Monolithiation of 5,5′‐Dibromo‐2,2′‐bithiophene Using Flow Microreactors: Mechanistic Implications and Synthetic Applications

The lithiation of 5,5′‐dibromo‐2,2′‐bithiophene with one equivalent of an alkyllithium such as n‐BuLi or s‐BuLi was studied by varying the residence time in flow microreactors. With a short residence time, the product 2,2′‐bithiophene (3) derived from dilithiation was obtained preferentially and a significant amount of the starting material 5,5′‐dibromo‐2,2′‐bithiophene remained unchanged. An increase in the residence time caused a higher yield of the product 5‐bromo‐2,2′‐bithiophene derived from monolithiation with expense in the yields of 2,2′‐bithiophene and 5,5′‐dibromo‐2,2′‐bithiophene. The lithiation using MeLi gave the product 5‐bromo‐2,2′‐bithiophene preferentially even with a very short residence time.     

Forgetting curve of cricket,Gryllus bimaculatus,derived by using serotonin hypothesis

It is thought that the adjustment of intraspecific aggression is an essential factor in the development of a social structure. To understand the natural laws for organizing the social structure, we focus on the fighting behavior of crickets, Gryllus bimaculatus, and investigate the neuronal mechanisms to adjust aggressiveness associated with a neuromodulatory biological amine: serotonin (5-HT).In this paper, we present a working theory of a neurophysiological mechanism based on the past biological studies on the 5-HT hypothesis, and a mathematical model of the mechanism. We analyzed this model and concluded that this neurophysiological mechanism makes the forgetting process slower. Next, we fitted our theoretical forgetting curve to an experimental curve and estimated the parameters of our model. These estimated values were in agreement with common belief in biological science.     

Postfunctionalization of aromatic polyamine by [2+2] cycloaddition of 7,7,8,8-tetracyanoquinodimethane with side chain alkynes

Electron-rich, side chain alkynes of an aromatic polyamine were functionalized by a [2+2] cycloaddition, followed by retro-cyclization with the electron-accepting 7,7,8,8-tetracyanoquinodimethane (TCNQ). ¹H NMR studies were used to optimize the reaction conditions. Mild heating to >50?°C afforded the postfunctionalized aromatic polyamines with the desired acceptor amounts. The quantitative TCNQ addition was demonstrated by the MALDI-TOF mass spectrum and elemental analysis. Introduction of the cyano-based acceptor moieties into the polymer side chains resulted in unusually strong intermolecular interactions. In addition to the ?ШC?? interactions of the extended acceptor moieties, these intermolecular forces were supposed to improve the thermal stability of the aromatic polymers. Furthermore, the donor?Cacceptor chromophores formed by this postfunctionalization displayed low energy charge-transfer bands and redox activities in both the anodic and cathodic directions. The straightforward postfunctionalization technique using the alkyne?CTCNQ addition is useful for the preparation of narrow band gap polymers in one step.     

Effect of friction stir processing on microstructure of laser clad cobalt-based alloy

(The microstructural refinement of cobalt-based alloy (Stellite No. 6) by laser cladding and friction stir processing (FSP) was studied. A nanometer-sized microstructure consisting of fine carbide (particle size: 100–200 nm) and a grain (grain size: 150–250 nm) was successfully fabricated by the FSP on the laser clad cobalt-based alloy. The nanostructured cobalt-based alloy (Stellite No. 6) had an extremely high hardness of about 750 HV.     

Metal powder bed fusion in high gravity

Many studies have focused on the stabilization of additive manufacturing (AM) in microgravity for its use in various space projects. Nevertheless, this paper presents a vital clue for innovating metal AM technologies from the perspective of high gravity. High-gravitational powder bed fusion has an excellent potential to address various challenges in AM, such as density enhancement, spatter suppression, and precise fabrication. This study summarizes an analogy among phenomena in different gravitational fields and establishes a combined machine for centrifuge and powder bed fusion. The results confirm the spatter suppression and fine-powder availability in high gravity, both theoretically and experimentally.     

