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An acid-base bifunctional zeolitic imidazolate framework catalyst (ZIF8-A61-SO3H) with amine and sulfonic acid groups was successfully prepared through simple two step post-synthetic modification: preparation of amine-functionalized ZIF-8 with amine contents of 61% (ZIF8-A61) by the ligand exchange of 2-mIM with 3-amino-1,2,4-triazole (Atz), followed by the sulfonic acid functionalization by the ring-opening reaction of 1,3-propanesultone with –NH2 groups in ZIF8-A61. Amine-functionalized ZIF8-A materials with difference amine contents (15%, 34%, and 61%, respectively) were also prepared by controlling the synthesis time. All obtained ZIF catalysts evaluated as a heterogeneous catalyst for one-pot deacetalization-Knoevenagel condensation tandem reaction. Compared with ZIF-8 and amine-functionalized ZIF-8 catalysts, ZIF8-A61-SO3H catalyst showed good catalytic performance with 100% conversion of the reactant and 98% selectivity of the final Knoevenagel product. An enhanced catalytic activity can be attributed to the co-existence of site-isolated acid-base groups on the ZIF8-A61-SO3H catalyst in close proximity. The heterogeneous nature of the catalytic system was confirmed by a hot-filtering test and the catalyst also exhibited reusable in the five repeated cycles. A plausible catalytic mechanism of deacetalization-Knoevenagel condensation reaction over ZIF8-A61-SO3H was also proposed.

In this study, polyphenylene sulfide (PPS) was introduced in polyphenylene ether (PPE) blend to improve the processability of PPE and to secure the flame retardancy of the blend without deteriorating physical properties. Through the study of the binary blend of PPE/PPS, it was found that the shear thinning behavior and the external lubrication effect of PPS can improve the processability of PPE. Thermal analysis of the blend showed that the glass transition temperature of the PPS component decreases by the plasticization while that of the PPE component increases by the anti-plasticization effect. The modulus of the binary blend increased with the PPS content, and the tensile strength decreased but followed the additive rule. The change in tensile properties can be explained by the synergy effect of partial miscibility between PPE and PPS due to structural similarity, and non-isotropic morphology formation. Impact strength increased sharply in PPE60 due to the mechanical grafting effect by co-continuous phase formation. In the ternary blend with SEBS-MAH applied to PPE60, the impact strength steep increased at a content of 10 wt% or more due to the dramatic morphology change based on the compatibilization effect. Flame retardancy of V0 was also observed in all compositions where SEBS-MAH was applied within 20 phr.

ER stress and activation of the unfolded protein response in the periphery as well as the central nervous system have been linked to various metabolic abnormalities. Chemically lowering protein kinase R–like ER kinase (PERK) activity within the hypothalamus leads to decreased food intake and body weight. However, the cell populations required in this response remain undefined. In the current study, we investigated the effects of proopiomelanocortin-specific (POMC-specific) PERK deficiency on energy balance and glucose metabolism. Male mice deficient for PERK in POMC neurons exhibited improvements in energy balance on a high-fat diet, showing decreased food intake and body weight, independent of changes in glucose and insulin tolerances. The plant-based inhibitor of PERK, celastrol, increases leptin sensitivity, resulting in decreased food intake and body weight in a murine model of diet-induced obesity (DIO). Our data extend these observations by demonstrating that celastrol-induced improvements in leptin sensitivity and energy balance were attenuated in mice with PERK deficiency in POMC neurons. Altogether, these data suggest that POMC-specific PERK deficiency in male mice confers protection against DIO, possibly providing a new therapeutic target for the treatment of diabetes and metabolic syndrome.

A catalytic hydrolysis rate of nerve agents can be a significant issue because of their severe toxicity which can lead to severe damage to human life. Regarding the issue, much effort has been given rise to the development of the various design of Zr(IV)-based MOF catalysts so that high catalytic performance. However, we still have feasibility issues. To this end, we turned our attention to develop the method for facile, scalable, and efficient synthesis of Zr(IV)-based MOFs (UiO-66) with high-performance hydrolysis by imparting enriched active sites to the catalysts, as well as to examine its feasibility using the combination of UiO-66 with the organic bases including 4-ethylmorpholine (4-EM) and linear-/ branch-type polyethyleneimine (PEI). The modulated UiO-66 catalysts were synthesized by varying the total reaction concentration. The synthesized three different UiO-66 catalysts were characterized and then applied for hydrolysis rates of the methylparaoxon (MPO) nerve agent simulant. From these investigations, we found that the highest concentration led to the smallest particle size (ca. 100 nm) and highest defect density (1.8 per cluster), resulting in 3-times higher catalytic activity (0.548 s−1) in turnover frequency (TOF) relative to that of the uncontrolled UiO-66 (ca. 580 nm and 1.6 per cluster) (0.188 s−1) which is prepared by the reported procedure. In addition, the reaction process significantly influenced on the catalytic activity of UiO-66, in which the simple change of the reagent mixing method led to a ca. 182-times difference in the catalytic activity for MPO hydrolysis despite using the same reagents including catalysts and bases. Importantly, we found that the reaction process-dependent catalytic activity of UiO-66 can be significantly associated with the chelation of Zr(IV) Lewis acidic active sites by base materials of 4-EM and PEI (Lewis base). Furthermore, the solid-state catalytic system based on the polymer composite of UiO-66S/LPEI10k on the cotton fabric was also examined for MPO hydrolysis at various relative humidity and temperature conditions to create actual atmosphere conditions, which gave the possibility for actual military applications such as protective suits and equipment. In addition, we schematically demonstrated the loss of active sites on UiO-66 by chelation effects based on experimental and density functional theory (DFT)-derived computational simulation because it is highly correlated to the feasibility of Zr(IV)-based MOF catalysts for detoxification of nerve agents. In addition, we carefully propose a plausible reaction mechanism step on the nucleophilic attack by hydroxide group on the basis of the computational simulation.

