Formation mechanism for hexagonal-structured self-assemblies of nanocrystalline titania templated by cetyltrimethylammonium bromide

Hexagonal-structured self-assemblies of nanocrystalline (anatase) titania templated by cetyltrimethylammonium bromide (C(16)H(33)N(CH(3))(3)Br; CTAB) (Hex-ncTiO(2)/CTAB Nanoskeleton) were formed after mixing of aqueous solutions containing CTAB spherical micelles and titanium oxysulfate acid hydrate (TiOSO(4).xH(2)SO(4).xH(2)O) as a titania precursor in the absence of any other additives. Formation mechanism of the Hex-ncTiO(2)/CTAB Nanoskeleton was examined in terms of the reaction temperature, titania precursor/CTAB mixing ratio, surfactant type, electrostatic interaction, micelle formation and molecular component. We found that crystal growth of crystalline (anatase) titania (polymorphic crystallization) was promoted with higher temperature and lower titania precursor content in aqueous solutions. In addition, we revealed that the crystalline (anatase) titania was formed in polycation, poly(allylamine hydrochloride ([CH(2)CH(CH(2)NH(2))HCl](n); PAH), and formamide (HCONH(2)) solutions. On the other hand, no titania formation was observed in anionic systems such as sodium dodecyl sulfate (CH(3)(CH(2))(11)OSO(3)Na; SDS) and poly(sodium 4-styrenesulfonate ([C(8)H(7)SO(3)Na](n); PSSS). This indicates that hydrolysis reaction of the titania precursor is initiated by not only cations but also nitrogen atoms in molecules and polymers. Hexagonally structure was formed in only cationic surfactant micellar solutions but not in polycation solutions and formamide.     

The excellent water-solubility of N-[3-(dimethyl-amino)propyl] docosanamide chloride : the most eco-friendly cationic hair conditioning agent

A new hair-conditioning agent, N-[3-(dimethylamino)propyl]docosanamide (APA-22) hydrochloric acid salt (APA-22 HCl), has excellent solubility in water with a solubility limit over 10-times larger than that of other APA hydrochloric salts with shorter alkyl chain lengths. The physicochemical characteristics of APA-22 HCl were studied at 25 degrees C by using equilibrium surface tension (gamma), solubilization of an oil-soluble dye, steady-state fluorescence, and chloride ion selective electrode techniques. The APA-22 HCl salt is considered to form an aggregate at a concentration, C(1), which is about twice the concentration of the solubility limit of APAs with shorter alkyl chains. At a higher concentration, C(2), the aggregates of APA-22 HCl start forming another kind of aggregate, which is able to solubilize oil-soluble materials. That is, C(1) is considered to represent the critical aggregation concentration (cac) and C(2) a morphology transition. In the concentration region between C(1) and C(2) the solutions are seemingly transparent whereas at above C(2) they appear bluish or translucent. Since the Krafft point of APA-22 HCl is 55 degrees C, all the solutions, including the aggregates, are thought to exist in metastable states. Notably, however, these metastable solutions do not change significantly over a few months. The excellent solubility of APA-22 HCl in water is considered to be a result of this unique stepwise aggregation with increasing concentration.     

Adsorption of cationic monomeric and gemini surfactants on montmorillonite and adsolubilization of vitamin E

Adsorption of a cationic gemini surfactant (1,2-bis(dodecyldimethylammonio) ethane dibromide, 12-2-12) and the corresponding monomeric surfactant (dodecyltrimethylammonium bromide, DTAB) on montmorillonite has been characterized with a combination of adsorption isotherm, interlayer spacing and FT-IR spectroscopic data. Adsolubilization of vitamin E into the adsorbed surfactant layers has also been studied. The adsorption isotherm data reveal that the adsorption of the two surfactants is driven by the two factors: one is the cation exchange that occurs on the interlayer basal planes and the other is the hydrophobic interaction between hydrocarbon chains of the surfactants. Although the adsorbed amount measured in the saturation region (in mol g(-1)) is almost identical for the two surfactants, the conformation of the intercalated surfactant molecules differs significantly from each other. The adsorption of DTAB results in a lateral bilayer arrangement in the limited interlayer space, whereas 12-2-12 gives a normal bilayer arrangement in the expanded interlayer space. Adsolubilization of vitamin E takes place into the adsorbed surfactant layers, and interestingly, all the vitamin E molecules added in the montmorillonite suspensions are hybridized at lower surfactant concentrations due to the great specific surface area of the clay material. Since the maximum adsolubilization amount is usually obtained just below the critical micelle concentration, the gemini surfactant is deemed to be more efficient than the corresponding monomeric one to achieve the great adsolubilization amount.     

