using both peptide-conjugated and peptide-free nanogels, with the intracellular uptake of peptide 563-conjugated nanogels by tumor cells being 60-fold higher than that of nanogels without the peptide. The findings suggest that the prepared nanogel holds great potential for various drug delivery applications due to its ease of synthesis, tunable functionality, non-toxicity, and enhanced intracellular uptake in the tumor region., (© 2023 The Authors. Macromolecular Bioscience published by Wiley-VCH GmbH.)

With their high volumetric capacity and electronic conductivity, sodium-selenium (Na-Se) batteries have attracted attention for advanced battery systems. However, the irreversible deposition of sodium selenide (Na 2 Se) results in rapid capacity degradation and poor Coulombic efficiency. To address these issues, cubic α-Mn 2 O 3 is introduced herein as an electrocatalyst to effectively catalyze Na 2 Se conversion and improve the utilization of active materials. The results show that the addition of 10 wt% Mn 2 O 3 in the selenium/Ketjen black (Se/KB) composite enhances the conversion from Na 2 Se to Se by lowering activation energy barrier and leads to fast sodium-ion kinetics and low internal resistance. Consequently, the Mn 2 O 3 -based composite delivers a high specific capacity of 635 mAh ⋅ g -1 at 675 mA ⋅ g -1 after 250 cycles as well as excellent cycling stability for 800 cycles with a high specific capacity of 317 mAh ⋅ g -1 even at the high current density of 3375 mA ⋅ g -1 . Due to the cubic Mn 2 O 3 electrocatalyst, the performance of the composites is superior to existing state-of-the-art Na-Se batteries reported in the literature., (© 2023 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

Herein, we report the design and synthesis of a layered redox-active, antiferromagnetic metal organic semiconductor crystals with the chemical formula [Cu(H 2 O) 2 V(µ-O)(PPA) 2 ] (where PPA is phenylphosphonate). The crystal structure of [Cu(H 2 O) 2 V(µ-O)(PPA) 2 ] shows that the metal phosphonate layers are separated by phenyl groups of the phenyl phosphonate linker. Tauc plotting of diffuse reflectance spectra indicates that [Cu(H 2 O) 2 V(µ-O)(PPA) 2 ] has an indirect band gap of 2.19 eV. Photoluminescence (PL) spectra indicate a complex landscape of energy states with PL peaks at 1.8 and 2.2 eV. [Cu(H 2 O) 2 V(µ-O)(PPA) 2 ] has estimated hybrid ionic and electronic conductivity values between 0.13 and 0.6 S m -1 . Temperature-dependent magnetization measurements show that [Cu(H 2 O) 2 V(µ-O)(PPA) 2 ] exhibits short range antiferromagnetic order between Cu(II) and V(IV) ions. [Cu(H 2 O) 2 V(µ-O)(PPA) 2 ] is also photoluminescent with photoluminescence quantum yield of 0.02%. [Cu(H 2 O) 2 V(µ-O)(PPA) 2 ] shows high electrochemical, and thermal stability., (© 2023 The Authors. Small published by Wiley-VCH GmbH.)

This work examines the influence of applied external voltage in bulk electrolysis on the excited-state properties of 8'-apo-β-carotenal in acetonitrile by steady-state and ultrafast time-resolved absorption spectroscopy. The data collected under bulk electrolysis were compared with those taken without applied voltage. The steady-state measurements showed that although intensity of the S 0 -S 2 absorption band varies with the applied voltage, the spectral position remain nearly constant. Comparison of transient absorption spectra shows that the magnitude of the ICT-like band decreases during the experiment under applied voltage condition, and is associated with a prolongation of the S 1 /ICT-like lifetime from 8 ps to 13 ps. Furthermore, switching off the applied voltage resulted in returning to no-voltage data within about 30 min. Our results show that the amplitude of the signal associated with the ICT state can be tuned by applying an external voltage., (© 2023 The Authors. ChemPlusChem published by Wiley-VCH GmbH.)

