Linear Backbone Research Articles

Pushing the Length Limit of Dihydrodiboraacenes: Synthesis and Characterizations of Boron‐Embedded Heptacene and Nonacene

AbstractBoron‐embedded heteroacenes (boraacenes) have attracted enormous interest in organic chemistry and materials science. However, extending the skeleton of boraacenes to higher acenes (N≥6) is synthetically challenging because of their limited stability under ambient conditions. Herein, we report the synthesis of boron‐embedded heptacene (DBH) and nonacene (DBN) as the hitherto longest boraacenes. The former is highly stable (even after 240 h in tetrahydrofuran), while the latter is air‐sensitive with the half‐life (t1/2) of 11.8 min. The structures of both compounds are verified by single‐crystal X‐ray diffraction, revealing a linear backbone with an antiaromatic C4B2core. Photophysical characterizations associated with theoretical calculations indicate that both compounds exhibit highly efficient anti‐Kasha emissions. Remarkably, the air‐stableDBHmanifests an ultrahigh photoluminescence quantum yield (PLQY) of 98±2 % and can be chemically reduced to its radical anion and dianion states, implying the value of boron‐doped higher acenes as novel functional materials.

Toy models of multibranched polymers: opened vs circular structures

We study the conformational properties of complex Gaussian polymers containing f c linear branches and f r closed loops, periodically tethered at n branching points to either a linear polymer backbone (generalized bottlebrush structures) or closed polymer ring (decorated ring structure). Applying the path integration method, based on Edwards continuous chain model, we obtain in particular the exact values for the size ratios comparing the gyration radii of considered complex structures and linear chains of the same total molecular weight, as functions of n, f c and f r . Compactification of the overall effective size of branched macromolecules with the increasing number of loops is quantitatively confirmed. Our results are supported by numerical estimates obtained by application of Wei’s method.

Backbone Configuration and Electronic Property Tuning of Imide‐Functionalized Ladder‐Type Heteroarenes‐Based Polymer Acceptors for Efficient All‐Polymer Solar Cells

AbstractElectron‐deficient ladder‐type π‐conjugated systems are highly desired for constructing polymer acceptors due to their unique electronic properties. Herein, two series of polymer acceptors PBTIn‐(F)T (n = 1–4) based on imide‐functionalized ladder‐type heteroarenes (BTIn) with tunable conjugation length are synthesized. Effects of their backbone configuration and electronic properties on film morphology and performance of all‐polymer solar cells (all‐PSCs) are systematically investigated through theoretical computation, Raman spectroscopy, grazing incidence wide‐angle X‐ray scattering, etc. It is found that the ladder‐type heteroarene size extension and polymer backbone fluorination gradually lower the frontier molecular orbital energy levels, leading to progressive bandgap narrowing with more efficient exciton dissociation. Furthermore, the centrosymmetric and axisymmetric characteristics of BTIn result in distinct backbone configuration with varied self‐aggregation and crystalline phases, hence determining the blend film morphology. The highest efficiencies in these two series are attained from PBTI3‐T and PBTI3‐FT with a curved backbone configuration. PBTI4‐(F)T with further extended heteroarenes shows linear backbone, negatively affecting film morphology and efficiency. This study provides fundamental material structure‐device performance correlations for ladder‐type heteroarenes‐based polymer acceptors for the first time and demonstrates that more extended ladder‐type backbones do not necessarily improve the device performance, offering guidelines for designing polymer acceptors to maximize all‐PSC performance.

