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Porosity control and structural analysis of metal–organic frameworks (MOFs) can be achieved using regioisomeric ligand mixtures. While ortho-dimethoxy-functionalized MOFs yielded highly porous structures and para-dimethoxy-functionalized MOFs displayed almost nonporous properties in their N2 isotherms after evacuation, regioisomeric ligand-mixed MOFs showed variable N2 uptake amount and surface area depending on the ligand-mixing ratio. The quantity of N2 absorbed was tuned between 20 and 300 cm3/g by adjusting the ligand-mixing ratio. Both experimental analysis and computational modeling were performed to understand the porosity differences between ortho- and para-dimethoxy-functionalized MOFs. Detailed structural analysis using X-ray crystallographic data revealed significant differences in the coordination environments of DMOF-[2,3-(OMe)2] and DMOF-[2,5-(OMe)2] (DMOF = dabco MOF, dabco = 1,4-diazabicyclo[2.2.0]­octane). The coordination bond between Zn2+ and carboxylate in the ortho-functionalized DMOF-[2,3-(OMe)2] was more rigid than that in the para-functionalized DMOF-[2,5-(OMe)2]. Quantum-chemical simulation also showed differences in the coordination environments of Zn secondary building unit surrounded by methoxy-functionalized ligands and pillar ligands. In addition, the binding energy differences between Zn2+ and regioisomeric ligands (ortho- and para-dimethoxy-functionalized benzene-1,4-dicarboxylates) explained the rigidity and porosity changes of the mixed MOFs upon evacuation and perfectly matched with experimental N2 adsorption and X-ray crystallography data.

Long-term stability of the solid electrolyte interphase (SEI) and cathode-electrolyte interface (CEI) layers formed on anodes and cathodes is imperative to mitigate the interfacial degradation of electrodes and enhance the cycle life of lithium-ion batteries (LIBs). However, the SEI on the anode and CEI on the cathode are vulnerable to the reactive species of PF

NaNO3 -promoted MgO composite materials have been prepared and their ability to sorb CO2 at a concentration relevant to CO2 capture from flue gas is explored. The uptake kinetics and capacities of sorbents of different NaNO3 /MgO ratios are measured at intermediate temperatures of 230-300 °C. The sorbent with a NaNO3 /MgO ratio of 0.10 has the highest 12 h sorption capacity among sorbents with different NaNO3 loadings, and the highest sorption capacity of 11.2 mmol CO2 g-1 is observed at 260 °C. Intriguingly, an induction period is observed in the initial stage of CO2 sorption. In situ XRD analysis, in situ FTIR spectroscopy, and a comparison of the CO2 sorption behavior under simulated flue gas conditions in comparison to prior studies employing pure CO2 indicated that the sorption of CO2 occurred through nucleation of MgCO3 crystallites in the material. The data indicate that the concentration of CO2 within the molten medium of NaNO3 , which is affected by both the solubility of CO2 in molten NaNO3 and the partial pressure of CO2 in the surrounding atmosphere, has a critical impact on the length of the induction period. A partially desorbed sample after sorption of CO2 displays much-improved sorption kinetics in the next cycle and was able to sorb and desorb CO2 over multiple cycles at isothermal conditions by simply switching the feed gas from CO2 to inert gas.

This paper reviews a previously-reported methodology for establishing feedback control of self-assembly. The methodology combines dimension reduction, supervised learning, and dynamic programming to obtain an optimal feedback control policy for reaching a desired assembled state. Sampled data are used in calculating the optimal feedback policy; this data can be generated using a predictive model (i.e. “simulated data”) or using experimental data. The control strategy is demonstrated, with both simulation and experimental results, for two applications: control of colloidal assembly (to produce perfect colloidal crystals) and control of crystallization from solution (to produce crystals of desired average size).