Scope: The purpose of this study was to look into the antiviral activity of a plant extract derived from the roots of the Saussurea lappa as a food supplement against SARS-CoV-2 infection., Methods and Results: Vero E6 cells are employed in the study to test the neutralizing effect of Saussurea lappa extract against the SARS-CoV-2 virus. For anti-viral activity detection, a sensitive real-time cell analyzer (xCELLigence RTCA) with a high repetition rate is used. A challenge experiment in mice is planned as a result of the in vitro analysis. A challenge test against SARS-CoV-2 is performed with 10 adult female K18-hACE2 transgenic mice in each group for this purpose. The mice in the S. lappa Group are gavaged 2 days before the virus is administered intranasally (i.n.). The control group received PBS instead of the extract. SARS-CoV-2 virus is administered i.n. under anesthesia for the first 3 days of the experiment, and S. lappa extract was administered by gavage in the afternoon. On the 10th day, mice in the S. lappa group survived the study, whereas animals in the control group grew ill and/or died. In this study, the extract protects the mice against the SARS-CoV-2 virus in 90% of the cases., Conclusions: This study demonstrates that the Saussurea plant has antiviral effects against SARS-CoV-2 in vitro and in animal models., (© 2023 The Authors. Molecular Nutrition & Food Research published by Wiley-VCH GmbH.)

Solid-state lithium batteries are promising and safe energy storage devices for mobile electronics and electric vehicles. In this work, we report a facile in situ polymerization of 1,3-dioxolane electrolytes to fabricate integrated solid-state lithium batteries. The in situ polymerization and formation of solid-state dioxolane electrolytes on interconnected carbon nanotubes (CNTs) and active materials is the key to realizing a high-performance battery with excellent interfacial contact among CNTs, active materials and electrolytes. Therefore, the electrodes could be tightly integrated into batteries through the CNTs and electrolyte. Electrons/ions enable full access to active materials in the whole electrode. Electrodes with a low resistance of 4.5 Ω □ -1 and high lithium-ion diffusion efficiency of 2.5×10 -11  cm 2  s -1 can significantly improve the electrochemical kinetics. Subsequently, the batteries demonstrated high energy density, amazing charge/discharge rate and long cycle life., (© 2023 Wiley-VCH GmbH.)

Transparent, dark orange Ba[Au(N 3 ) 4 ] 2  ⋅ 4 H 2 O was synthesized by reaction of Ba(N 3 ) 2 and AuCl 3 or HAuCl 4 in aqueous solution. The novel barium tetraazidoaurate(III) tetrahydrate crystallizes in the monoclinic space group Cc (no. 9) with a=1813.68(17) pm, b=1737.95(11) pm, c=682.04(8) pm and β=108.849(4)°. The predominant structural features of Ba[Au(N 3 ) 4 ] 2  ⋅ 4 H 2 O are two crystallographically independent discrete anions [Au(N 3 ) 4 ] - with gold in a tetragonal planar coordination by nitrogen. Vibrational spectra show good agreement with those of other azidoaurates(III). Upon drying, this salt was shown to be a highly explosive material., (© 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Photodynamic therapy (PDT) is an innovative, non-invasive and highly selective therapeutic modality for tumours and non-malignant diseases. BODIPY based molecules can function as new generation photosensitizers (PSs) in various PDT applications. Despite numerous conjugated PS systems are available, BODIPYs containing erlotinib lagged behind other photosensitizer units. In this study, smart photosensitizers containing BODIPY, erlotinib and hydrophilic units were prepared for the first time, their physicochemical properties and PDT effects were investigated. Compared with non-halogenated compound, halogenated derivatives possessed much lower fluorescence profile as well as the good ROS generation ability under red light. In vitro PDT studies were performed on both healthy (PNT1a) and prostate cancerous cells (PC3) to determine the selectivity of the compounds on cancerous cells and their effects under light. The halogenated conjugates, exposed to low dose of light illumination exhibited potent activity on cancer cell viability and the calculated IC 50 values proved the high phototoxicity of the photosensitizers. It was also determined that the PSs have very low dark toxicity and that the light illumination and ROS formation are required for the initiation of the cell death mechanism. As a result, erlotinib modified BODIPYs could serve as promising agents in anticancer photodynamic therapy., (© 2022 Wiley-VCH GmbH.)