Tunable metallic-like transport in polypyrrole

Abstract Conjugated polymers (CPs), organic macromolecules with a linear backbone of alternating C–C and C=C bonds, possess unique semiconductive properties, providing new opportunities for organic electronics, photonics, information, and energy devices. Seeking the metallic or metallic-like, even superconducting properties beyond semiconductivity in CPs is always one of the ultimate goals in polymer science and condensed matter. Only two metallic and semi-metallic transport cases—aniline-derived polyaniline and thiophene-derived poly(3,4-ethylenedioxythiophene)—have been reported since the development of CPs for four decades. Controllable synthesis is a key challenge in discovering more cases. Here we report the metallic-like transport behavior of another CP, polypyrrole (PPy). We observe that the transport behavior of PPy changes from semiconductor to insulator-metal transition, and gradually realizes metallic-like performance when the crystalline degree increases. Using a generalized Einstein relation model, we rationalized the mechanism behind the observation. The metallic-like transport in PPy demonstrates electron strong correlation and phonon–electron interaction in soft condensation matter, and may find practical applications of CPs in electrics and spintronics.

Fracture Behavior of Polyrotaxane-Toughened Poly(Methyl Methacrylate).

The fracture behavior of polyrotaxane (PR)-modified poly(methyl methacrylate) (PMMA) was investigated. PR is a supramolecule with rings threaded onto a linear backbone chain, which is capped by bulky end groups to prevent the rings from de-threading. The ring structure is α-cyclodextrin (CD), and it can be functionalized to enhance its affinity with the hosting polymer matrix. Adding only 1 wt % of PR containing methacrylate functional groups (mPR) at the terminal of some of the polycaprolactone-grafted chains on CD promotes massive crazing, resulting in a significant improvement in fracture toughness while maintaining the modulus and transparency of the PMMA matrix. Dynamic mechanical analysis and atomic force microscopy studies reveal that mPR strongly interact with PMMA, leading to higher molecular mobility and enhanced molecular cooperativity during deformation. This molecular cooperativity may be responsible for the formation of massive crazing in a PMMA matrix, which leads to greatly improved fracture toughness.

Swelling of asymmetric pom-pom polymers in dilute solutions

In this paper we continue our recent analysis [K. Haydukivska et al., J. Mol. Liq., 2021, 328, 115456] of complex molecules with two branching points at both ends of the linear backbone with f1 and f2 side arms starting from them, known as the pom-pom polymers. Here, we analyze the asymmetric case, f1 ≠ f2, by applying both the analytical approach, based on the direct polymer renormalization, and computer simulations using both dissipative particle dynamics and Monte Carlo methods. We study the role played by the molecular asymmetry of average polymer conformations, considering the infinite dilution regime and good solvent conditions.The quantitative estimates are reported for the set of universal size and shape characteristics of such molecules and for their individual branches, all the functions of f1 and f2. In particular, we evaluate the size ratio of the gyration radii of symmetric and asymmetric pom-pom topologies with the same molecular weight and quantitatively reveal an increase of the effective size of a molecule caused by its asymmetry. We also introduce and analyse the asymmetry factor and estimate the shift of the center of mass caused by the presence of side stars, which can serve as another characteristic of the asymmetry of pom-pom structure.

Glycosaminoglycan-like sulfated polysaccharides from Vibrio diabolicus bacterium: Semi-synthesis and characterization

Sulfated glycosaminoglycan (GAG) analogues derived from plant, algae or microbial sourced polysaccharides are highly interesting in order to gain bioactivities similar to sulfated GAGs but without risks and concerns derived from their typical animal sources. Since the exopolysaccharide (EPS) produced by the bacterium Vibrio diabolicus HE800 strain from deep-sea hydrothermal vents is known to have a GAG-like structure with a linear backbone composed of unsulfated aminosugar and uronic acid monomers, its structural modification through four different semi-synthetic sulfation strategies has been performed. A detailed structural characterization of the six obtained polysaccharides revealed that three different sulfation patterns (per-O-sulfation, a single N-sulfation and a selective primary hydroxyls sulfation) were achieved, with molecular weights ranging from 5 to 40 kDa. A Surface Plasmonic Resonance (SPR) investigation of the affinity between such polysaccharides and a set of growth factors revealed that binding strength is primarily depending on polysaccharide sulfation degree.