Quantitative analysis of α-mangostin in hydrophilic ointment using near-infrared spectroscopy

The objective of this research was to quantify the α-mangostin content in mangosteen pericarp (MP) ointment as a colloidal dispersion using near-infrared (NIR) spectroscopy. Various concentrations of MP (IP and EP) ointments containing both internal and external pericarps were prepared and the NIR spectra of these ointments were measured. The NIR spectrum of each ointment was correlated with α-mangostin concentration by partial least square (PLS) regression. Validation of the models was performed and their predictive ability was also investigated. The equation and R² value for the prediction of α-mangostin concentration in IP ointment were y?=?0.9843x?+?0.4441 and 0.9730 and those in EP ointment were y?=?0.9569x?+?0.1142 and 0.9136, respectively. The biases of the IP and EP ointment models were 0.23 and 0.00, respectively. The results showed that NIR could be a useful tool for the quality control of herbal medicine in hydrophilic ointment without any sample preparation. It could predict α-mangostin content in hydrophilic ointment at very low concentration with sufficient accuracy.     

Characterization of alternative plasticizers in poly(vinyl chloride) sheets for blood containers

This study aimed to optimize the ratio of dioctyl 4‐cyclohexene‐1,2‐dicarboxylate (DOTH) and di‐isononyl‐cyclohexane‐1,2‐dicarboxylate (DINCH^®) for use as plasticizers in poly(vinyl chloride) (PVC) sheets. We also evaluated the biological safety of DOTH for its potential to be part of a safe PVC‐based blood container. The suppression of hemolysis in mannitol‐adenine‐phosphate / red cell concentrates (MAP/RCC) with DOTH/(DINCH^®‐PVC) sheets and the elution of plasticizers from the sheets increased with higher DOTH compositions. The properties of the PVC sheet containing DOTH and DINCH^® in the ratio of 25:33 parts against PVC 100 parts as a weight were almost identical to the PVC sheet made of di(2‐ethylhexyl) phthalate. From a subchronic toxicity test, DOTH did not show any adverse effects on all organs, including the testes, epididymis, liver, and kidneys. The no‐observed‐adverse‐effect level was 300 mg/kg body weight/day in a rat. These results suggest that DOTH/DINCH^® (25:33) is a promising candidate for the replacement of di(2‐ethylhexyl) phthalate in blood containers. J. VINYL ADDIT. TECHNOL., 22:520–528, 2016. © 2015 Society of Plastics Engineers     

Platelet-Released Growth Factors Influence Wound Healing-Associated Genes in Human Keratinocytes and Ex Vivo Skin Explants

Platelet-released growth factors (PRGFs) or other thrombocyte concentrate products, e.g., Platelet-Rich Fibrin (PRF), have become efficient tools of regenerative medicine in many medical disciplines. In the context of wound healing, it has been demonstrated that treatment of chronic or complicated wounds with PRGF or PRF improves wound healing in the majority of treated patients. Nevertheless, the underlying cellular and molecular mechanism are still poorly understood. Therefore, we aimed to analyze if PRGF-treatment of human keratinocytes caused the induction of genes encoding paracrine factors associated with successful wound healing. The investigated genes were Semaphorin 7A (SEMA7A), Angiopoietin-like 4 (ANGPLT4), Fibroblast Growth Factor-2 (FGF-2), Interleukin-32 (IL-32), the CC-chemokine-ligand 20 (CCL20), the matrix-metalloproteinase-2 (MMP-2), the chemokine C-X-C motif chemokine ligand 10 (CXCL10) and the subunit B of the Platelet-Derived Growth Factor (PDGFB). We observed a significant gene induction of SEMA7A, ANGPLT4, FGF-2, IL-32, MMP-2 and PDGFB in human keratinocytes after PRGF treatment. The CCL20- and CXCL10 gene expressions were significantly inhibited by PRGF therapy. Signal transduction analyses revealed that the PRGF-mediated gene induction of SEMA7A, ANGPLT4, IL-32 and MMP-2 in human keratinocytes was transduced via the IL-6 receptor pathway. In contrast, EGF receptor signaling was not involved in the PRGF-mediated gene expression of analyzed genes in human keratinocytes. Additionally, treatment of ex vivo skin explants with PRGF confirmed a significant gene induction of SEMA7A, ANGPLT4, MMP-2 and PDGFB. Taken together, these results describe a new mechanism that could be responsible for the beneficial wound healing properties of PRGF or related thrombocytes concentrate products such as PRF.