Single-Site Modifications and Their Effect on the Folding Stability of <i>m</i>-Phenylene Ethynylene Oligomers

The folded structure of a m-phenylene ethynylene oligomer is tolerant to single-site modifications to both the backbone sequence and end groups. The helical structure is reinforced by multiple noncovalent interactions, allowing the oligomer sequence to be customized without a significant change in stability in most cases. The small changes that are observed are consistent with the expected behavior of π-stacked systems and demonstrate subtle control over folding through single-site modifications

Image_1_Pleiotrophin Expression and Actions in Pancreatic β-Cells.jpeg

Pleiotrophin (PTN) is a heparin-binding cytokine that is widely expressed during early development and increases in maternal circulation during pregnancy.Aged PTN-deficient mice exhibit insulin resistance, suggesting a role in metabolic control. The objectives of this study were to determine if PTN is expressed in mouse pancreatic β-cells in young vs. adult animals, and its effects on DNA synthesis, β-cell gene expression and glucose-stimulated insulin secretion (GSIS). The Ptn gene was expressed in isolated fractions of young mouse β-cells, especially within immature β-cells with low glucose transporter 2 expression. Expression was retained in the adult pancreas but did not significantly change during pregnancy. PTN and its receptor, phosphotyrosine phosphatase-β/ζ, were also expressed in the proliferative INS1E β-cell line. Fluorescence immunohistochemistry showed that PTN peptide was present in islets of Langerhans in adult mice, associated predominantly with β-cells. The percentage of β-cells staining for PTN did not alter during mouse pregnancy, but intense staining was seen during β-cell regeneration in young mice following depletion of β-cells with streptozotocin. Incubation of INS1E cells with PTN resulted in an increased DNA synthesis as measured by Ki67 localization and increased expression of Pdx1 and insulin. However, both DNA synthesis and GSIS were not altered by PTN in isolated adult mouse islets. The findings show that Ptn is expressed in mouse β-cells in young and adult life and could potentially contribute to adaptive increases in β-cell mass during early life or pregnancy.</p

Image_2_Pleiotrophin Expression and Actions in Pancreatic β-Cells.jpeg

Pleiotrophin (PTN) is a heparin-binding cytokine that is widely expressed during early development and increases in maternal circulation during pregnancy.Aged PTN-deficient mice exhibit insulin resistance, suggesting a role in metabolic control. The objectives of this study were to determine if PTN is expressed in mouse pancreatic β-cells in young vs. adult animals, and its effects on DNA synthesis, β-cell gene expression and glucose-stimulated insulin secretion (GSIS). The Ptn gene was expressed in isolated fractions of young mouse β-cells, especially within immature β-cells with low glucose transporter 2 expression. Expression was retained in the adult pancreas but did not significantly change during pregnancy. PTN and its receptor, phosphotyrosine phosphatase-β/ζ, were also expressed in the proliferative INS1E β-cell line. Fluorescence immunohistochemistry showed that PTN peptide was present in islets of Langerhans in adult mice, associated predominantly with β-cells. The percentage of β-cells staining for PTN did not alter during mouse pregnancy, but intense staining was seen during β-cell regeneration in young mice following depletion of β-cells with streptozotocin. Incubation of INS1E cells with PTN resulted in an increased DNA synthesis as measured by Ki67 localization and increased expression of Pdx1 and insulin. However, both DNA synthesis and GSIS were not altered by PTN in isolated adult mouse islets. The findings show that Ptn is expressed in mouse β-cells in young and adult life and could potentially contribute to adaptive increases in β-cell mass during early life or pregnancy.</p