Herein, a simple way of tuning the optical and structural properties of porphyrin-based hydrogen-bonded organic frameworks (HOFs) is reported. By inserting transition metal ions into the porphyrin cores of GTUB-5 (p-H 8 -TPPA (5,10,15,20-Tetrakis[p-phenylphosphonic acid] HOF), the authors show that it is possible to generate HOFs with different band gaps, photoluminescence (PL) life times, and textural properties. The band gaps of the resulting HOFs (viz., Cu-, Ni-, Pd-, and Zn-GTUB-5) are measured by diffuse reflectance and PL spectroscopy, as well as calculated via DFT, and the PL lifetimes are measured. Across the series, the band gaps vary over a narrow range from 1.37 to 1.62 eV, while the PL lifetimes vary over a wide range from 2.3 to 83 ns. These differences ultimately arise from metal-induced structural changes, viz., changes in the metal-to-nitrogen distances, number of hydrogen bonds, and pore volumes. DFT reveals that the band gaps of Cu-, Zn-, and Pd- GTUB-5 are governed by highest occupied/lowest unoccupied crystal orbitals (HOCO/LUCO) composed of π- orbitals on the porphyrin linkers, while that of Ni-GTUB-5 is governed by a HOCO and LUCO composed of Ni dorbitals. Overall, our findings show that metal-insertion can be used to optimize HOFs for optoelectronics and small-molecule capture applications., (© 2022 The Authors. Small published by Wiley-VCH GmbH.)

A critical factor in developing an efficient photosensitizer-gold nanoparticle (PS-AuNP) hybrid system with improved plasmonic photosensitization is to allocate a suitable space between AuNPs and PS. Poly(amidoamine) (PAMAM) dendrimer is selected as a spacer between the PS and confeito-like gold nanoparticles (confeito-AuNPs), providing the required distance (≈2.5-22.5 nm) for plasmon-enhanced singlet oxygen generation and heat production upon 638-nm laser irradiation and increase the cellular internalization of the nanoconjugates. The loading of the PS, tetrakis(4-carboxyphenyl) porphyrin (TCPP), and modified zinc phthalocyanine (ZnPc1) onto PAMAM-confeito-AuNPs demonstrate better in vitro cancer cell-killing efficacy, as the combined photothermal-photodynamic therapies (PTT-PDTs) outperforms the single treatment modalities (PTT or PDT alone). These PS-PAMAM-confeito-AuNPs also demonstrate higher phototoxicity than photosensitizers directly conjugated to confeito-AuNPs (TCPP-confeito-AuNPs and ZnPc1-confeito-AuNPs) against all breast cancer cell lines tested (MDA-MB-231, MCF7, and 4T1). In the in vivo studies, TCPP-PAMAM-confeito-AuNPs are biocompatible and exhibit a selective tumor accumulation effect, resulting in higher antitumor efficacy than free TCPP, PAMAM-confeito-AuNPs, and TCPP-confeito-AuNPs. In vitro and in vivo evaluations confirm PAMAM effectiveness in facilitating cellular uptake, plasmon-enhanced singlet oxygen and heat generation. In summary, this study highlights the potential of integrating a PAMAM spacer in enhancing the plasmon effect-based photothermal-photodynamic anticancer treatment efficiency of PS-decorated confeito-AuNPs., (© 2022 Wiley-VCH GmbH.)