Development of new hole-transport layer (HTL) materials for organic photovoltaic (OPV) applications is one crucial issue to mitigate such limitations of low power efficiency, processibility, and stability derived from poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) as a common HTL material. To this end, poly(3-hexylthiophene) (P3HT)-based diblock copolymers including the different ratios between polystyrene (PSty) or/and poly(neopentyl styrene sulfonate) (PNSS) as a second block segment were designed and then used for incorporating with single wall carbon nanotubes (SWCNTs) to form potentially self-dopable nanocomposites. The structure of fabricated P3HT-based diblock copolymer/SWCNT nanocomposites was examined by microscopic and spectroscopic characterizations, exhibiting a charge transfer behavior between P3HT and SWCNT, and growth of the P3HT crystalline phase along the SWCNT surface with a form of the conducting path. The acquired SWCNT nanocomposites exhibited good solubility and dispersion in various organic solvents including toluene, chlorobenzene, THF, chloroform, and DMF, which are good solvents for the PSty or/and PNSS neutral second block. The concept for the neutralized second block by protecting groups can prevent the poisoning ITO substrate by water contamination as shown in the conventional aqueous PEDOT-PSS solution. Notably, the PNSS constituent in the nanocomposite was merely acidified to give in-situ sulfonic acid groups in PSty by simple thermolysis process at 160 °C for 30 min after a solution process for fabrication of a thin film. The thermolysis step provided efficient doping of P3HT by PSS, in which the thiophene groups worked as Bronsted base are protonated by taking protons from sulfonic acid groups and then lead to a form of ionic bonds between cationic thiophene and anionic sulfonate groups. In addition, the formed ionic bonds in the nanocomposites led to an insoluble thin film, which has a good advantage for the further solvent process without substantial damages. The beneficial features of the conducting path along SWCNT and the efficient doping of P3HT by PSS in the acquired nanocomposites led to ca. 5-fold higher electrical conductivity (3.16 S cm−1) and similar work function (5.1 eV) in comparison to water contained commercial PEDOT:PSS (0.6 S cm−1 and 5.0 eV, respectively). As such, the rationally designed potentially self-dopable SWCNT nanocomposites can be one of the promising alternatives beyond the commercial PEDOT: PSS HTL material.

All organisms begin protein synthesis with methionine (Met). The resulting initiator Met of nascent proteins is irreversibly processed by Met aminopeptidases (MetAPs). N-terminal (Nt) Met excision (NME) is an evolutionarily conserved and essential process operating on up to two-thirds of proteins. However, the universal function of NME remains largely unknown. MetAPs have a well-known processing preference for Nt-Met with Ala, Ser, Gly, Thr, Cys, Pro, or Val at position 2, but using CHX-chase assays to assess protein degradation in yeast cells, as well as protein-binding and RT-qPCR assays, we demonstrate here that NME also occurs on nascent proteins bearing Met–Asn or Met–Gln at their N termini. We found that the NME at these termini exposes the tertiary destabilizing Nt residues (Asn or Gln) of the Arg/N-end rule pathway, which degrades proteins according to the composition of their Nt residues. We also identified a yeast DNA repair protein, MQ-Rad16, bearing a Met–Gln N terminus, as well as a human tropomyosin–receptor kinase–fused gene (TFG) protein, MN-TFG, bearing a Met–Asn N terminus as physiological, MetAP-processed Arg/N-end rule substrates. Furthermore, we show that the loss of the components of the Arg/N-end rule pathway substantially suppresses the growth defects of naa20Δ yeast cells lacking the catalytic subunit of NatB Nt acetylase at 37 °C. Collectively, the results of our study reveal that NME is a key upstream step for the creation of the Arg/N-end rule substrates bearing tertiary destabilizing residues in vivo.

Abstract Background Lanreotide is a long-acting somatostatin analogue with proven antitumour effects against well-differentiated (WD) gastroenteropancreatic-neuroendocrine tumours (GEP-NETs). However, there are no globally established prognostic factors associated with the efficacy of lanreotide as a treatment for GEP-NETs. We investigated the prognostic value of [68Ga]Ga-DOTA-TOC positron emission tomography (PET)/computed tomography (CT) somatostatin receptor imaging for patients with WD GEP-NETs treated with lanreotide. Methods In this retrospective study, we included 31 patients with unresectable or metastatic WD GEP-NETs who received lanreotide and underwent [68Ga]Ga-DOTA-TOC PET/CT before receiving lanreotide. We captured the following clinicopathological variables: Eastern Cooperative Oncology Group (ECOG) performance status, primary tumour site, NET World Health Organization grade, existence of carcinoid symptoms, previous surgery, previous chemotherapy, and hepatic tumour volume assessed by CT or magnetic resonance imaging (MRI). We also assessed the following [68Ga]Ga-DOTA-TOC PET/CT variables: Krenning score, tumour-to-liver ratio (TLR), maximum standardized uptake value (SUVmax), whole tumour volume (WTV), and total receptor expression (TRE, WTV multiplied by SUVmean). The associations between these markers and progression-free survival (PFS) with lanreotide were analysed. Results The mean age was 55.1 ± 15.5 years (range 16.0–81.0). The most common primary tumour site was the pancreas, followed by the stomach, and rectum. The median PFS interval with lanreotide was 14.4 months (range 1.3–34.9), with identified disease progression in 20 patients (64.5%). Among the [68Ga]Ga-DOTA-TOC PET/CT variables, TLR (< 8.1 vs. ≥ 8.1; p = 0.013), SUVmax (< 42.9 vs. ≥ 42.9; p = 0.037), and WTV (≥ 58.9 cm3 vs. < 58.9 cm3; p = 0.030) were significantly associated with PFS in the univariate analyses, but only TLR (hazard ratio 3.182 [95% CI 1.189–8.514], p = 0.021) remained an independent factor for PFS in the multivariate analysis. Conclusions Low TLR, determined via [68Ga]Ga-DOTA-TOC PET/CT, can be a factor of worse prognosis in patients with advanced WD GEP-NETs treated with lanreotide.

A series of UV-curable hybrid composite blends containing a carboxylic acid functionalized polyimidewith varying amounts of high molecular weight (~1 K) PEG-grafted ladder-structured polysilsesquioxanes copolymerized with methacryl groups were fabricated and their structural, thermal, mechanical, and surface properties characterized. At a composite weight ratio of polyimide above 50 wt.%, a stark shift from amorphous to crystalline polyethylene glycol (PEG) phases were observed, accompanied by a drastic increase in both surface moduli and brittleness index. Moreover, fabricated composites were shown to have a wide range water contact angle, 9.8&deg, &ndash, 73.8&deg, attesting to the tunable surface properties of these amphiphilic hybrid polymer composites. The enhanced mechanical properties, combined with the utility of tunable surface hydrophilicity allows for the possible use of these hybrid polymer composites to be utilized as photosensitive polyimide negative photoresists for a myriad of semiconductor patterning processes.