9,9'-Spirobifluorene-based closo-o-carboranyl (SFC1 and SFC2) compounds and their nido-derivatives (nido-SFC1 and nido-SFC2) were prepared and characterized. The two closo-compounds displayed major absorption bands assignable to π-π* transitions involving the spirobifluorene group, as well as weak intramolecular charge-transfer (ICT) transitions between the o-carboranes and their spirobifluorene moieties. The nido-compounds exhibited slightly blueshifted absorption bands resulting from the absence of the ICT transitions corresponding to the o-carborane moieties due to the anionic character of the nido-o-carboranes. While SFC1 exhibited only high-energy emissions in THF at 298 K (only from locally excited (LE) states assignable to π-π* transitions on the spirobifluorene group), remarkable emissions in the low-energy region were observed in the rigid state such as in THF at 77 K and in the film state. SFC2 displayed intense emissions in the low-energy region in all states. The fact that neither of the nido-derivatives of SFC1 and SFC2 exhibited low-energy emissions and the TD-DFT calculation results of each closo-compound clearly verified that the low-energy emission was based on ICT-based radiative decay. The conformational barriers from each relative energy calculation upon changing the dihedral angles around the o-carborane cages for both compounds confirmed that the rotation of the o-carborane cages and terminal phenyl rings for SFC1 is freer than that for SFC2.

The effect of metal on the degree of flexibility upon evacuation of metal-organic frameworks (MOFs) has been revealed with positional control of the organic functionalities. Although Co-, Cu-, and Zn-based DMOFs (DMOF = DABCO MOF, DABCO = 1,4-diazabicyclo[2.2.2]octane) with ortho-ligands (2,3-NH2 Cl) have frameworks that are inflexible upon evacuation, MOFs with para-ligands (2,5-NH2 Cl) showed different N2 uptake amounts after evacuation by metal exchange. Considering that the structural analyses were not fully sufficiently different to explain the drastic changes in N2 adsorption after evacuation, quantum chemical simulation was explored. A new index (η) was defined to quantify the regularity around the metal based on differences in the oxygen-metal-oxygen angles. Within 2,5-NH2 Cl, the η value becomes larger as the metal are varied from Co to Zn. A large η value means that the structures around the metal center are less ordered. These results can be used to explain flexibility changes upon evacuation by altering the metal cation in this regioisomeric system.

A series of dimeric aluminum compounds [Al(OCMe2 CH2 N(R)CH2 X)]2 [X=pyridin-2-yl, R=H (PyrH ); X= pyridin-2-yl, R=Me (PyrMe ); X=furan-2-yl, R=H (FurH ); X= furan-2-yl, R=Me (FurMe ); X=thiophen-2-yl, R=H (ThioH ); X= thiophen-2-yl, R=Me (ThioMe )] containing heterocyclic pendant group attached to the nitrogen catalyze the coupling of CO2 with epoxides under ambient conditions. In a comparison of their catalytic activities with those of aluminum complexes without pendant groups at N [X=H, R=H (HH ); X=H, R=Me (HMe )] or with non-heterocyclic pendant groups [X=CH2 CH2 OMe, R=H (OMeH ); X=CH2 CH2 NMe2 , R=H (NMe2H ); X=CH2 CH2 NMe2 , R=Me (NMe2Me )], complexes containing heterocycles, in conjunction with (nBu)4 NBr as a cocatalyst, show higher catalytic activities for the synthesis of cyclic carbonates under the same ambient conditions. The best catalyst system for this reaction is PyrH /(nBu)4 NBr system, which gives a turnover number of 99 and a turnover frequency of 4.1 h-1 , making it 14- and 20-times more effective than HH /(nBu)4 NBr and HMe /(nBu)4 NBr, respectively. Although there are no direct interactions between the aluminum and the heteroatoms in the heterocyclic pendants, electronic effects combined with the increased local concentration of CO2 around the active centers influences the catalytic activity in the coupling of CO2 with epoxides. In addition, PyrH /(nBu)4 NBr shows broad epoxide substrate scope and seven terminal epoxides and two internal epoxides undergo the designed reaction.

