Cation‐Transporting Peptides: Scaffolds for Functionalized Pores?

Protein pores that selectively transport ions across membranes are among nature’s most efficient machines. The selectivity of these pores can be exploited for ion sensing and water purification. Since it is difficult to reconstitute membrane proteins in their active form for practical applications it is desirable to develop robust synthetic compounds that selectively transport ions across cell membranes. One can envision tuning the selectivity of pores by incorporating functional groups inside the pore. Readily accessible octapeptides containing (aminomethyl)benzoic acid and alanine are reported here that preferentially transport cations over halides across the lipid bilayer. Ion transport is hypothesized through pores formed by stable assemblies of the peptides. The aromatic ring(s) appear to be proximal to the pore and could be potentially utilized for functionalizing the pore interior.     

meso‐Tritolylcorrole‐Functionalized Single‐walled Carbon Nanotube Donor?Acceptor Nanocomposites for NO2 Detection

meso‐Tritolylcorrole‐functionalized single‐walled carbon nanotubes (TTC‐SWNT) donor‐acceptor (D–A) heterojunction nanocomposite film was fabricated on a polycarbonate membrane through filtration and non‐covalent functionalization, providing an excellent sensing platform with low‐cost, high flexibility and good gas accessibility. The TTC‐SWNTs nanocomposite displays a fast and sensitive response to nitrogen dioxide with a limit of detection of 10 ppb (S/N=3). The sensing response was significantly amplified compared to the unmodified one, which was ascribed to a D–A heterojunction at the interface between electron donor TTC and electron acceptor SWNTs. This study provides a simple route to fabricate low‐cost and highly sensitive donor‐acceptor nanocomposite‐based gas sensors.     

Rare‐Earth‐Metal Alkylaluminates Supported by N‐Donor‐Functionalized Cyclopentadienyl Ligands: C?H Bond Activation and Performance in Isoprene Polymerization

Homoleptic tetramethylaluminate complexes [Ln(AlMe₄)₃] (Ln=La, Nd, Y) reacted with HCp^NMe2 (Cp^NMe2=1‐[2‐(N,N‐dimethylamino)‐ethyl]‐2,3,4,5‐tetramethyl‐cyclopentadienyl) in pentane at ?35 °C to yield half‐sandwich rare‐earth‐metal complexes, [{C₅Me₄CH₂CH₂NMe₂(AlMe₃)}Ln(AlMe₄)₂]. Removal of the N‐donor‐coordinated trimethylaluminum group through donor displacement by using an equimolar amount of Et₂O at ambient temperature only generated the methylene‐bridged complexes [{C₅Me₄CH₂CH₂NMe(μ‐CH₂)AlMe₃}Ln(AlMe₄)] with the larger rare‐earth‐metal ions lanthanum and neodymium. X‐ray diffraction analysis revealed the formation of isostructural complexes and the C? H bond activation of one aminomethyl group. The formation of Ln(μ‐CH₂)Al moieties was further corroborated by ¹³C and ¹H‐¹³C HSQC NMR spectroscopy. In the case of the largest metal center, lanthanum, this C? H bond activation could be suppressed at ?35 °C, thereby leading to the isolation of [(Cp^NMe2)La(AlMe₄)₂], which contains an intramolecularly coordinated amino group. The protonolysis reaction of [Ln(AlMe₄)₃] (Ln=La, Nd) with the anilinyl‐substituted cyclopentadiene HCp^AMe2 (Cp^AMe2=1‐[1‐(N,N‐dimethylanilinyl)]‐2,3,4,5‐tetramethylcyclopentadienyl) at ?35 °C generated the half‐sandwich complexes [(Cp^AMe2)Ln(AlMe₄)₂]. Heating these complexes at 75 °C resulted in the C? H bond activation of one of the anilinium methyl groups and the formation of [{C₅Me₄C₆H₄NMe(μ‐CH₂)AlMe₃}Ln(AlMe₄)] through the elimination of methane. In contrast, the smaller yttrium metal center already gave the aminomethyl‐activated complex at ?35 °C, which is isostructural to those of lanthanum and neodymium. The performance of complexes [{C₅Me₄CH₂CH₂NMe(μ‐CH₂)AlMe₃}‐ Ln(AlMe₄)], [(Cp^AMe2)Ln(AlMe₄)₂], and [{C₅Me₄C₆H₄NMe(μ‐CH₂)AlMe₃}Ln(AlMe₄)] in the polymerization of isoprene was investigated upon activation with [Ph₃C][B(C₆F₅)₄], [PhNMe₂H][B(C₆F₅)₄], and B(C₆F₅)₃. The highest stereoselectivities were observed with the lanthanum‐based pre‐catalysts, thereby producing polyisoprene with trans‐1,4 contents of up to 95.6 %. Narrow molecular‐weight distributions (M_w/M_n<1.1) and complete consumption of the monomer suggested a living‐polymerization mechanism.     