Packing density of glycolipid biosurfactant monolayers give a significant effect on their binding affinity toward immunoglobulin G

Mannosylerythritol lipid-A (MEL-A) is one of the most promising glycolipid biosurfactants, and abundantly produced by Pseudozyma yeasts. MEL-A gives not only excellent self-assembling properties but also a high binding affinity toward human immunoglobulin G (HIgG). In this study, three kinds of MEL-A were prepared from methyl myristate [MEL-A (m)], olive oil [MEL-A (o)], and soybean oil [MEL-A (s)], and the effect of interfacial properties of each MEL-A monolayer on the binding affinity toward HIgG was investigated using surface plasmon resonance (SPR) and the measurement of surface pressure (pi)-area (A) isotherms. Based on GC-MS analysis, the main fatty acids were C(8) and C(10) acids in all MEL-A, and the content of unsaturated fatty acids was 0% for MEL-A (m), 9.1% for MEL-A (o), 46.3% for MEL-A (s), respectively. Interestingly, the acid content significantly influenced on their binding affinity, and the monolayer of MEL-A (o) gave a higher binding affinity than that of MEL-A (m) and MEL-A (s). Moreover, the mixed MEL-A (o)/ MEL-A (s) monolayer prepared from 1/1 molar ratio, which comprised of 27.8% of unsaturated fatty acids, indicated the highest binding affinity. At the air/water interface, MEL-A (o) monolayer exhibited a phase transition at 13 degrees C from a liquid condensed monolayer to a liquid expanded monolayer, and the area per molecule significantly expanded above 13 degrees C, while the amount of HIgG bound to the liquid expanded monolayer was much higher than that bound to liquid condensed monolayer. The binding affinity of MEL-A toward HIgG is thus likely to closely relate to the monolayer packing density, and may be partly controlled by temperature.     

One‐Pot/Four‐Step/Palladium‐Catalyzed Synthesis of Indole Derivatives: The Combination of Heterogeneous and Homogeneous Systems

One‐pot, four‐step syntheses of indoles using both solid‐supported heterogeneous and homogeneous palladium catalysts and reagents were carried out. Such a combination of these two‐phase catalysts and reagents causes a dramatic increase in yield, and it is a simple process. The presented methodology is effective for four‐step reactions to provide various functionalized indoles.     

Evaluation of hydrogen absorption behaviour during acid etching for surface modification of commercial pure Ti, Ti-6Al-4V and Ni-Ti superelastic alloys

The hydrogen absorption behaviour during acid etching for the surface modification of commercial pure Ti, Ti-6Al-4V and Ni-Ti superelastic alloys has been investigated on the basis of the surface morphology, electrochemical behaviour and hydrogen thermal desorption analysis. To simulate the conventional acid etching for the improvement of the biocompatibility of Ti alloys, the specimens are immersed in 1 M HCl, 1 M H₂SO₄ or 0.5 M HCl + 0.5 M H₂SO₄ aqueous solution at 60 °C. Upon immersion, commercial pure Ti absorbs substantial amounts of hydrogen irrespective of the type of solution. In H₂SO₄ or HCl + H₂SO₄ solutions, the hydrogen absorption occurs for a short time (10 min). For Ti-6Al-4V alloy, no hydrogen absorption is observed in HCl solution, whereas hydrogen absorption occurs in other solutions. For Ni-Ti superelastic alloy, the amount of absorbed hydrogen is large, resulting in the pronounced degradation of the mechanical properties of the alloy even for an immersion time of 10 min, irrespective of the type of solution. The hydrogen absorption behaviour is not necessarily consistent with the morphologies of the surface subjected to corrosion and the shift of the corrosion potential. The hydrogen thermal desorption behaviour of commercial pure Ti and Ni-Ti superelastic alloy are sensitively changed by acid etching conditions. The present results suggest that the evaluation of hydrogen absorption is needed for each condition of acid etching, and that the conventional acid etching often leads to hydrogen embrittlement.     

Evaluation of hydrogen absorption properties of Ti–0.2 mass% Pd alloy in fluoride solutions

The hydrogen absorption properties of Ti–0.2 mass% Pd (Ti–0.2Pd) alloy in 2.0% and 0.2% acidulated phosphate fluoride (APF) and neutral 2.0% NaF solutions (25 °C) has been evaluated by hydrogen thermal desorption analysis. During the early stage of immersion (120 h) in the 2.0% APF solution, the amount of absorbed hydrogen was lower than 500 mass ppm. A thermal desorption of hydrogen primary appearing with a peak at 500–600 °C and a broad desorption ranging from 100 to 400 °C were observed. In the 0.2% APF solution, the amount of absorbed hydrogen saturated at 100–200 mass ppm; the thermal desorption of hydrogen appeared with a single peak at 550 °C. In the 2.0% NaF solution, hydrogen absorption was negligible even after 1000 h of immersion, although corrosion pits were observed. The results of the present study suggest that the hydrogen absorption of Ti–0.2Pd alloy, as compared with commercial pure titanium, is suppressed in fluoride solutions.     