Nanotheranostic tailor-made carriers are potent platforms for the treatment of cancer that propound a number of advantages over conventional agents for photodynamic therapy (PDT). Herein, four new heavy atom free amphiphilic glucose-BODIPY-fullerene dyads (14-17) endowed with carbohydrate units in the styryl units, which can also form nanomicelles (14-17NM) with Tween 80 for PDT are reported. Glucose-BODIPY-fullerene systems (14-17) and related nanomicelles (14-17NM) have been prepared to emcee efficient singlet oxygen generation upon light irradiation. In vitro anti-tumor effects of the compounds 14-17 and 14-17NM in the presence of light and in darkness have been investigated with K562 human chronic myelogenous leukemia suspension cells. Anti-tumor toxicity upon light irradiation was due to the formation of singlet oxygen and reactive oxygen species (ROS). This study may provide an accomplished example of efficient PDT applications based on nanovehicles fabricated with universal spin converter, fullerene, light harvesting unit, BODIPY dyes conjugated with targeting units to fight against cancer., (© 2021 Wiley-VCH GmbH.)

Herein, we report on the synthesis of a microporous, three-dimensional phosphonate metal-organic framework (MOF) with the composition Cu 3 (H 5 -MTPPA) 2  ⋅ 2 NMP (H 8 -MTPPA=methane tetra-p-phenylphosphonic acid and NMP=N-methyl-2-pyrrolidone). This MOF, termed TUB1, has a unique one-dimensional inorganic building unit composed of square planar and distorted trigonal bipyramidal copper atoms. It possesses a (calculated) BET surface area of 766.2 m 2 /g after removal of the solvents from the voids. The Tauc plot for TUB1 yields indirect and direct band gaps of 2.4 eV and 2.7 eV, respectively. DFT calculations reveal the existence of two spin-dependent gaps of 2.60 eV and 0.48 eV for the alpha and beta spins, respectively, with the lowest unoccupied crystal orbital for both gaps predominantly residing on the square planar copper atoms. The projected density of states suggests that the presence of the square planar copper atoms reduces the overall band gap of TUB1, as the beta-gap for the trigonal bipyramidal copper atoms is 3.72 eV., (© 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

The covalent attachment of molecular photosensitizers (PS) to polyoxometalates (POMs) opens new pathways to PS-POM dyads for light-driven charge-transfer and charge-storage. Here, we report a synthetic route for the covalent linkage of BODIPY-dyes to Anderson-type polyoxomolybdates by using CLICK chemistry (i. e. copper-catalyzed azide-alkyne cycloaddition, CuAAC). Photophysical properties of the dyad were investigated by combined experimental and theoretical methods and highlight the role of both sub-components for the charge-separation properties. The study demonstrates how CLICK chemistry can be used for the versatile linkage of organic functional units to molecular metal oxide clusters., (© 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

The ability to tune the optical features of BODIPY materials in the solid state is essential for their photorelated application and requires efficient control of the crystal packing. In this study, such control of BODIPY supramolecular assemblies was achieved by deliberate design and synthesis of a BODIPY containing a strong halogen-bond (XB) acceptor (-NO 2 ) and donor (I, Br) to mediate XB interactions. The di-halogenated structures formed isostructural mono-coordinate motif B3, B4 (1D tubular structure) and symmetric bifurcated motif B4-II (1D zigzag chains structure) through N-O⋅⋅⋅I, Br XB interactions. These XB interactions promote singlet-to-triplet intersystem crossing and triplet-to-singlet reverse intersystem crossing due to partial delocalization of oxygen electrons onto Br and I, which leads to unexpected fluorescence enhancement of B4-II. Finally, the indirect optical band gaps of B3, B4 and B4-II were amenable to tuning in the range of 1.85-2.50  eV by XB-driven crystal packings., (© 2020 Wiley-VCH GmbH.)

A one-dimensional nanotubular metal-organic framework (MOF) [Ni(Cu-H 4 TPPA)]⋅2 (CH 3 ) 2 NH 2 + (H 8 TPPA=5,10,15,20-tetrakis[p-phenylphosphonic acid] porphyrin) constructed by using the arylphosphonic acid H 8 TPPA is reported. The structure of this MOF, known as GTUB-4, was solved by using single-crystal X-ray diffraction and its geometric accessible surface area was calculated to be 1102 m 2  g -1 , making it the phosphonate MOF with the highest reported surface area. Due to the extended conjugation of its porphyrin core, GTUB-4 possesses narrow indirect and direct bandgaps (1.9 eV and 2.16 eV, respectively) in the semiconductor regime. Thermogravimetric analysis suggests that GTUB-4 is thermally stable up to 400 °C. Owing to its high surface area, low bandgap, and high thermal stability, GTUB-4 could find applications as electrodes in supercapacitors., (© 2020 The Authors. Published by Wiley-VCH GmbH.)