Dendron‐Functionalized Core–Shell Superparamagnetic Nanoparticles: Magnetically Recoverable and Reusable Catalysts for Suzuki C?C Cross‐Coupling Reactions

A metallodendron functionalized with dicyclohexyldiphosphino palladium complex was synthesized. The metallodendron was grafted onto core–shell superparamagnetic nanoparticles (γ‐Fe₂O₃/polymer, 200–500 nm) to give optimal catalytic reactivity in cross‐coupling reactions. The grafted nanoparticles were used as recoverable and reusable catalysts for Suzuki C? C cross‐coupling reactions. They showed remarkable reactivity towards iodo‐ and bromoarenes under mild conditions, and unprecedented reactivity towards chloroarenes. On completion of the catalytic reaction, the catalysts were readily recovered by using a simple magnet to attract the superparamagnetic grafted nanoparticles. Catalysts were recovered more than 25 times with almost no discernable loss of reactivity.     

Synthesis of 2‐ and 2,7‐Functionalized Pyrene Derivatives: An Application of Selective C?H Borylation

An efficient synthetic route to 2‐ and 2,7‐substituted pyrenes is described. The regiospecific direct C? H borylation of pyrene with an iridium‐based catalyst, prepared in situ by the reaction of [{Ir(μ‐OMe)cod}₂] (cod=1,5‐cyclooctadiene) with 4,4′‐di‐tert‐butyl‐2,2′‐bipyridine, gives 2,7‐bis(Bpin)pyrene ( 1 ) and 2‐(Bpin)pyrene ( 2 , pin=OCMe₂CMe₂O). From 1 , by simple derivatization strategies, we synthesized 2,7‐bis(R)‐pyrenes with R=BF₃K ( 3 ), Br ( 4 ), OH ( 5 ), B(OH)₂ ( 6 ), and OTf ( 7 ). Using these nominally nucleophilic and electrophilic derivatives as coupling partners in Suzuki–Miyaura, Sonogashira, and Buchwald–Hartwig cross‐coupling reactions, we obtained 2,7‐bis(R)‐pyrenes with R=(4‐CO₂C₈H₁₇)C₆H₄ ( 8 ), Ph ( 9 ), C≡CPh ( 10 ), C≡C[{4‐B(Mes)₂}C₆H₄] ( 11 ), C≡CTMS ( 12 ), C≡C[(4‐NMe₂)C₆H₄] ( 14 ), C≡CH ( 15 ), N(Ph)[(4‐OMe)C₆H₄] ( 16 ), and R=OTf, R′=C≡CTMS ( 13 ). Lithiation of 4 , followed by reaction with CO₂, yielded pyrene‐2,7‐dicarboxylic acid ( 17 ), whilst borylation of 2‐tBu‐pyrene gave 2‐tBu‐7‐Bpin‐pyrene ( 18 ) selectively. By similar routes (including Negishi cross‐coupling reactions), monosubstituted 2‐R‐pyrenes with R=BF₃K ( 19 ), Br ( 20 ), OH ( 21 ), B(OH)₂ ( 22 ), [4‐B(Mes)₂]C₆H₄ ( 23 ), B(Mes)₂ ( 24 ), OTf ( 25 ), C≡CPh ( 26 ), C≡CTMS ( 27 ), (4‐CO₂Me)C₆H₄ ( 28 ), C≡CH ( 29 ), C₃H₆CO₂Me ( 30 ), OC₃H₆CO₂Me ( 31 ), C₃H₆CO₂H ( 32 ), OC₃H₆CO₂H ( 33 ), and O(CH₂)₁₂Br ( 34 ) were obtained from 2 . These derivatives are of synthetic and photophysical interest because they contain donor, acceptor, and conjugated substituents. The crystal structures of compounds 4 , 5 , 7 , 12 , 18 , 19 , 21 , 23 , 26 , and 28 – 31 have also been obtained from single‐crystal X‐ray diffraction data, revealing a diversity of packing modes, which are described in the Supporting Information. A detailed discussion of the structures of 1 and 2 , their polymorphs, solvates, and co‐crystals is reported separately.     