An approach to the design of a series of quinolinol-based indium complexes that can exhibit different optical properties is proposed. Mono-incorporated (Inq1 and InMeq1), bis-incorporated (InMeq2), and tris-incorporated (Inq3 and InMeq3) indium quinolinate complexes have been prepared. These complexes have also been characterized by X-ray crystallography. The photophysical properties of these complexes have also been examined by a combination of experimental and theoretical techniques. The indium complexes with a single quinolinol ligand (Inq1 and InMeq1) showed higher quantum efficiency than those with two or three quinolinate ligands; in particular, InMeq1 exhibited the highest quantum yield [ΦPL = 59% in poly(methyl methacrylate) film]. The insights into the nature of these findings were obtained by the sequential synthesis of the quinolinol-based indium luminophores and a detailed investigation of their structural stability.

A series of triphenylamine (TPA)-containing salen-Al assembly dyads, [salen(3- tBu-5-R)2Al(OC6H4- p-N(C6H5)2)] [salen = N, N'-bis(salicylidene)ethylenediamine; R = H (D1), tBu (D2), Ph (D3), OMe (D4), and NMe2 (D5)], were prepared in good yield (50-80%) and fully characterized by NMR spectroscopy and elemental analysis. Both the UV/vis absorption and photoluminescence (PL) spectra of D1-D4, except for D5, in a tetrahydrofuran solution exhibited dual patterns, which are assignable to the salen-Al-centered π-π* transition (low-energy region) and the TPA-centered π-π* transition (high-energy region). In particular, the emission spectra of the dyads displayed interesting dual-emissive patterns via a significant intramolecular energy transfer (IET) process between the salen-Al moiety and TPA group. Notably, this IET process was systematically tuned by varying the substituents and dominantly observed in the rigid state. More interestingly, compared to the salen-Al complexes (A1-A4) without the TPA group, D1-D4 exhibited enhanced quantum efficiencies. Time-dependent density functional theory calculations on the S1-optimized structures of D1-D5 further supported these experimental results by indicating the existence of independent transition states between the salen-Al moiety and TPA group in the assembly dyads. The present study reports the first example of salen-Al complexes bearing electron-rich TPA moieties.

Genome-wide mapping of lamin-B1-genome interactions has shown that gene-poor and transcriptionally inactive genomic regions are associated with the nuclear lamina. Numerous studies have suggested that lamins, the major structural components of the nuclear lamina, play a role in global chromatin organization and gene expression. How lamins could influence the 3D genome organization and transcription from the nuclear periphery has, however, remained unclear. Our recent studies showed that lamins differentially regulate distinct lamina-associated chromatin domains (LADs) at the nuclear periphery, which can in turn influence global 3D genome organization and gene expression. In this Extra View, we discuss how by using various genomics tools, it has become possible to reveal the functions of lamins in orchestrating 3D genome organization and gene expression. Abbreviations: 3D: three dimensional; LAD: lamina-associated chromatin domain; 3C: Chromosome Conformation Capture; TAD: topologically associated domain; HiLands: Histone and lamina landscape; NL: nuclear lamina; mESC: mouse embryonic stem cell; DamID: DNA adenine methyltransferase identification

The carborane (CB)-functionalized ligand was installed in a variety of MOFs through postsynthetic ligand exchange processes. This methodology is a general method for preparing o-CB-functionalized MOFs with known frameworks. Furthermore, the photoluminescence (PL) spectra revealed intriguing aggregation-induced emission (AIE) features following the systematic incorporation of o-CB functionalities into framework-type materials.

Amyotrophic lateral sclerosis (ALS) is a devastating neurodegenerative disorder that is characterized pathologically by the loss of motor neurons. Mutations in the TAF15 gene have been implicated in the pathogenesis of ALS. TATA-binding protein associated factor 15 (TAF15) accumulates as cytoplasmic aggregates in neuronal cells, the clearance of which may be a therapeutic strategy for ALS. However, the identification of a novel regulator for protection against a TAF15-induced proteinopathy and the exact pathogenic mechanism of TAF15-induced neurodegeneration remain to be elucidated. Here, we show that parkin directly binds to TAF15 and that parkin overexpression can suppress the defective phenotypes, including the life span and locomotive activity of a TAF15-induced proteinopathy. We also found that overexpression of parkin in neuronal cells leads to a reduction in TAF15 levels, because of the E3 ubiquitin ligase activity of parkin. Our study provides in vivo evidence supporting the use of parkin for neuroprotection in a TAF15-induced proteinopathy and offers new insights into the pathogenic mechanisms underlying TAF15-induced ALS.