Table_1_Pleiotrophin Expression and Actions in Pancreatic β-Cells.docx

Pleiotrophin (PTN) is a heparin-binding cytokine that is widely expressed during early development and increases in maternal circulation during pregnancy.Aged PTN-deficient mice exhibit insulin resistance, suggesting a role in metabolic control. The objectives of this study were to determine if PTN is expressed in mouse pancreatic β-cells in young vs. adult animals, and its effects on DNA synthesis, β-cell gene expression and glucose-stimulated insulin secretion (GSIS). The Ptn gene was expressed in isolated fractions of young mouse β-cells, especially within immature β-cells with low glucose transporter 2 expression. Expression was retained in the adult pancreas but did not significantly change during pregnancy. PTN and its receptor, phosphotyrosine phosphatase-β/ζ, were also expressed in the proliferative INS1E β-cell line. Fluorescence immunohistochemistry showed that PTN peptide was present in islets of Langerhans in adult mice, associated predominantly with β-cells. The percentage of β-cells staining for PTN did not alter during mouse pregnancy, but intense staining was seen during β-cell regeneration in young mice following depletion of β-cells with streptozotocin. Incubation of INS1E cells with PTN resulted in an increased DNA synthesis as measured by Ki67 localization and increased expression of Pdx1 and insulin. However, both DNA synthesis and GSIS were not altered by PTN in isolated adult mouse islets. The findings show that Ptn is expressed in mouse β-cells in young and adult life and could potentially contribute to adaptive increases in β-cell mass during early life or pregnancy.</p

Barrierless Switching between a Liquid and Superheated Solid Catalyst during Nanowire Growth

Knowledge of nucleation and growth mechanisms is essential for the synthesis of nanomaterials, such as semiconductor nanowires, with shapes and compositions precisely engineered for technological applications. Nanowires are conventionally grown by the seemingly well-understood vapor–liquid–solid mechanism, which uses a liquid alloy as the catalyst for growth. However, we show that it is possible to instantaneously and reversibly switch the phase of the catalyst between a liquid and superheated solid state under isothermal conditions above the eutectic temperature. The solid catalyst induces a vapor–solid–solid growth mechanism, which provides atomic-level control of dopant atoms in the nanowire. The switching effect cannot be predicted from equilibrium phase diagrams but can be explained by the dominant role of the catalyst surface in modulating the kinetics and thermodynamics of phase behavior. The effect should be general to metal-catalyzed nanowire growth and highlights the unexpected yet technologically relevant nonequilibrium effects that can emerge in the growth of nanoscale systems

Addition of Bromine Chloride and Iodine Monochloride to Carbonyl-Conjugated, Acetylenic Ketones: Synthesis and Mechanisms^†

The reactions of 3-butyn-2-one (1), 3-hexyn-2-one (2), and 4-phenyl-3-butyn-2-one (3) with bromine chloride (BrCl) and iodine monochloride (ICl) in CH2Cl2, CH2Cl2/pyridine, and MeOH are described. The data show that the major products in CH2Cl2 are (Z)-AM (anti-Markovnikov) regioisomers. With the exception of 3 and ICl, the (E)-AM regioisomers predominate when pyridine was added as an acid scavenger. Minor amounts of the M regioisomers were formed with 1 and 2 and BrCl. The percentage of M regioisomer increased significantly with 1 and BrCl in MeOH, but MeOH had little affect on the other reactions. Isolation and stability of the products are discussed. Detailed evidence for the structures of the products, involving a combination of MS, 1H and 13C NMR, and IR, is presented; HRMS analyses are provided as proofs for all of the products. The acid-catalyzed mechanism and the halonium ion mechanism are considered as possible pathways in the formation of the products

Capillarity-Driven Welding of Semiconductor Nanowires for Crystalline and Electrically Ohmic Junctions

Semiconductor nanowires (NWs) have been demonstrated as a potential platform for a wide-range of technologies, yet a method to interconnect functionally encoded NWs has remained a challenge. Here, we report a simple capillarity-driven and self-limited welding process that forms mechanically robust and Ohmic inter-NW connections. The process occurs at the point-of-contact between two NWs at temperatures 400–600 °C below the bulk melting point of the semiconductor. It can be explained by capillarity-driven surface diffusion, inducing a localized geometrical rearrangement that reduces spatial curvature. The resulting weld comprises two fused NWs separated by a single, Ohmic grain boundary. We expect the welding mechanism to be generic for all types of NWs and to enable the development of complex interconnected networks for neuromorphic computation, battery and solar cell electrodes, and bioelectronic scaffolds

Reactions of Carbonyl-Conjugated Alkynes with <i>N</i>-Bromosuccinimide and <i>N</i>-Iodosuccinimide in DMF/H₂O and Methanol/Sulfuric Acid: Syntheses of Dihalo Diketones, Dihalo Ketoesters, and Dihalo Acetals^†