Palladium‐Catalyzed C?S Activation/Aryne Insertion/Coupling Sequence: Synthesis of Functionalized 2‐Quinolinones

The insertion of an aryne into a C S bond can suppress the addition of an S nucleophile to the aryne in the presence of palladium. Catalyzed by Pd(OAc)₂, a wide range of α‐carbamoyl ketene dithioacetals readily react with arynes to selectively afford functionalized 2‐quinolinones in high yields under neutral reaction conditions by a C S activation/aryne insertion/intramolecular coupling sequence. The attractive feature of the new strategy also lies in the versatile transformations of the alkythio‐substituted quinolinone products.     

Isolation of Functionalized Phenolic Monomers through Selective Oxidation and C?O Bond Cleavage of the β‐O‐4 Linkages in Lignin

Functionalized phenolic monomers have been generated and isolated from an organosolv lignin through a two‐step depolymerization process. Chemoselective catalytic oxidation of β‐O‐4 linkages promoted by the DDQ/tBuONO/O₂ system was achieved in model compounds, including polymeric models and in real lignin. The oxidized β‐O‐4 linkages were then cleaved on reaction with zinc. Compared to many existing methods, this protocol, which can be achieved in one pot, is highly selective, giving rise to a simple mixture of products that can be readily purified to give pure compounds. The functionality present in these products makes them potentially valuable building blocks.     

A Straightforward Synthesis of 2‐[1‐Alkyl‐5,6‐bis(alkoxycarbonyl)‐1,2,3,4‐tetrahydro‐2‐oxopyridin‐3‐yl]acetic Acid Derivatives via Domino Michael Addition?Cyclization Reaction

A new and efficient synthesis of 2‐[1‐alkyl‐5,6‐bis(alkoxycarbonyl)‐1,2,3,4‐tetrahydro‐2‐oxopyridin‐3‐yl]acetic acid derivatives by a one‐pot three‐component reaction between primary amine, dialkyl acetylenedicarboxylate, and itaconic anhydride (=3,4‐dihydro‐3‐methylidenefuran‐2,5‐dione) is reported. The reaction was performed without catalyst and under solvent‐free conditions with excellent yields. Notably, the ready availability of the starting materials, and the high level of practicability of the reaction and workup make this approach an attractive complementary method to access to unknown 2‐[1‐alkyl‐5,6‐bis(alkoxycarbonyl)‐1,2,3,4‐tetrahydro‐2‐oxopyridin‐3‐yl]acetic acid derivatives. The structures were corroborated spectroscopically (IR, ¹H‐ and ¹³C‐NMR, and EI‐MS) and by elemental analyses. A plausible mechanism for this type of domino Michael addition? cyclization reaction is proposed (Scheme 2).     

A Triphenylphosphonium Functionalized AIE Conjugated Macrocyclic Tetramal&mide for Mitochondrial-targeting Bioimaging

Developme nt of subcellular orga nelle-targeted bioimagi ng probes is of great imports nee in the field of early detection of diseases and exploring the behaviors of subcellular organelles.Herein,we present a triphenyIphosphonium functionalized conjugated macrocyclic tetramaleimide(TPP-CMT)as a mitochondrial-targeting bioimaging probe.The core of TPP-CMT is obtained by connecting two pyrenes and two benzenes through four maleimides.This unique structure endows TPP-CMT with exceptional far red/near-i nfirared aggregati on-induced emissi on(FR/NIR-AIE)characteristics.TPP-CMT is an excelle nt fluoresce nt emitter in most solve nts and eve n in solid states.The qua ntum yield of TPP-CMT was higher tha n 27% when dissolved in comm on middle-polarity orga nic solve nt and this value remained at 28.2% in its solid state.The in troducti on of four triphe ny Iphosph onium on maleimide positions endows TPP-CMT with mitochondrial-targeting ability.Thanks to the FR/NIR-AIE characteristics and the mitochondri-al-targeti ng ability,this well-desig ned fluoresce nt probe was successfully employed for mitochondrial targeti ng bioimaging of HeLa and HepG2 cells.     