Herein, we report the third generation of fluorescent probes (arylphosphonic acids) to target calcifications, particularly hydroxyapatite (HAP). In this study, we use highly conjugated porphyrin-based arylphosphonic acids and their diesters, namely 5,10,15,20-tetrakis[m-(diethoxyphosphoryl)phenyl]porphyrin (m-H 8 TPPA-OEt 8 ) and 5,10,15,20-tetrakis [m-phenylphosphonic acid]porphyrin (m-H 8 TPPA), in comparison with their positional isomers 5,10,15,20-tetrakis[p-(diisopropoxyphosphoryl)phenyl]porphyrin (p-H 8 TPPA-iPr 8 ) and 5,10,15,20-tetrakis [p-phenylphosphonic acid]porphyrin (p-H 8 TPPA), which have phosphonic acid units bonded to sp 2 carbon atoms of the fluorescent core. The conjugation of the fluorescent core is thus extended to the (HAP) through sp 2 -bonded -PO 3 H 2 units, which generates increased fluorescence upon HAP binding. The resulting fluorescent probes are highly sensitive towards the HAP in rat bone sections. The designed probes are readily taken up by cells. Due to the lower reported toxicity of (p-H 8 TPPA), these probes could find applications in monitoring bone resorption or adsorption, or imaging vascular or soft tissue calcifications for breast cancer diagnosis etc., (© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