The following terminal, carbonyl-conjugated alkynes were reacted with N-bromosuccinimide (NBS) and N-iodosuccinimide (NIS) in MeOH/H2SO4 to give dibromo and diiodo acetals in the indicated yields:  3-butyn-2-one, 1:  NBS (75%), NIS (95%); 1-phenyl-1-propyn-1-one, 2:  NBS (90%), NIS (40%); 1-hexyn-3-one, 3:  NBS (90%), NIS (70%); methyl propiolate, 4:  NBS (20%, not isolated), NIS (95%). 4,4-Dimethyl-1-pentyn-3-one (5) gave only a trace of dibromo acetal and no diiodo acetal; tribromide and tetrabromide were the major products. NBS and NIS reactions required, respectively, 20% and 33 wt % of H2SO4. The reaction was unsuccessful with internal alkynes 4-phenyl-3-butyn-2-one and 3-hexyn-2-one which gave only complex mixtures of products. Alkyne 2 gave a significant yield of acetal-ketal in addition to the dihalo acetals. Both the dibromo acetal-ketal and diiodo acetal-ketal were isolated, but only the former could be hydrolyzed to the dibromo acetal. Internal, carbonyl-conjugated alkynes reacted with NBS and NIS in H2O/DMF (40:60) to give the following products in the indicated yields:  4-phenyl-3-butyn-2-one (6):  1-phenyl-3,3-dibromo-1,3-butanedione (17, 70%), 1-phenyl-3,3-diiodo-1,3-butanedione (21, 95%); 3-hexyn-2-one (7):  3,3-dibromo-2,4-hexanedione (18, 80%), 3,3-diiodo-2,4-hexanedione (22, 95%); methyl 3-phenyl-2-propynoate (8): methyl 2,2-dibromo-3-keto-3-phenylpropanoate (19, 43%), methyl 2,2-diiodo-3-keto-3-phenylpropanoate (23, 95%); methyl 2-pentynoate (9):  methyl 2,2-dibromo-3-ketopentanoate (20, 80%), methyl 2,2-diiodo-3-ketopentanoate (24, 95%). All reactions, except for 6 and 8 with NBS, required H2SO4. The terminal, carbonyl-conjugated alkyne, 3-butyn-2-one, did not give products, possibly because of oxidation of the intermediate aldehyde by NBS and NIS. Mechanisms involving electrophilic attack by halogen on the triple bond and an acid-catalyzed mechanism are discussed

All-in-One Derivatized Tandem p⁺n‑Silicon–SnO₂/TiO₂ Water Splitting Photoelectrochemical Cell

Mesoporous metal oxide film electrodes consisting of derivatized 5.5 μm thick SnO₂ films with an outer 4.3 nm shell of TiO₂ added by atomic layer deposition (ALD) have been investigated to explore unbiased water splitting on p, n, and p⁺n type silicon substrates. Modified electrodes were derivatized by addition of the water oxidation catalyst, [Ru­(bda)­(4-O­(CH₂)₃PO₃H₂)-pyr)₂], <b>1</b>, (pyr = pyridine; bda = 2,2′-bipyridine-6,6′-dicarboxylate), and chromophore, [Ru­(4,4′-PO₃H₂-bpy) (bpy)₂]²⁺, <b>RuP</b>²⁺, (bpy = 2,2′-bipyridine), which form 2:1 <b>RuP</b>²⁺/<b>1</b> assemblies on the surface. At pH 5.7 in 0.1 M acetate buffer, these electrodes with a fluorine-doped tin oxide (FTO) back contact under ∼1 sun illumination (100 mW/cm²; white light source) perform efficient water oxidation with a photocurrent of 1.5 mA/cm² with an 88% Faradaic efficiency (FE) for O₂ production at an applied bias of 600 mV versus RHE (ACS Energy Lett., 2016, 1, 231−236). The SnO₂/TiO₂–chromophore–catalyst assembly was integrated with the Si electrodes by a thin layer of titanium followed by an amorphous TiO₂ (Ti/<i>a-</i>TiO₂) coating as an interconnect. In the integrated electrode, p⁺n-Si–Ti/<i>a</i>-TiO₂–SnO₂/TiO₂|-2<b>RuP</b>²⁺/<b>1</b>, the p⁺n-Si junction provided about 350 mV in added potential to the half cell. In photolysis experiments at pH 5.7 in 0.1 M acetate buffer, bias-free photocurrents approaching 100 μA/cm² were obtained for water splitting, 2H₂O → 2H₂ + O₂. The FE for water oxidation was 79% with a hydrogen efficiency of ∼100% at the Pt cathode