A series of indium complexes with salen ligands bridged by aryl groups such as [Ar-{N CH(C6H2-3-tBu-5-R)}2]In-Me (Ar = 4,5-dimethyl-1,2-phenylene, 1,2-phenylene, and 3,4-naphthylene; R = H, Br, tBu, Me, OMe, NMe2, and NMe3+) were prepared and fully identified by NMR spectroscopy and elemental analysis. All indium complexes are highly stable in air and aqueous solutions. Among these complexes, the structurally characterized complexes [(4,5-dimethylphenylene)bis(3-tert-butyl-5-methylsalicylideneiminato)-κN,N′,O,O']methylindium(III) and [(2,3-naphthanlene)bis(3-tert-butyl-5-methylsalicylideneiminato)-κN,N′,O,O']methylindium(III) have slightly distorted square-pyramidal geometries around the central indium atoms. The UV/Vis absorption and emission spectra of all indium complexes exhibited significant intramolecular charge transfer (ICT) transitions assigned to the aryl salen-centered π-π* transitions, which displayed a gradual bathochromic shift, resulting from the electronic alteration of the substituent at the C5 position of phenoxy ring. Furthermore, the emission bands also gradually red-shifted as the electron-donating effect of bridging aryl groups decreased. In particular, the emission spectra of the indium complexes were observed in the visible region ranging from green (ca. 500 nm) to deep red (ca. 700 nm). The colors were obtained by manipulating the HOMO and LUMO energy levels, which was further supported by both electrochemical data and theoretical calculations.

Fabry disease is a lysosomal storage disease with an X-linked heritage caused by absent or decreased activity of lysosomal enzymes named alpha-galactosidase A (&alpha, gal A). Among the various manifestations of Fabry disease, Fabry nephropathy significantly affects patients&rsquo, morbidity and mortality. The cellular mechanisms of kidney damage have not been elusively described. Necroptosis is one of the programmed necrotic cell death pathways and is known to play many important roles in kidney injury. We investigated whether RIPK3, a protein phosphokinase with an important role in necroptosis, played a crucial role in the pathogenesis of Fabry nephropathy both in vitro and in vivo. The cell viability of podocytes decreased after lyso-Gb3 treatment in a dose-dependent manner, with increasing RIPK3 expression. Increased reactive oxygen species (ROS) generation after lyso-Gb3 treatment, which was alleviated by GSK&rsquo, 872 (a RIPK3 inhibitor), suggested a role of oxidative stress via a RIPK3-dependent pathway. Cytoskeleton rearrangement induced by lyso-Gb3 was normalized by the RIPK3 inhibitor. When mice were injected with lyso-Gb3, increased urine albuminuria, decreased podocyte counts in the glomeruli, and effaced foot processes were observed. Our results showed that lyso-Gb3 initiated albuminuria, a clinical manifestation of Fabry nephropathy, by podocyte loss and subsequent foot process effacement. These findings suggest a novel pathway in Fabry nephropathy.

An iridium-catalyzed C–H amidation for the syntheses of unsymmetrical urea was developed using carbamoyl azides (R(R′)N–C(O)-N3) as the nitrogen source. A combination of iridium and silver gave an ...

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The review includes scientific literatures published in the year of 2017 regarding the uses of biofilm and bioreactor to treat wastewater. Topics considered are: biofilm formation and factors that impact biofilm formation; extracellular polymeric substance from biofilms; biofilm consortia and quorum sensing; biofilm associated phage; biofilm reactors; and biofilm in bioelectrochemical systems.

A variety of metal-organic frameworks (MOFs) have been reported as efficient catalysts for CO2 fixation reactions, such as cycloaddition to cyclic carbonates. The permanent porosity of the frameworks and the Lewis acidity of the MOF metal sites have been considered as the major contributors to the catalytic activity in the cycloaddition of CO2. In this study, we have, instead, focused on the effects of the organic functional groups for effective catalytic ability. A total of eight different functionalized Zr-based MOFs were tested. It was revealed that the non-functionalized pristine UiO-66 MOF (UiO = University of Oslo) showed the best conversion at low temperature (77% at 50 °C), whereas the hydroxy-functionalized UiO-66-OH MOF displayed the best conversion at high temperature (91% at 140 °C). The Zr-MOF could be recycled up to four times without a significant decrease in the reactivity.