Perilipin 2 (PLIN2) is a major lipid droplet (LD)-associated protein that regulates intracellular lipid homeostasis and LD formation. Under lipid-deprived conditions, the LD-unbound (free) form of PLIN2 is eliminated in the cytosol by an as yet unknown ubiquitin (Ub)-proteasome pathway that is associated with the N-terminal or near N-terminal residues of the protein. Here, using HeLa, HEK293T, and HepG2 human cell lines, cycloheximide chase, in vivo ubiquitylation, split-Ub yeast two-hybrid, and chemical cross-linking–based reciprocal co-immunoprecipitation assays, we found that TEB4 (MARCH6), an E3 Ub ligase and recognition component of the Ac/N-end rule pathway, directly targets the N-terminal acetyl moiety of Nα-terminally acetylated PLIN2 for its polyubiquitylation and degradation by the 26S proteasome. We also show that the TEB4-mediated Ac/N-end rule pathway reduces intracellular LD accumulation by degrading PLIN2. Collectively, these findings identify PLIN2 as a substrate of the Ac/N-end rule pathway and indicate a previously unappreciated role of the Ac/N-end rule pathway in LD metabolism.

Carbon molecular sieve (CMS) membranes are a promising candidate for natural gas processing due to their peculiar pore structure-induced excellent separation performance. Formulating ultrathin, defect-free CMS hollow fiber membranes is, however, still challenging due to damage on porous sub-structures induced by thermal relaxation of polymer chains during pyrolysis. Herein, we report a new methodology enabling high separation performance and good plasticization resistance in CMS fiber membranes by uniform integration of double-stranded polysilsesquioxanes into the polyimide matrix. Our polyimide/ladder-structured polysilsesquioxane CMS fibers substantially enhanced CO2 permeance by as much as 546% compared to the precursor fiber analogues due to the thin molecular sieve selective layer. Also, poly(dimethylsiloxane) coating delayed physical aging, still showing a high CO2 permeance of 354 GPU with CO2/CH4 selectivity of 56 after 72 days of aging. Furthermore, they exhibited excellent plasticization resistance up to a CO2 partial pressure of 13.2 bar with CO2/CH4 separation factor of 74 for an equimolar CO2/CH4 feed mixture.

Lanreotide autogel is a long-acting somatostatin analogue with proven efficacy and safety in patients with well-differentiated (WD) gastroenteropancreatic-neuroendocrine tumors (GEP-NETs) in a prior randomized phase III trial (CLARINET). However, the CLARINET study only enrolled patients with Ki-67 index10%, and few patients of Asian ethnicity were included. We retrospectively analyzed the efficacy and safety of lanreotide in Korean patients with GEP-NETs in the daily practice setting. Between January 2015 and May 2018, 64 patients with metastatic WD GEP-NETs received lanreotide at Asan Medical Center, Seoul, Korea. Of them, 45 (70.3%) patients who received lanreotide as monotherapy were included in the current analysis. The most common primary tumor site was the pancreas (n = 22, 48.9%), followed by the rectum (10, 22.2%) and the small bowel (7, 15.6%). According to RECIST v1.1, a partial response was achieved in one patient (2.2%) and stable disease was achieved in 40 patients (88.9%). The median progression-free survival (PFS) was 16.4 months (95% confidence interval, 9.5-23.3 months). There were no differences in PFS according to the primary tumor site (p = 0.77). Hepatic tumor volume 25% and prior systemic therapy were significantly associated with poorer PFS in the multivariate analysis. Lanreotide is well-tolerated and effective for Korean patients with GEP-NETs in the daily practice setting.

Well-defined methacrylate based amphiphilic block copolymers (BCs) consisting of poly(methyl methacrylate) (PMMA) and poly(ethylene glycol) methacrylate (PPEGMA) were synthesized by atom transfer radical polymerization (ATRP) and used as additives in DMAc casting solution to fabricate poly(vinylidene fluoride) (PVDF) ultra-filtration (UF) membranes in non-solvent induced phase separation (NIPS) process, where the amphiphilic BC additives hydrophilically altered PVDF with PPEGMA block segment by strong interaction with the other PMMA block segment, which reduced water resistance to the PVDF polymer solution during phase separation. FT-IR and XPS studies showed carbonyl groups of BCs in the PVDF membranes, which were not changed even after IPA treatment, indicating that BCs in the membrane were very stable. Obtained PVDF membranes with BCs showed porous surface layer and finger-like pore structures with macrovoids on the sublayers, of which sizes were increased with the increase of BC contents, which were then compared to the pristine PVDF membranes and the PVDF membrane with corresponding other additives such as hydrophobic PMMA, hydrophilic PPEGMA, LiCl and BC/LiCl. Obtained PVDF membranes showed MWCO with 100 K PEO and the best water flux (140 LMH) was achieved in the PVDF membrane with BC/LiCl additive, which was almost 4 times higher than the pristine PVDF membrane. In addition, the PVDF membranes with BC and BC/LiCl additives improved the anti-fouling property for BSA protein, of which reversible fouling resistance ratio was ca. 7 times higher than that of the pristine PVDF membrane.

Depression causes mental and physical changes which affect quality of life. It is estimated to become the second most prevalent disease, but despite its commonness, the pathophysiology of depression remains unclear and medicine is not sufficiently protective. p-Coumaric acid (p-CA) is a dietary phenolic acid which has been proven to have antifungal, anti-HIV, anti-melanogenic, antioxidant and anti-inflammatory effects. Considering these effects, we investigated whether p-CA can prevent depressive symptoms by reducing inflammatory cytokines in animals injected with lipopolysaccharide (LPS). Changes in despair-related behaviors, inflammatory cytokines, neurotrophic factors and synaptic activity were measured. In these animals, p-CA improved despair-related behavioral symptoms induced by LPS in the forced swim test (FST), tail suspension test (TST) and sucrose splash test (SST). p-CA also prevented the increase of inflammatory cytokines in the hippocampus such as cycloxigenase-2 and tumor necrosis factor-α due to LPS. Similarly, it prevented the reduction of brain-derived neurotrophic factor (BDNF) by LPS. Electrophysiologically, p-CA blocked the reduction of long-term depression in LPS-treated organotypic tissue slices. In conclusion, p-CA prevented LPS-induced depressive symptoms in animals, as determined by behavioral, biochemical and electrophysiological measures. These findings suggest the potential use of p-CA as a preventive and therapeutic medicine for depression., Graphical Abstract

