Sub‐5 nm Dendrimer Directed Self‐Assembly with Large‐Area Uniform Alignment by Graphoepitaxy

Directed self‐assembly (DSA) using soft materials is an important method for producing periodic nanostructures because it is a simple, cost‐effective process for fabricating high‐resolution patterns. Most of the previously reported DSA methods exploit the self‐assembly of block copolymers, which generates a wide range of nanostructures. In this study, cylinders obtained from supramolecular dendrimer films with a high resolution (<5 nm) exhibit planar ordering over a macroscopic area via guiding topographical templates with a high aspect ratio (>10) and high spatial resolution (≈20 nm) of guiding line patterns. Theoretical and experimental studies reveal that this property is related to geometrical anchoring on the meniscus region and physical surface anchoring on the sidewall. Furthermore, this DSA of dendrimer cylinders is demonstrated by the non‐regular geometry of the patterned template. The macroscopic planar alignment of the dendrimer nanostructure reveals an extremely small feature size (≈4.7 nm) on the wafer scale (>16 cm²). This study is expected to open avenues for the production of a large family of supramolecular dendrimers with different phases and feature dimensions oriented by the DSA approach.     

Approaching Ultrastable High‐Rate Li–S Batteries through Hierarchically Porous Titanium Nitride Synthesized by Multiscale Phase Separation

Porous architectures are important in determining the performance of lithium–sulfur batteries (LSBs). Among them, multiscale porous architecutures are highly desired to tackle the limitations of single‐sized porous architectures, and to combine the advantages of different pore scales. Although a few carbonaceous materials with multiscale porosity are employed in LSBs, their nonpolar surface properties cause the severe dissolution of lithium polysulfides (LiPSs). In this context, multiscale porous structure design of noncarbonaceous materials is highly required, but has not been exploited in LSBs yet because of the absence of a facile method to control the multiscale porous inorganic materials. Here, a hierarchically porous titanium nitride (h‐TiN) is reported as a multifunctional sulfur host, integrating the advantages of multiscale porous architectures with intrinsic surface properties of TiN to achieve high‐rate and long‐life LSBs. The macropores accommodate the high amount of sulfur, facilitate the electrolyte penetration and transportation of Li⁺ ions, while the mesopores effectively prevent the LiPS dissolution. TiN strongly adsorbs LiPS, mitigates the shuttle effect, and promotes the redox kinetics. Therefore, h‐TiN/S shows a reversible capacity of 557 mA h g^?1 even after 1000 cycles at 5 C rate with only 0.016% of capacity decay per cycle.     

Angiotensin converting enzyme inhibitory benzopyranoids from Angelica gigas

Angiotensin converting enzyme (ACE) plays a major role in the regulation of blood pressure. The potential antihypertensive activity of Angelica gigas was evaluated in vitro by its ability to inhibit ACE. A methanol extract of A. gigas roots exerted an inhibitory effect against ACE and was fractionated using several organic solvents, including dichloromethane, ethyl acetate, and n-butanol. The n-butanol soluble fraction, which manifested potent ACE inhibitory properties, was further purified via repeated silica gel and RP-18 column chromatography. Three benzopyriansides, such as nodakenin (1), umbelliferone (2), and umbelliferone 6-carboxylic acid (3) were isolated from A. gigas roots. Compounds 1–3 inhibited ACE activity in a dose-dependent manner, with IC₅₀ values of 63.95±0.16, 190.49±0.54, and 158.35±1.53 μM, respectively. The inhibition kinetics analyzed by Lineweaver-Burk plots revealed that the three compounds showed a mixed-type inhibition. The equilibrium constants for the inhibitor binding (K_i) of 1, 2, and 3 were estimated to be 1.56×10^?4, 4.70×10^?4, and 2.17×10^?4 M, respectively. We used A. gigas roots to isolate nodakinin, umbelliferone, and umbelliferone 6-carboxylic acid and tested their inhibition efficacy against ACE for the first time.     