Novel scorpionate-type organocatalysts capable of effectively coupling carbon dioxide and epoxides under mild conditions to afford cyclic propylene carbonates were developed. On the basis of a combined experimental and computational study, a precise mechanistic proposal was developed and rational optimization strategies were identified. The epoxide ring-opening, which requires an iodide as a nucleophile, was enhanced by utilizing an immonium functionality that can form an ion pair with iodide, making the ring-opening process intramolecular. The CO2 activation and cyclic carbonate formation were catalyzed by the concerted action of two hydrogen bonds originating from two phenolic groups placed at the claw positions of the scorpionate scaffold. Electronic tuning of the hydrogen bond donors allowed to identify a new catalyst that can deliver >90% yield for a variety of epoxide substrates within 7 h at room temperature under a CO2 pressure of only 10 bar, and is highly recyclable.

Epitaxial Ge layers have been grown on Si (001) substrates by metalorganic chemical vapor deposition (MOCVD) using an isobutylgermane (IBuGe) metalorganic source. Low and high temperature two-step growth and post annealing techniques are employed to overcome the lattice mismatch problem between Ge and Si. It is demonstrated that high quality Ge epitaxial layers can be grown on Si (001) by using IBuGe with surface RMS roughness of 2 nm and an estimated threading dislocation density of 4.9 × 107 cm −2. Furthermore, single-junction Ge solar cells have been directly grown on Si substrates with an in situ MOCVD growth. The epitaxial Ge p-n junction structures are investigated with transmission electron microscopy and electrochemical C-V measurements. As a result, a power conversion efficiency of 1.69% was achieved for the Ge solar cell directly grown on Si substrate under AM1.5G condition.

New titanium complexes, TiLCl2(THF) and TiL2, containing the tridentate chiral Schiff-base ligand, L, prepared from the condensation reaction of 2,4-pentadione and (1R,2S)-(−)-1-aminoindanol, were synthesized and characterized by various analytical methods including X-ray crystallography. Ligand L acted as a dianionic tridentate ligand and, owing to a chiral center in the aminoindanol part, imparted chirality to its titanium complexes. The newly synthesized titanium complexes and previously reported analogous Ti complexes were used as catalysts in the cycloaddition of CO2 to propylene oxide as the first representatives of titanium complexes with tridentate Schiff base ligands to have been used for this purpose. These complexes provided high selectivity toward cyclic propylene carbonate (>99%) and showed considerable activities with TOF values up to 131 h−1 in comparison with the previously reported catalyst systems.

Postsynthetic treatments are well-known and important functionalization tools of metal-organic frameworks (MOFs). Herein, we have developed a practical and rapid postsynthetic ligand exchange (PSE) strategy using a defect-controlled MOF. An increase in the number of defects amounts to MOFs with enhanced rates of ligand exchange in a shorter time frame. An almost quantitative exchange was achieved by using the most defective MOFs. This PSE strategy is a straightforward method to introduce a functionality into MOFs including bulky or catalytically relevant moieties. Furthermore, some mechanistic insights into PSE were revealed, allowing for a sequential ligand exchange and the development of multifunctional MOFs with controlled ligand ratios.

A novel class of salen-Al/carbazole dyads (D1 and D2) was synthesized and fully identified. The emission spectra of the dyads presented intriguing dual-emission patterns via an intramolecular energy transfer (IET) state in solution. Furthermore, the IET feature of the dyads was clearly observed in the rigid state. Interestingly, the emission efficiency of the dyads was enhanced by the significant IET process from the carbazole group to the salen-Al moiety. Particularly, D1 exhibited a nearly three-fold enhanced luminescence efficiency compared to the corresponding mononuclear aluminum complexes (A1). Such an emission process of these guest-host systems was further supported by theoretical calculation.