Two series of water-soluble metalloporphyrin-cored amphiphilic star block copolymers were synthesized by controlled radical polymerizations such as atom transfer radical polymerization (ATRP) and reversible addition fragmentation chain transfer (RAFT), which gave eight amphiphilic block copolymer arm chains consisting of poly(n-butyl acrylate-b-poly(ethylene glycol) methyl ether methacylate) (PnBA-b-PEGMEMA, Mn,GPC = 78,000, Mw/Mn = 1.2, 70 wt% of PPEGMEMA) and poly(styrene-b-2-dimethylamino ethyl acrylate) (PS-b-PDMAEA, Mn,GPC = 83,000, Mw/Mn = 1.2, 67 wt% of PDMAEA), yielding porphyrin(Pd)-(PnBA-b-PPEGMEMA)8 and porphyrin(Pd)-(PS-b-PDMAEA)8, respectively. Obtained metalloporphyrin polymer photocatalysts were homogeneously solubilized in water to apply to the removal of chlorophenols in water, and was distinguished from conventional water-insoluble small molecular metalloporphyrin photocatalysts. Notably, we found that the water-soluble star block copolymers with hydrophobic–hydrophilic core–shell structures more effectively decomposed the chlorophenol, 2,4,6-trichlorophenol (2,4,6-TCP), in water under visible light irradiation (k = 1.39 h−1, t1/2 = 0.5 h) in comparison to the corresponding water-soluble star homopolymer, because the hydrophobic core near the metalloporphyrin effectively captured and decomposed the hydrophobic chlorophenols in water.

Blends of poly(2,6-dimethyl-1,4-phenylene ether) (PPE) and poly(phenylene sulfide) (PPS) have shown potential as a new class of high-performance engineering plastics by reciprocally complementing the drawbacks of each component. However, improving their inherently poor toughness remains a challenge. Here, we report the design of PPE/PPS-based quaternary blends with increased impact strength without a significant loss of mechanical and flame-retardant properties. Introducing reactive polystyrene (RPS) with an oxazoline functional group as a compatibilizer improved the miscibility between the discrete PPE domain and continuous PPS matrix phases. The impact modifier styrene-ethylene-butadiene-styrene (SEBS) was compatibilized within the PPS matrix phase in the presence of RPS, enabling extraordinary impact strength. The tensile strength of the quaternary blends decreased slightly with increasing SEBS content, but the values exceeded the criteria for engineering plastic. All quaternary blends passed the V-0 grade in the UL-94 test because of the inherently excellent flame retardancy of the majority components.

A new method for enhancing condensable gas-induced plasticization resistance of aromatic polyimides (PIs) as well as increasing the flux of gas penetrants with negligible selectivity loss was demonstrated via a so-called bromination/debromination-induced thermal crosslinking. Our newly developed crosslinking approach essentially loosened the polymeric chain packing of 6FDA-Durene PIs by forming ethylene crosslinking bonds, while retaining its rigid PI backbone. As the degree of crosslinking increased, the permeability increased with trivial selectivity loss. Notably, the 75% bromination/debromination-induced crosslinked PI membranes drastically improved CO2 and C3H6 permeabilities by as much as 157% and 172%, respectively, compared to those of the pristine-PI analogs due to the debromination-induced free volume enhancement, while maintaining good selectivity due to the crosslinked ethylene bridges. As a result, outstanding separation performances for CO2/N2, CO2/CH4 and C3H6/C3H8 gas pairs have been obtained, and most importantly, a high tolerance to CO2- or C3H6-induced plasticization was observed up to CO2 or C3H6 pressure of 24 and 10 atm, respectively. Our current crosslinking approach can be extended to industrially attractive hollow fiber forms of various aromatic PIs for high plasticization resistance as well as high flux.

Pourable and room temperature flowable ladder-structured polysilsesquioxanes were synthesized and applied as functional optical hard coatings. Organic functional group type (propyl, hexyl, octyl, dodecyl) and their copolymer composition with UV-curable methylacryloxypropyl group were selected as to control both pre-cured viscosity and final mechanical properties independent of molecular weight. Ladder-structured polysilsesquioxanes with longer alkyl side chains exhibited higher fluidity and flexibility while maintaining its optical property and mechanical strength. The solvent-free processability of our synthesized materials along with their superior optical and mechanical properties over commercial solvent-based hard coatings suggest the high value of our hybrid materials for the coatings industry.

Increases in human life expectancy have led to increases in the prevalence of senile dementia and neurodegenerative diseases. This is a major problem because there are no curative treatments for these diseases, and patients with unmanaged cognitive and neurodegenerative symptoms experience many social problems. Sulforaphane is a type of organosulfur compound known as an isothiocyanate. It is derived from glucoraphanin, a compound found in cruciferous vegetables such as broccoli, brussels sprouts, and cabbages, via an enzymatic reaction that is triggered by plant damage (e.g., chewing). Sulforaphane exhibits activity against cancer, inflammation, depression, and severe cardiac diseases. It can also alleviate oxidative stress and neural dysfunction in the brain. However, there is insufficient knowledge about the electrophysiological and behavioral basis of the effects of sulforaphane on learning and memory. Therefore, we evaluated whether acute sulforaphane administration affected long-term potentiation (LTP) in organotypic cultured rat hippocampal tissues. We also measured the effect of sulforaphane on the performance of three behavioral tests, the Y-maze test, the passive avoidance test, and the Morris water maze, which assess short-term memory, avoidance memory, and short and long-term spatial memory, respectively. We found that sulforaphane increased the total field excitatory postsynaptic potential (fEPSP) in a dose-dependent manner after high frequency stimulation and attenuated scopolamine-induced interference of the fEPSP in the hippocampal CA1 area. Sulforaphane also restored cognitive function and inhibited memory impairment as indicated by the alleviation of the negative neurological effects of scopolamine, i.e, a lowered ratio of spontaneous alternation in the Y-maze, a reduced step-through latency in the passive avoidance test, and an increased navigation time in the Morris water maze. These results indicate that sulforaphane can effectively prevent the attenuation of LTP and cognitive abilities induced by cholinergic and muscarinic receptor blockade. Further research is warranted to explore the potential therapeutic and prophylactic utility of sulforaphane for improving learning and memory, especially in those suffering from neurodegenerative disorders.

Neuroinflammation plays a critical role in the pathogenesis of degenerative brain diseases such as Alzheimer's disease and Parkinson's disease. Microglia are the major components of the brain immune system that regulate inflammatory processes. Activated microglia release pro-inflammatory factors and cytokines, resulting in neuronal cell death. We focused on inhibiting the activation of microglia from a stimulus as a strategy to search for neuroprotective drugs. Rhei Undulati Rhizoma (RUR) is traditionally used to treat various inflammatory disorders. In this study, we investigated whether RUR modulates inflammatory processes in lipopolysaccharide (LPS)-stimulated BV2 microglia cells and the mouse brain. RUR exerted anti-neuroinflammatory effects by inhibiting the production of nitric oxide and reactive oxygen species induced by LPS via the downregulation of transcription factors such as inducible nitric oxide synthase and cyclooxygenase-2 (COX-2) without causing cytotoxicity. RUR also regulated mitogen-activated protein kinase pathway by inhibiting phosphorylation of p38 and c-Jun N-terminal kinases and translocation of nuclear factor kappa B. Moreover, RUR attenuated LPS-induced glial activation and COX-2 expression in the substantia nigra and hippocampus of the mouse brain. These results indicate that RUR is a potential candidate to treat neurodegenerative diseases by regulating neuroinflammation.