Comparative studies on major nutritional components of black waxy rice with giant embryos and its rice bran

The concentration of nutrients in brown rice is mainly associated with embryo size. Various beneficial components have been purified from rice bran. Recently developed black waxy rice with a giant embryo (‘Milyang 263’, BGE), which is the ge ^t mutant of the GE gene, was selected and analyzed to produce high quality nutritional components. γ-Aminobutyric acid (GABA) content in BGE rice bran, one of the most important nutritional compounds in rice, showed a 10.6-fold increase (2.66±0.48 mg/g) compared to that of BGE brown rice (0.25±0.01 mg/g). In addition, brown rice and BGE rice bran showed enriched amylopectin (94.5±0.5 and 97.0±0.0%) and bioactive anthocyanin [Cy-3-G: 75.15±4.18 (brown rice), 82.97±0.81 (rice bran) and Pn-3-G: 1.52±0.50 (brown rice), 4.33±0.20 (rice bran); mg/100 g] contents. These results suggest that BGE rice bran can be used as an excellent raw material to efficiently produce high quality essential amino acids, cyanidin-3 glycoside-enriched anthocyanins, and GABA.     

Dry sol-gel polycondensation of hydrosilanes to organosilicas catalyzed by colloidal nickel nanoparticles

The dry sol-gel polycondensation at toluene in ambient air atmosphere of p-X-C6H4SiH3 (X = H, CH3, CH3O, F, Cl) to silica p-X-C6H4SiO15 in high yield, catalyzed by colloidal nickel nanoparticles in-situ generated from nickelocene(II), nickel(II) acetate, and bis(1,5-cyclooctadiene)nickel(0), is described. Similar catalytic activities were observed for the catalysts. Similarly, the dry sol-gel polyco-condensation p-X-C6H4SiH3 (X = CH3, CH3O, F, Cl):C6H4SiH3 (9:1 mole ratio) at toluene in ambient air atmosphere of was performed to yield co-silicas (p-X-C6H4SiO1.5)9(p-X-C6H4SiO1.5)1 in high yield using nickelocene. The co-gels with higher molecular weights and TGA residue yield were obtained when compared to the homogels. The highest yield, molecular weight, polydispersity index, and TGA residue yield were obtained for p-Cl-C6H4SiH3. Some degree of unreacted Si-H bonds still remained in the gel matrix because of steric bulkiness. All the insoluble gels adopt an amorphous structure with a smooth surface. A plausible mechanism for the dry sol-gel reaction was suggested.     

Occurrence, synthesis, and mammalian cell cytotoxicity and genotoxicity of haloacetamides: an emerging class of nitrogenous drinking water disinfection byproducts

The haloacetamides, a class of emerging nitrogenous drinking water disinfection byproduct (DBPs), were analyzed for their chronic cytotoxicity and for the induction of genomic DNA damage in Chinese hamster ovary cells. The rank order for cytotoxicity of 13 haloacetamides was DIAcAm > IAcAm > BAcAm > TBAcAm > BIAcAm > DBCAcAm > CIAcAm > BDCAcAm > DBAcAm > BCAcAm > CAcAm > DCAcAm > TCAcAm. The rank order of their genotoxicity was TBAcAm > DIAcAm approximately equal to IAcAm > BAcAm > DBCAcAm > BIAcAm > BDCAcAm > CIAcAm > BCAcAm > DBAcAm > CAcAm > TCAcAm. DCAcAm was not genotoxic. Cytotoxicity and genotoxicity were primarily determined by the leaving tendency of the halogens and followed the order I > Br > > Cl. With the exception of brominated trihaloacetamides, most of the toxicity rank order was consistent with structure-activity relationship expectations. For di- and trihaloacetamides, the presence of at least one good leaving halogen group (I or Br but not Cl) appears to be critical for significant toxic activity. Log P was not a factor for monohaloacetamides but may play a role in the genotoxicity of trihaloacetamides and possible activation of dihaloacetamides by intracellular GSH and -SH compounds.     