Development of Selective TGR5 Ligands Based on the 5,6,7,8-Tetrahydro-5,5,8,8-tetramethylnaphthalene Skeleton

TGR5, a G-protein-coupled receptor (GPCR), plays an important role in several physiological functions. TGR5 activation through bile acids induces an increase in energy expenditure. Therefore, synthetic TGR5 ligands could be useful for the treatment of obesity or dyslipidemia. In this study, we designed and synthesized a set of TGR5 ligands with a 5,6,7,8-tetrahydro-5,5,8,8-tetramethylnaphthalene (TMN) skeleton, and evaluated their TGR5 agonistic activity. We also investigated the selectivity of the synthesized compounds for TGR5 relative to the farnesoid X receptor (FXR) and retinoic acid receptor (RAR). Our results show that compound 4 b [N-(2-chlorophenyl)-5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-naphthalenecarboxamide] exhibited potent TGR5 agonist activity with an IC₅₀ value of 8.4 nM without significant cytotoxicity. In addition, compound 4 b showed only slight agonistic activity toward FXR and RAR at 1 μM treatment. These data indicate that compound 4 b is a selective TGR5 agonist, and could be a promising therapeutic agent for dyslipidemia.     

Emerging Immunotherapy for Acute Myeloid Leukemia

Several immune checkpoint molecules and immune targets in leukemic cells have been investigated. Recent studies have suggested the potential clinical benefits of immuno-oncology (IO) therapy against acute myeloid leukemia (AML), especially targeting CD33, CD123, and CLL-1, as well as immune checkpoint inhibitors (e.g., anti-PD (programmed cell death)-1 and anti-CTLA4 (cytotoxic T-lymphocyte-associated protein 4) antibodies) with or without conventional chemotherapy. Early-phase clinical trials of chimeric antigen receptor (CAR)-T or natural killer (NK) cells for relapsed/refractory AML showed complete remission (CR) or marked reduction of marrow blasts in a few enrolled patients. Bi-/tri-specific antibodies (e.g., bispecific T-cell engager (BiTE) and dual-affinity retargeting (DART)) exhibited 11–67% CR rates with 13–78% risk of cytokine-releasing syndrome (CRS). Conventional chemotherapy in combination with anti-PD-1/anti-CTLA4 antibody for relapsed/refractory AML showed 10–36% CR rates with 7–24 month-long median survival. The current advantages of IO therapy in the field of AML are summarized herein. However, although cancer vaccination should be included in the concept of IO therapy, it is not mentioned in this review because of the paucity of relevant evidence.     

Chemokines Up-Regulated in Epithelial Cells Control Senescence-Associated T Cell Accumulation in Salivary Glands of Aged and Sjögren’s Syndrome Model Mice

Immunosenescence is characterized by age-associated changes in immunological functions. Although age- and autoimmune-related sialadenitis cause dry mouth (xerostomia), the roles of immunosenescence and cellular senescence in the pathogenesis of sialadenitis remain unknown. We demonstrated that acquired immune cells rather than innate immune cells infiltrated the salivary glands (SG) of aged mice. An analysis of isolated epithelial cells from SG revealed that the expression levels of the chemokine CXCL13 were elevated in aged mice. Senescence-associated T cells (SA-Ts), which secrete large amounts of atypical pro-inflammatory cytokines, are involved in the pathogenesis of metabolic disorders and autoimmune diseases. The present results showed that SA-Ts and B cells, which express the CXCL13 receptor CXCR5, accumulated in the SG of aged mice, particularly females. CD4⁺ T cells derived from aged mice exhibited stronger in vitro migratory activity toward CXCL13 than those from young mice. In a mouse model of Sjögren’s syndrome (SS), SA-Ts also accumulated in SG, presumably via CXCL12-CXCR4 signaling. Collectively, the present results indicate that SA-Ts accumulate in SG, contribute to the pathogenesis of age- and SS-related sialadenitis by up-regulating chemokines in epithelial cells, and have potential as therapeutic targets for the treatment of xerostomia caused by these types of sialadenitis.