Carbon nanotubes (CNTs) with hydrophobic and atomically smooth inner channels are promising for building ultrahigh-flux nanofluidic platforms for energy harvesting, health monitoring, and water purification. Conventional wisdom is that nanoconfinement effects determine water transport in CNTs. Here, using full-atomistic molecular dynamics simulations, it is shown that water transport behavior in CNTs strongly correlates with the electronic properties of single-walled CNTs (metallic (met) vs semiconducting (s/c)), which is as dominant as the effect of nanoconfinement. Three pairs of CNTs (i.e., (8,8) met , 10.85 Å vs (9,7) s/c , 10.88 Å; (9,8) s/c , 11.53 Å vs (10,7) met , 11.59 Å; and (9,9) met , 12.20 Å vs (10,8) s/c , 12.23 Å) are used to investigate the roles of diameter and metallicity. Specifically, the (9,8) s/c can restrict the hydrogen-bonding-mediated structuring of water and give the highest reduction in carbon-water interaction energy, providing an extraordinarily high water flux, around 250 times that of the commercial reverse osmosis membranes and approximately fourfold higher than the flux of the state-of-the-art boron nitrate nanotubes. Further, the high performance of (9,8) s/c is also reproducible when embedded in lipid bilayers as synthetic high-water flux porins. Given the increasing availability of high-purity CNTs, these findings provide valuable guides for realizing novel CNT-enhanced nanofluidic systems., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Herein, the first semiconducting and magnetic phosphonate metal-organic framework (MOF), TUB75, is reported, which contains a 1D inorganic building unit composed of a zigzag chain of corner-sharing copper dimers. The solid-state UV-vis spectrum of TUB75 reveals the existence of a narrow bandgap of 1.4 eV, which agrees well with the density functional theory (DFT)-calculated bandgap of 1.77 eV. Single-crystal conductivity measurements for different orientations of the individual crystals yield a range of conductances from 10 -3 to 10 3 S m -1 at room temperature, pointing to the directional nature of the electrical conductivity in TUB75. Magnetization measurements show that TUB75 is composed of antiferromagnetically coupled copper dimer chains. Due to their rich structural chemistry and exceptionally high thermal/chemical stabilities, phosphonate MOFs like TUB75 may open new vistas in engineerable electrodes for supercapacitors., (© 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The molecular design, synthesis, and characterization of an acceptor-donor-acceptor (A-D-A) semiconductor BDY-Ph-2T-Ph-BDY comprising a central phenyl-bithiophene-phenyl π-donor and BODIPY π-acceptor end-units is reported. The semiconductor shows an optical band gap of 2.32 eV with a highly stabilized HOMO/LUMO (-5.74 eV/-3.42 eV). Single-crystal X-ray diffraction (XRD) reveals D-A dihedral angle of ca. 66° and strong intermolecular "C-H ⋅⋅⋅ π (3.31 Å)" interactions. Reduced π-donor strength, increased D-A dihedral angle, and restricted intramolecular D-A rotations allows for both good fluorescence efficiency (Φ F =0.30) and n-channel OFET transport (μ e =0.005 cm 2 /V ⋅ s; I on /I off =10 4 -10 5 ). This indicates a much improved (6-fold) fluorescence quantum yield compared to the meso-thienyl BODIPY semiconductor BDY-4T-BDY. Photophysical studies reveal important transitions between locally excited (LE) and twisted intramolecular charge-transfer (TICT) states in solution and the solid state, which could be controlled by solvent polarity and nano-aggregation. This is the first report of such high emissive characteristics for a BODIPY-based n-channel semiconductor., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A new family of porous metal-organic frameworks (MOFs), namely alkali phosphonate MOFs, is reported. [Na 2 Cu(H 4 TPPA)]⋅(NH 2 (CH 3 ) 2 ) 2 (GTUB-1) was synthesized using the tetratopic 5,10,15,20-tetrakis[p-phenylphosphonic acid] porphyrin (H 8 -TPPA) linker with planar X-shaped geometrical core. GTUB-1 is composed of rectangular void channels with BET surface area of 697 m 2  g -1 . GTUB-1 exhibits exceptional thermal stability. The toxicity analysis of the (H 8 -TPPA) linker indicates that it is well tolerated by an intestinal cell line, suggesting its suitability for creating phosphonate MOFs for biological applications., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Over the last decades, the fabrication of 3D tissues has become commonplace in tissue engineering and regenerative medicine. However, conventional 3D biofabrication techniques such as scaffolding, microengineering, and fiber and cell sheet engineering are limited in their capacity to fabricate complex tissue constructs with the required precision and controllability that is needed to replicate biologically relevant tissues. To this end, 3D bioprinting offers great versatility to fabricate biomimetic, volumetric tissues that are structurally and functionally relevant. It enables precise control of the composition, spatial distribution, and architecture of resulting constructs facilitating the recapitulation of the delicate shapes and structures of targeted organs and tissues. This Review systematically covers the history of bioprinting and the most recent advances in instrumentation and methods. It then focuses on the requirements for bioinks and cells to achieve optimal fabrication of biomimetic constructs. Next, emerging evolutions and future directions of bioprinting are discussed, such as freeform, high-resolution, multimaterial, and 4D bioprinting. Finally, the translational potential of bioprinting and bioprinted tissues of various categories are presented and the Review is concluded by exemplifying commercially available bioprinting platforms., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

An entirely earth-abundant chromophore-relay water oxidation catalyst triad system, which is robust and efficient at neutral pH, is presented. The synthesis involves the coordination of a porphyrin derivative to a bridging Fe(CN) 5 group, which is then reacted with Co ions to prepare a covalently linked chromophore-Prussian blue analogue assembly. Light-driven water oxidation studies in the presence of an electron scavenger indicate that the triad is active and it maintains a steady activity for at least three hours. Transient absorption experiments and computational studies reveal that the Fe(CN) 5 group is more than a linker as it takes part in electron-transfer and co-operates with porphyrin in the charge separation process., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