In this paper, the effects of hydrogen (H 2 ) plasma treatment on the molybdenum (Mo)-doped indium oxide (InO) thin film that was formed on glass using the polymer-assisted deposition (PAD) process were investigated. The sheet resistance for the sample treated at the ICP power of 15 W was quenched to 167 Ω/sq. from the 680 Ω/sq. for the as-deposited sample. Compared with the as-deposited sample, both the mobility and the concentration of the sample treated at the 15 W ICP power were also increased simultaneously, resulting in an increased conductivity. From these results, it was concluded that the H 2 plasma treatment is an efficient method for the enhancement of the electrical property, as well as to remove nano-sized cracks on the surface of the PAD-Mo-doped InO without a deterioration the optical transmittance.

Most inorganic nucleating agents for poly(ethylene terephthalate) (PET) have limited nucleating ability due to poor compatibility with PET. Polyhedral oligomeric silsesquioxanes (POSS) is a type of cage-shaped organic/inorganic hybrid nanoparticles with three different particle sizes: octameric (T8), decameric (T10), and dodecameric (T12). POSS is considered as a promising nucleating agent for PET because the inorganic moieties contribute to high thermal stability and nucleation and the organic moieties can be tethered to PET chains. In contrast to T8 POSS, the nucleation ability of T12 POSS for PET has been poorly reported. In this study, our newly synthesized aminopropyl functionalized T12 POSS (A-POSS) is proposed as a potential nucleating agent for PET. The amine group of A-POSS is able to be chemically conjugated to PET chains, thereby giving a more homogeneous dispersion of T12 POSS in PET than non-functional T12 Phenyl POSS (N-POSS). Its PET composites gave a ∼1.2 fold higher crystallization temperature and ∼2.7 fold higher shear-induced crystallization rate over pristine PET. Such nucleating effects for PET is more effective than those of non-functional T12 POSS and the more widely studied T8 POSS. This strategy is potentially beneficial for the high-shear melt processes of PET such as spinning and film extrusion.

Heteroleptic ruthenium-complexed ladder-like structured polysilsesquioxane (LPSQ-Ru) was synthesized by post coordination reaction of bidentate ligand side chains in LPSQ with reactive Ru(II) complexes, which was well characterized by 1H and 29Si NMR, FT-IR, and spectroscopic techniques. The photophysical properties of LPSQ-Ru were examined by UV and PL analyses in both solution and solid states, comparing to analogous polymers of ruthenium-complexed polystyrene (PS-Ru). Obtained absorptions of LPSQ-Ru and PS-Ru were broadened ranging from 390-490 nm regardless of the states. However, LPSQ-Ru exhibited higher and shaper PL emission spectrum in comparison to that of PS-Ru, particularly in the solid state, because Ru-complexes in LPSQ were much effectively isolated, preventing their aggregations due to the rigid double strained siloxane backbone. This extinguished photophysical property in LPSQ-Ru kept after intensive thermal treatment at 250 °C for 90 min, which was not achieved in PS-Ru (~5-fold decrease). These differences originated from the backbone structures were also appeared in electrochemical properties in the solid states.

A multifunctional crosslinkable and ionic-group functionalized ladder-like polysilsesquioxane was synthesized and utilized for the fabrication of hybrid ionogels for lithium ion batteries. The ionic-group functionalized ladder-like polysilsesquioxane combined the synergistic effects of hybrid materials in improving the thermal stability of conventional battery electrolytes, whilst maintain facile solution processability and chemically crosslinkable function in ionic conducting ionic liquid electrolyte media. Fabricated iongel electrolytes exhibiting exceptional thermal stability, mechanical properties, high ionic conductivity, and electrochemical stability. Lithium ion batteries fabricated with the hybrid ionic ladder-like polysilsesquioxane ionogels exhibited initial discharge capacities on par with neat liquid electrolytes, good rate performance, as well as stable cyclability and excellent Coulombic efficiency.

Increasing the rating of the HVDC cable causes an inevitable increase in the heat generated inside cable. Thus, it is necessary to improve the thermal conductivity of the Cross-linked polyethylene (XLPE) insulation material used in the extruded cable for effective thermal management. Also, several methods have been pro-posed so far to increase the thermal conductivity of XLPE. However, the influence of the filler addition on the thermal conductivity has been mainly studied experimentally so far. Therefore, numerical analysis was performed to investigate the effect of filler size and its content on thermal conductivity of XLPE. In the modelling of XLPE composite for numerical analysis spherical Al2O3 particles with a radius of 25, 50, 100 and 200 nm were considered. Additionally, filler contents were considered with up to 20 wt%. Numerical analysis of XLPE composite model showed that the effective thermal conductivity increased with the smaller filler size. Also, as the content of filler increased, the effective thermal conductivity increased. A coupled electro-thermal model considering the previously derived thermal conductivities was used to investigate the influence of the thermal conductivity of XLPE on temperature and electric field distribution. From the simulation results it can be concluded that, higher thermal conductivity of XLPE can reduce the thermal and electrical stress of the cable. Therefore, it is considered that the smaller the size of the filler added to the insulation or the larger the content of the filler, the thermal and electrical stress in the cable can be reduced.

Spontaneous abortion represents a common form of embryonic loss caused by early pregnancy failure. In the present study, we investigated the prophylactic effects of bee venom phospholipase A2 (bvPLA2), a regulatory T cell (Treg) inducer, on a lipopolysaccharide (LPS)-induced abortion mouse model. Fetal loss, including viable implants, the fetal resorption rate, and the fetal weight, were measured after LPS and bvPLA2 treatment. The levels of serum and tissue inflammatory cytokines were determined. To investigate the involvement of the Treg population in bvPLA2-mediated protection against fetal loss, the effect of Treg depletion was evaluated following bvPLA2 and LPS treatment. The results clearly revealed that bvPLA2 can prevent fetal loss accompanied by growth restriction in the remaining viable fetus. When the LPS-induced abortion mice were treated with bvPLA2, Treg cells were significantly increased compared with those in the non-pregnant, PBS, and LPS groups. After LPS injection, the levels of proinflammatory cytokines were markedly increased compared with those in the PBS mouse group, while bvPLA2 treatment showed significantly decreased TNF-&alpha, and IFN-&gamma, expression compared with that in the LPS group. The protective effects of bvPLA2 treatment were not detected in Treg-depleted abortion-prone mice. These findings suggest that bvPLA2 has protective effects in the LPS-induced abortion mouse model by regulating Treg populations.