Essential contribution of caspase 3/CPP32 to apoptosis and its associated nuclear changes

Caspases are fundamental components of the mammalian apoptotic machinery, but the precise contribution of individual caspases is controversial. CPP32 (caspase 3) is a prototypical caspase that becomes activated during apoptosis. In this study, we took a comprehensive approach to examining the role of CPP32 in apoptosis using mice, embryonic stem (ES) cells, and mouse embryonic fibroblasts (MEFs) deficient for CPP32. CPP32(ex3-/-) mice have reduced viability and, consistent with an earlier report, display defective neuronal apoptosis and neurological defects. Inactivation of CPP32 dramatically reduces apoptosis in diverse settings, including activation-induced cell death (AICD) of peripheral T cells, as well as chemotherapy-induced apoptosis of oncogenically transformed CPP32(-/-) MEFs. As well, the requirement for CPP32 can be remarkably stimulus-dependent: In ES cells, CPP32 is necessary for efficient apoptosis following UV- but not gamma-irradiation. Conversely, the same stimulus can show a tissue-specific dependence on CPP32: Hence, TNFalpha treatment induces normal levels of apoptosis in CPP32 deficient thymocytes, but defective apoptosis in oncogenically transformed MEFs. Finally, in some settings, CPP32 is required for certain apoptotic events but not others: Select CPP32(ex3-/-) cell types undergoing cell death are incapable of chromatin condensation and DNA degradation, but display other hallmarks of apoptosis. Together, these results indicate that CPP32 is an essential component in apoptotic events that is remarkably system- and stimulus-dependent. Consequently, drugs that inhibit CPP32 may preferentially disrupt specific forms of cell death.     

Self-propagation Combustion Behavior with Varying Al/Ni Ratios in Compression-Bonded Ni-sputtered Al Foil Multilayers

Compression-bonded Ni-sputtered Al foil multilayers with various atomic ratios of Al/Ni are fabricated with various bilayer thicknesses. The microstructures that are formed after the self-propagating combustion using laser ignition result in equilibrium phases in the Al/Ni binary system. Homogeneous intermetallic compounds for Al₃Ni₂ and AlNi are obtained for the first time in the micrometer-scale multilayers through controlling the Ni layer thickness. The onset temperatures of the multilayers are below 800 K (527 °C) for all multilayer samples. The maximum temperatures correspond to the liquidus temperatures of the intermetallic compounds. The self-propagating direction is divided into a transverse propagating direction and a gross propagating direction. The measured gross propagation velocities vary widely without exhibiting a clear trend. However, the transverse propagation velocity is dependent on the measured maximum temperatures, while the effects of the bilayer thickness are not discernible. The measured transverse propagation velocities are similar to the reported propagation velocities for sputtered multilayers with similar bilayer thicknesses.     

粉末冶金制备的Ti35Nb2．5Sn5HA生物复合材料的组织与性能研究

采用高能机械球磨和脉冲电流活化烧结方法制备了一种新型的不含Al、V等有毒元素的口钛合金基体的Ti35Nb2．5Sn5HA生物复合材料。研究了不同机械球磨时间球磨的Ti35Nb2．5Sn5HA粉末以及用这几种粉末烧结制备的样品微观组织和显微硬度变化,球磨时间对烧结复合材料的微观组织和性能的影响。结果表明：随着球磨时间的增加,Ti35Nb2．5Sn5HA粉末的颗粒尺寸逐渐减小,Nh和Sn开始与Ti发生固溶,形成Ti的过饱和固溶体,而且α-Ti也开始向β-Ti转化。当球磨时间达到12h,球磨粉末中α-Ti完全转化为β-Ti,粉末颗粒的平均尺寸为500nm左右。12h球磨的粉末烧结制备的复合材料具有超细晶粒尺寸,晶粒平均尺寸为200nm,这种复合材料的维氏显微硬度可以达到10187．3MPa。     

Updates on the Risk of Neuropsychiatric and Gastrointestinal Comorbidities in Rosacea and Its Possible Relationship with the Gut–Brain–Skin Axis

Rosacea is a common chronic cutaneous inflammatory disorder. Recently, patients with rosacea were identified as having a higher risk of developing various comorbidities such as cardiovascular disease, psychiatric disorders, neurologic disorders, and gastrointestinal disorders. However, the risks of some comorbidities in patients with rosacea are somewhat contradictory, depending upon the study design. Moreover, pathomechanisms associated with the comorbidities of patients with rosacea remain poorly elucidated. The purpose of this review was to provide the most up-to-date evidence on the risks of neuropsychiatric and gastrointestinal comorbidities in patients with rosacea. Moreover, the molecular pathomechanisms associated with neuropsychiatric and gastrointestinal comorbidities in patients with rosacea were evaluated based on recent studies. This review was also intended to focus more on the role of the gut–brain–skin axis in the association of neuropsychiatric and gastrointestinal comorbidities in rosacea.