NAD(P) + dependent formate dehydrogenase (FDH) is an oxidoreductase used as a biocatalyst to regenerate NAD(P)H in reductase-mediated chiral synthesis reactions. Solvent stability and the need to reduce NADP + to NADPH, due to the high cost of NADPH, are required features in the industrial usage of FDHs. Therefore, we aimed to identify a novel, robust NADP + dependent FDH and evaluate the effect of N- and C- terminus His tag extensions on protein solubility and activity. Herein, we report a novel, DMSO tolerant formate dehydrogenase (BdFDH), which has dual coenzyme specificity and tolerance to acidic pH, from Burkholderia dolosa PC543. N- and C-terminus His-tagged BdFDHs were expressed separately in Escherichia coli BL21 (DE3). The C-terminal His-tagged BdFDH was soluble and active whereas the N-terminal version was not. The enzyme displays dual coenzyme specificity and resistance to some organic solvents, particularly DMSO, and is able to tolerate acidic pH conditions. The apparent K M values for NADP + , NAD + and sodium formate (with NADP + ), are 1.17, 14.7 and 5.66 mM, respectively. As a result, due to its DMSO tolerance and coenzyme preference, this enzyme can be utilized as an NAD(P)H recycler in several biotransformations particularly when carried out under acidic conditions. Moreover, it can be said that the position of the His tag extension may affect the enzyme solubility and functionality., (© 2018 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim.)

Phthalocyanine derivatives do not cease to gain attention due to their numerous properties and applications (e.g., sensor, PDT). This makes them a unique scaffold for the design of new material. In this context, we were interested to develop the synthesis of an imino nitroxide-substituted phthalocyanine by Ullman's procedure; a challenge due to the intrinsic low solubility of most phthalocyanine derivative in much solvents. To overcome this solubility problem, we designed a phthalocyanine with bulky neopentyl substituents in peripheral positions as counterpart to the imino nitroxide moieties. The imino nitroxide-substituted phthalocyanine was obtained by condensation of a monoformyl-substituted phthalocyanine with 2,3-bis(hydroxylamino)-2,3-dimethylbutane in refluxing THF-MeOH (2:1) mixture in the presence of p-toluenesulfonic acid monohydrate, follow by oxidation with PbO 2 . Characterization was performed by electrochemistry, UV/Vis and EPR spectroscopy in solution as well as SQUID in solid state., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

An optimized nucleophilic synthetic approach featuring mild conditions and microwave energy was utilized to circumvent the classical Ullman procedure and access a polynitronyl nitroxide radical easily and in pure form. The simultaneous controlled introduction of preformed nitronyl nitroxide radicals on a cyclotriphosphazene core leads to a novel polyphosphazene monomer which is suitable for both n- and a p-type redox-active material in organic rechargeable batteries as demonstrated by electrochemistry. Additionally, absorption spectra and square-wave voltammetry were utilized to quantify the number of nitronyl nitroxide radical units on the cyclotriphosphazene scaffold., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Chemical tuning of nanoporous, solid sorbents for ideal CO 2 binding requires unhindered amine functional groups on the pore walls. Although common for soluble organics, post-synthetic reduction of nitriles in porous networks often fails due to insufficient and irreversible metal hydride penetration. In this study, a nanoporous network with pendant nitrile groups, microsphere morphology was synthesized in large scale. The hollow microspheres were easily decorated with primary amines through in situ reduction by widely available boranes. The CO 2 capture capacity of the modified sorbent was increased to up to four times that of the starting nanoporous network with a high heat of adsorption (98 kJ mol -1 ). The surface area can be easily tuned between 1 and 354 m 2  g -1 . The average particle size (ca. 50 μm) is also quite suitable for CO 2 capture applications, such as those with fluidized beds requiring spheres of micron sizes., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Nitroxide free radicals have been used to study the inner space of one of Rebek's water-soluble capsules. EPR and (1) H NMR spectroscopy, ESI-MS, and DFT calculations showed a preference for the formation of 1:2 complexes. EPR titrations allowed us to determine binding constants (Ka ) in the order of 10(7)  M(-2) . EPR spectral-shape analysis provided information on the guest rotational dynamics within the capsule. The interplay between optimum hydrogen bonding upon capsule formation and steric strain for guest accommodation highlights some degree of flexibility for guest inclusion, particularly at the center of the capsule where the hydrogen bond seam can be barely distorted or slightly disturbed., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)