Membrane-based separation technology is attractive for upgrading small-scale natural gas due to the benefits of the pressure-driven process with a small footprint. Very few carbon molecular sieve (CMS) membranes with high N2/CH4 separation efficiency have been reported since the relationship between CMS structure and separation performance has not been fully elucidated. Here, we report the significance of controlling the effective pore size in our newly developed hybrid CMS matrix for enhanced N2/CH4 selectivity based on experimental characterizations and density functional theory (DFT) calculations. A new class of CMS membranes with an excellent N2/CH4 selectivity is demonstrated by pyrolysis of a homogeneous, hydrogen-bonded blend of BTDA-Durene:DABA (3:2) polyimide and ladder-structured poly(phenyl-co-3-(2-aminoethylamino)propyl)silsesquioxane (LPDA64). DFT calculations suggest that electron accumulation at SiOx phases of hybrid CMS membranes strongly hinders the diffusion of CH4 compared to N2 due to a larger electron overlap, resulting in a smaller effective pore size. Moreover, elevating the pyrolysis temperatures enhanced the N2/CH4 solubility selectivity due to the strong repulsive interaction between the newly formed ultramicropores with CH4. As a result, the hybrid CMS membranes showed an excellent single gas and N2/CH4/C2H6 (20/76/4) mixed gas N2/CH4 selectivity (28 and 16, respectively).

A new methodology for fabrication of inorganic–organic hybrid ionogels and scaffolds is developed through facile cross-linking and solution extraction of a newly developed ionic polyhedral oligomeric silsesquioxane with inorganic core. Through design of various cationic tertiary amines, as well as cross-linkable functional groups on each arm of the inorganic core, high-performance ionogels are fabricated with excellent electrochemical stability and unique ion conduction behavior, giving superior lithium ion battery performance. Moreover, through solvent extraction of the liquid components, hybrid scaffolds with well-defined, interconnected mesopores are utilized as heterogeneous catalysts for the CO2-catalyzed cycloaddition of epoxides. Excellent catalytic performance, as well as highly efficient recyclability are observed when compared to other previous literature materials.

An in-depth examination of the self-healing properties of both dienophile and diene functionalized ladder-like structured polysilsesquioxane copolymers and terpolymers was investigated. Through functionalization of both diene and dienophile on the double-stranded siloxane backbone with ternary n-alkyl functional groups acting as chain mobility control, the effect of chain mobility and chemical structure on self-healing and mechanical properties were elucidated. All of the single component self-healing hybrid materials exhibited fast healing times (∼5 min), and their de-crosslinked adducts exhibited exceptional retention of solubility in common organic solvents for good reusability, all while having inherent high thermal stability and optical transparency.

A series of trimethylsilyl-capped hybrid ladder-like polysilsesquioxane (LPSQ-TMS) derivatives were synthesized comprising an inorganic backbone functionalized with various organic side moieties and compositional ratios with application towards gate dielectrics or surface modifying materials. The surface energy (γ) and roughness (Rq) values of the LPSQ-TMS coated SiO2 dielectrics were considerably affected by the side moieties of the polymer series; methyl, n-propyl, phenyl (P), naphthyl (N), methacryloxypropyl (MA), and fluorooctyl moieties. The γ values varied from 17.0 to 42.0 mJ m−2, while the Rq values also ranged from 0.34 to 1.10 nm. On polymer-treated SiO2 dielectrics possessing smooth and semiconductor-compatible surface properties, pentacene developed terrace-like crystallites formed through layer-by-island growth modes, a stark contrast to the three-dimensionally grown crystal islands formed on rough or extremely hydrophobic surfaces, which led to unfavorable conduction pathways. Depending on the order of conjugation and interconnections between the pentacene domains, the average mobility (μFET) values of the resulting 50 nm thick pentacene organic field-effect transistors were varied by two orders of magnitude and reached 0.8 cm2 V−1 s−1, specifically, for both the P- and MA-substituted LPSQ-TMS treated SiO2 dielectrics (γ = 37.0 mJ m−2 and Rq = 0.40 nm). Moreover, we were able to demonstrate that a thermally cured 500 nm thick LPSQ-TMS layer on an Au gate-patterned flexible polyimide substrate could yield pentacene OFETs with μFET values as high as 0.60 cm2 V−1 s−1, comparable to that of the LPSQ-TMS treated SiO2 system. Also, the proper introduction of organic substituents to LPSQ improved the gate-bias stress stability for high performance OFETs.

An investigation into the hydrolysis kinetics of an aqueous base-catalyzed sol-gel reaction yielding ladder-like polysilsesquioxanes was studied using NMR. Under various variables of monomer concentration, water concentration, solvent type, and monomer type, the various effects on molecular weight and degree of condensation were elucidated. Moreover, the various rate orders and rate constants were calculated and compared with previous reports of the hydrolysis of organosilane precursors. Through this study we were able to ascertain the optimal conditions of hydrolysis-polycondensation for obtaining highly condensed, high molecular weight ladder-like polysilsesquioxanes.

Boron containing ionogels were fabricated through chemical crosslinking of boron allyloxide with polyethylene glycol dimethacrylate in an ionic liquid electrolyte solution to obtain mechanically robust gels. Because of the relatively small concentration of crosslinking agent required to fully solidify the ionic liquid electrolyte, good characters of high ionic conductivity, high thermal stability, and good electrochemical stability were observed. A spectroscopic investigation of the boronic ionogels revealed that the lithium mobility was noticeably enhanced compared with ionogels fabricated without the boronic crosslinker, leading to promising Li-ion battery performance at elevated temperatures.