Gerührt oder geschüttelt? James‐Bond‐Cocktail

Starting from perfluoroheptane, saturated aqueous potassium carbonate solution, methanol, toluene and suitable dyes, a three‐phasic mixture is prepared initially. After shaking – not only stirring – four layers develop. Addition of pentane changes the sequence of two layers. The layers are added in a new sequence and the way of mixing demonstrates the complexity of multi‐phasic systems.     

A Triphenylphosphonium Functionalized AIE Conjugated Macrocyclic Tetramal&mide for Mitochondrial-targeting Bioimaging

Developme nt of subcellular orga nelle-targeted bioimagi ng probes is of great imports nee in the field of early detection of diseases and exploring the behaviors of subcellular organelles.Herein,we present a triphenyIphosphonium functionalized conjugated macrocyclic tetramaleimide(TPP-CMT)as a mitochondrial-targeting bioimaging probe.The core of TPP-CMT is obtained by connecting two pyrenes and two benzenes through four maleimides.This unique structure endows TPP-CMT with exceptional far red/near-i nfirared aggregati on-induced emissi on(FR/NIR-AIE)characteristics.TPP-CMT is an excelle nt fluoresce nt emitter in most solve nts and eve n in solid states.The qua ntum yield of TPP-CMT was higher tha n 27% when dissolved in comm on middle-polarity orga nic solve nt and this value remained at 28.2% in its solid state.The in troducti on of four triphe ny Iphosph onium on maleimide positions endows TPP-CMT with mitochondrial-targeting ability.Thanks to the FR/NIR-AIE characteristics and the mitochondri-al-targeti ng ability,this well-desig ned fluoresce nt probe was successfully employed for mitochondrial targeti ng bioimaging of HeLa and HepG2 cells.     

C?C Cross‐Coupling Reactions of O6‐Alkyl‐2‐Haloinosine Derivatives and a One‐Pot Cross‐Coupling/O6‐Deprotection Procedure

Reaction conditions for the C? C cross‐coupling of O⁶‐alkyl‐2‐bromo‐ and 2‐chloroinosine derivatives with aryl‐, hetaryl‐, and alkylboronic acids were studied. Optimization experiments with silyl‐protected 2‐bromo‐O⁶‐methylinosine led to the identification of [PdCl₂(dcpf)]/K₃PO₄ in 1,4‐dioxane as the best conditions for these reactions (dcpf=1,1′‐bis(dicyclohexylphosphino)ferrocene). Attempted O⁶‐demethylation, as well as the replacement of the C‐6 methoxy group by amines, was unsuccessful, which led to the consideration of Pd‐cleavable groups such that C? C cross‐coupling and O⁶‐deprotection could be accomplished in a single step. Thus, inosine 2‐chloro‐O⁶‐allylinosine was chosen as the substrate and, after re‐evaluation of the cross‐coupling conditions with 2‐chloro‐O⁶‐methylinosine as a model substrate, one‐step C? C cross‐coupling/deprotection reactions were performed with the O⁶‐allyl analogue. These reactions are the first such examples of a one‐pot procedure for the modification and deprotection of purine nucleosides under C? C cross‐coupling conditions.     

Dense or Porous Packing? Two‐Dimensional Self‐Assembly of Star‐Shaped Mono‐, Bi‐, and Terpyridine Derivatives

The self‐assembly behavior of five star‐shaped pyridyl‐functionalized 1,3,5‐triethynylbenzenes was studied at the interface between an organic solvent and the basal plane of graphite by scanning tunneling microscopy. The mono‐ and bipyridine derivatives self‐assemble in closely packed 2D crystals, whereas the derivative with the more bulky terpyridines crystallizes with porous packing. DFT calculations of a monopyridine derivative on graphene, support the proposed molecular model. The calculations also reveal the formation of hydrogen bonds between the nitrogen atoms and a hydrogen atom of the neighboring central unit, as a small nonzero tunneling current was calculated within this region. The title compounds provide a versatile model system to investigate the role of multivalent steric interactions and hydrogen bonding in molecular monolayers.