In this study, the effect of novel BMP-2-loaded photo-cured hydrogels on in vitro and in vivo osteogenesis were explored. The well-defined HA-heparin hydrogel was prepared by a photopolymerization of aminoethyl methacrylate (AEMA) grafted hyaluronic acid (HA) and AEMA-grafted heparin. Subsequently, the resulting hydrogels contained BMP-2 at different concentrations. First, a series of BMP-2-loaded hydrogels were characterized to determine their mechanical properties and release profiles. The results from rheology, swelling ratio, and release kinetics suggest that BMP-2 contained HA-g-Hhep gel (B/HA-g-Hhep gel) had sustained release during 4 weeks with minimal initial burst. Furthermore, the released BMP-2 maintained its biological activity. MTT and live/dead assays showed that the B/HA-g-Hhep gel had good biocompatibility to be used as a scaffold for bone regeneration. In vivo studies of B/HA-g-Hhep gel exhibited significantly enhanced osteogenesis, compared with other types of HA-heparin hydrogels. These excellent results indicated that B/HA-g-Hhep gel has a great potential for a controlled release of growth factor, leading to a good bone regeneration. Open image in new window

Korean red pine (Pinus densiflora Sieb. et Zucc.) bark is a by-product of the wood industry and contains a high level of antioxidative phenolics including flavonoids, which have a variety of beneficial health effects. This study aimed to investigate the antihypertensive effects of P. densiflora bark extract (Korean red pine bark extract, KRPBE) in spontaneously hypertensive rats (SHRs). A group of Wistar-Kyoto rats (WKRs) as a normotensive group was orally fed tap water. Four groups of SHRs were orally fed tap water, captopril (a positive control), 50 mg/kg/day of KRPBE, and 150 mg/kg/day of KRPBE, respectively. Blood pressure of rats was measured once every week for seven weeks of oral administration. After seven weeks, the lungs, kidneys, and serum were collected from rats, then angiotensin-converting enzyme (ACE) activity, angiotensin II content, and malondialdehyde (MDA) content were determined. Blood pressure of the captopril- and KRPBE-treated groups was significantly lower than that of the SHR control group. The ACE activity, angiotensin II content, and MDA content significantly decreased in the captopril- and KRPBE-treated groups than those in the SHR control group. High-performance liquid chromatography analysis revealed six phenolics in KRPBE: protocatechuic acid, procyanidin B1, catechin, caffeic acid, vanillin, and taxifolin. KRPBE, which contains plenty of antioxidative phenolics, has antihypertensive effects partly due to reduction of ACE activity and angiotensin II content, and its antioxidative effect.

A series of well-defined hard–soft–hard triblock copolymers were synthesized by Ru-based atom transfer radical polymerization (ATRP) (MWD < 1.26) in order to examine their electromechanical properties under electric fields. The obtained methacrylate based triblock copolymers consisted of poly(dodecyl methacrylate) (PDMA) soft middle block segments and three different hard block segments with poly(methyl methacrylate) (PMMA), poly(tert-butyl methacrylate) (PtBMA), and their random copolymers (PMTDTMTs). Polar acidified triblock copolymers were also prepared by deprotecting tert-butyl groups in tBMA-incorporating hard block segments through simple thermal treatment at 200 °C for 120 min, which in situ gave poly(methacrylic acid) (PMAA) and its random copolymers (PAMDMA) in the hard block segments. SAXS and AFM studies indicated that these triblock copolymers showed well-organized phase separations with different domain sizes, which were strongly dependent on the amount of bulky PtBMA or polar PMAA in the hard block segments. In addition, these triblock copolymers had a variety of morphologies affecting their mechanical (elastic modulus) and electrical (dielectric constant) properties, leading to a tuning of their electromechanical properties. The transverse strains of these triblock random copolymers as a function of an applied electric field indicated that the PTMDMT series possessed the best electromechanical properties, exhibiting an 11-fold enhancement relative to the corresponding acidified polymer PAMDMA at 50 Vpp μm−1 due to a dramatic decrease of the elastic modulus from 4.04 to 0.05 MPa in spite of an increase of the dielectric constant from 3.6 to 5.1. In situ SAXS analysis under an electric field showed that these bulk strains originated from nano-structured microdomain changes.

We present a new polyethylene glycol-functionalized polysilsesquioxane, a ladder-like structured poly(poly(ethylene oxide)-co-methacryloxypropyl)silsesquioxane) (PEO-SQ) hybrid-type polymer gelator to fabricate hybrid ionogel electrolytes for lithium ion capacitors. The organic-inorganic hybrid polymer gelator contains not only an inorganic ladder-like polysilsesquioxane backbone for the thermal and electrochemical stability, but also dual organic pendant groups consisting of free-dangling PEO chains and unsaturated methacryloxypropyl groups for enhanced lithium ion dissociation and thermal curing function, respectively. The successful crosslinking of 1 M LiTFSI in N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (BMPTFSI) ionic liquid with only a small amount of PEO-SQ hybrid crosslinker (5 wt%) gave non-leaking ionogels with high thermal stability (⿼400 °C), large ionic conductivities, and excellent lithium ion capacitor C-rate performance and cyclability, comparable to those of neat ionic liquid electrolyte and superior over conventional organic ionogels fabricated with organic crosslinkers without PEO-moeities.

Poly(vinylidenefluoride-co-trifluoroethylene) (PVDF-TrFE)/SWCNT nanocomposites with ultra-low percolation threshold were prepared by interfacial control using a block copolymer comapatibilizer. For this, a well-defined block copolymer of poly(3-hexylthiophene) (P3HT) and poly(methyl methacrylate) (PMMA) (P3HT-b-PMMA) was synthesized by combination of GRIM and ATRP (Mn = 24 K, Mw/Mn = 1.25), where the P3HT block segment wrapped the SWCNTs by π–π interaction and the resulting PMMA block segment dangled from the SWCNTs, which gave de-bundled SWCNTs without any aggregations for over 5 months in most common organic solvents for PMMA. The block copolymer coated SWCNT (TMCNT) was then mixed with PVDF-TrFE to prepare PVDF-TrFE/SWCNT nanocomposites (PVT-TMCNT), which enabled excellent dispersion of SWCNT in a PVDF-TrFE matrix without aggregation due to the miscibility of the PMMA on TMCNT and PVDF-TrFE. Obtained PVT-TMCNT showed large enhancements of the electrical conductivity and the dielectric constant with ultra-low percolation threshold (fc = 0.07 wt.%) due to excellent interfacial control by the block copolymer comapatibilizer between SWCNT and PVDF-TrFE. Improved ferroelectric properties of PVT-TMCNT were also observed by an increase of field-induced polarization response, which was almost over 10-times higher than for neat PVDF-TrFE.

Compatible hybrid composites (PVLPMA) comprising of poly(vinylidene fluoride) (PVDF) and UV-curable ladder-like polysilsesquioxane (LPMASQ) were investigated for maximizing synergetic effects in various properties. The PVDF fluoropolymer was found to be well-incorporated with the LPMASQ inorganic filler because of good hydrogen-bonding, and the compatibility rigorously investigated by FT-IR, DSC, and WAXS studies. In addition, the crosslinkable function arising from the methacryl-group of the LPMASQ inorganic filler with the aid of the radical source was evaluated from the analysis of various properties. After UV-crosslinking, PVLPMA hybrid composites showcased enhanced mechanical properties such as elastic modulus, surface modulus, and surface hardness with accordance to the increasing the LPMASQ quantity. In addition, hydrophobicity was observed through the increase in the water contact angle up to 115°, a value much larger than that of neat PVDF and cured LPMASQ. Furthermore, the enhanced electrical stability of PVLPMA hybrid composites was obtained through examination of dielectric properties and breakdown strength in comparison to neat PVDF. These PVDF-LPMASQ organic-inorganic compatible hybrid composites with enhanced properties arising from the good compatibility and synergetic effects can be applicable in the various fields supplanting neat PVDF.

Through fine-tuning of the myriad of reaction conditions for an aqueous base-catalyzed hydrolysis–polycondensation reaction, a facile synthesis of structurally controlled polyphenylsilsesquioxanes was developed. Mechanism and kinetic studies indicated that the condensation reaction proceeded through a T1 structured dimer, which was quantitatively and in situ formed through mild hydrolysis of a phenyltrimethoxysilane (PTMS) monomer, to give either the cage-structured polyhedral oligomeric silsesquioxanes (POSS) or the corresponding ladderlike silsesquioxane (LPSQ) with excellent yields. Ladderlike and POSS materials were selectively achieved at higher and lower initial concentrations of PTMS, respectively, and an in-depth spectroscopic analysis of both compounds clearly revealed their structural differences with different molecular weights.

For the insulation design of dc high-temperature superconducting (HTS) equipment, dc electric field analysis should be performed. As the dc electric field distribution is mainly determined by the relative electrical conductivities of the various insulating materials used, the conductivities of these materials should be precisely measured. In particular, in cryogenic environment, the measurement of electrical conductivity could not be easily conducted due to the difficulty of measuring extremely low leakage current. In this paper, investigation on the measurement of volume and surface electrical conductivity of various cryogenic insulants, including polypropylene laminated paper (PPLP), Kraft, and glass fiber reinforced plastic (GFRP), was carried out. For the measurement of volume electrical conductivity in LN2, the infiltration of LN 2 into the specimen should be considered in order to avoid inaccurate measuring data. Thus, in order to increase the reliability for volume electrical conductivity, the PPLP specimen deposited by copper was adopted, and the comparison between ordinary PPLP and PPLP with copper deposition was made. As a result, it was suggested that the copper deposition could be a valid method to prevent the infiltration of LN 2 when the electrical conductivity of thin paper was measured. Consequently, volume and surface electrical conductivity values of PPLP, Kraft, and GFRP have been measured and summarized.

In bacteria, nascent proteins bear the pretranslationally generated N-terminal (Nt) formyl-methionine (fMet) residue. Nt-fMet of bacterial proteins is a degradation signal, termed fMet/N-degron. By contrast, proteins synthesized by cytosolic ribosomes of eukaryotes were presumed to bear unformylated Nt-Met. Here we found that the yeast formyltransferase Fmt1, although imported into mitochondria, could also produce Nt-formylated proteins in the cytosol. Nt-formylated proteins were strongly up-regulated in stationary phase or upon starvation for specific amino acids. This up-regulation strictly required the Gcn2 kinase, which phosphorylates Fmt1 and mediates its retention in the cytosol. We also found that the Nt-fMet residues of Nt-formylated proteins act as fMet/N-degrons and identified the Psh1 ubiquitin ligase as the recognition component of the eukaryotic fMet/N-end rule pathway, which destroys Nt-formylated proteins.

In oriental medicine, curcumin is used to treat inflammatory diseases, and its anti-inflammatory effect has been reported in recent research. In this feasibility study, the hepatoprotective effect of curcumin was investigated using a rat liver cirrhosis model, which was induced with dimethylnitrosamine (DMN). Together with biochemical analysis, we used a magnetic resonance-based electrical conductivity imaging method to evaluate tissue conditions associated with a protective effect. The effects of curcumin treatment and lactulose treatment on liver cirrhosis were compared. Electrical conductivity images indicated that liver tissues damaged by DMN showed decreased conductivity compared with normal liver tissues. In contrast, cirrhotic liver tissues treated with curcumin or lactulose showed increased conductivity than tissues in the DMN-only group. Specifically, conductivity of cirrhotic liver after curcumin treatment was similar to that of normal liver tissues. Histological staining and immunohistochemical examination showed significant levels of attenuated fibrosis and decreased inflammatory response after both curcumin and lactulose treatments compared with damaged liver tissues by DMN. The conductivity imaging and biochemical examination results indicate that curcumin’s anti-inflammatory effect can prevent the progression of irreversible liver dysfunction.

A series of organic–inorganic hybrid spin-on-glass polymethylsilsesquioxanes were synthesized utilizing a cyclic siloxane precursor, 1,3,5,7-tetramethyl-1,3,5,7-tetrahydroxyl cyclosiloxane (MT4-OH), copolymerized with methyltriethoxysilane (MTES) at various comonomer ratios. By selectively introducing this 2-D cyclic crosslinker, we were able to obtain spin-on-glass hybrimers with low dielectric constant (2.5–2.7), high nanoindentation modulus (5–10.5 GPa), with high thermal stability (>700 °C) without the use of porogens or additives. The use of the cyclic monomer MT4-OH greatly increased the mechanical properties, which allowed for impeccable reliability of a variety of patterns obtained through etching and chemical mechanical planarization processes, while maintaining optimal gap-filling properties. Due to the superior dielectric, mechanical, and integrated processing of these materials, these hybrids derived from MT4-OH may be utilized as next generation spin-on-glass low-dielectric constant materials.

A series of PEO-functionalized, ladder-like structured polysilsesquioxane copolymers were synthesized and utilized for the fabrication of PEGylated hybrid ionogels through chemical crosslinking of the ionic liquid, 1 M LiTFSI in N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide. Through systematic variance of the copolymer concentration of methacryloxypropyl- and PEG groups, we were able to demonstrate enhanced ionic conductivity and lithium ion dissociation as the PEO content increased. Through an in-depth spectroscopic investigation of the ion conduction behavior of these PEGylated hybrid ionogels and comparison with hybrid ionogels without PEG groups, we were able to demonstrate how the enhancement in lithium ion battery performance for PEGylated hybrid iongels could be achieved at identical crosslinker concentrations.