Computational design of ratiometric two-photon fluorescent Zn2+ probes based on quinoline and di-2-picolylamine moieties

To improve two-photon absorption (TPA) response of a newly synthesized probe, a series of ratiometric two-photon fluorescent Zn2+ sensors based on quinoline and DPA moieties have been designed. The one-photon absorption, TPA, and emission properties of the experimental and designed probes before and after coordination with Zn2+ are investigated employing the density functional theory in combination with response functions. The design consists of two levels. In the first level of design, five probes are constructed through using several electron acceptors or donors to increase accepting or donating ability of the fluorophores. It shows that all the designed probes have stronger TPA intensities at longer wavelengths with respect to the experimental probe because of the increased intra-molecular charge transfer. Moreover, it is found that the probe 4 built by adding an acyl unit has the largest TPA cross section among the designed structures due to the form of longer conjugated length and more linear backbone. One dimethylamino terminal attached along the skeleton can improve TPA intensity more efficiently than two side amino groups. Therefore, in the second level of design, a new probe 7 is formed by both an acyl unit and a dimethylamino terminal. It exhibits that the TPA cross sections of probe 7 and its zinc complex increase dramatically. Furthermore, the fluorescence quantum yields of the designed probes 4 and 7 are calculated in a new way, which makes use of the relation between the computed difference of dipole moment and the measured fluorescence quantum yield. The result shows that our design also improves the fluorescence quantum yield considerably. All in all, the designed probes 4 and 7 not only possess enhanced TPA intensities but also have large differences of emission wavelength upon Zn2+ coordination and strong fluorescence intensity, which demonstrates that they are potential ratiometric two-photon fluorescent probes.

Arabinoxylans: A new class of food ingredients arising from synergies with biorefining, and illustrating the nature of biorefinery engineering

Arabinoxylans (AX) are hemicellulose polysaccharides comprising a linear backbone of xylose sugars with arabinose residues attached along the chain. They offer interesting functional properties that could have application as a new class of food ingredients or for non-food applications. The emergence in recent decades of biorefineries gives a context in which commercial production of a portfolio of AX products could be feasible, through integration with bioethanol production, using ethanol to precipitate the AX. Extending the concept, AX fractions of different functionality can be precipitated at different ethanol concentrations, giving further scope for efficiencies through bioethanol pinch analysis, while producing a portfolio of products with different potential markets and end uses. The current work demonstrates the potential of AX fractions extracted from sugarcane bagasse as bread ingredients. Bagasse AX fractions increased the water absorption in dough formulations, by more than double their own weight for fractions larger than 10 kDa, and increased dough development time in a Chopin Mixolab. As well as promising in their own right, AX also illustrate the more general opportunity for synergies between biorefining and the food industry, with the rise of biorefineries giving opportunities to provide the food industry with new ingredients not currently available.

Announcement of the 2022 winners of the Spychala and Women in Science Awards

Announcement of the 2022 winners of the Spychala and Women in Science Awards

Structural characterization and protective effects of polysaccharide from Gracilaria lemaneiformis on LPS-induced injury in IEC-6 cells

This study was aimed to characterize Gracilaria lemaneiformis polysaccharides and evaluate their protective effects on Lipopolysaccharide-induced injury in IEC-6 cells. The G. lemaneiformis polysaccharide was degraded by UV/H2O2 treatment and purified to three fractions named GLP-1.0 M, GLP-1.4 M and GLP-1.6 M. The purified fractions were mainly composed of galactose, glucose and xylose. The structural analysis showed that GLP-1.6 M was a typical sulfated red alga polysaccharide containing the linear backbone of β-(1 → 3)- and α-(1 → 4)-linked galactosyl residues, anhydro-galactose units. In the Lipopolysaccharide-induced IEC-6 cells model, GLP-1.6 M exerted the strongest in vitro anti-inflammatory activity by inhibiting the release and expressions of tumor necrosis factor-α, interleukin-6 and interleukin-1β by 89.93%, 67.82% and 38.06%, respectively. Meanwhile, GLP-1.6 M enhanced the intestinal barrier function via up-regulating the expressions of tight junctions and mucin. Therefore, the purified polysaccharide from G. lemaneiformis could be a promising candidate for maintaining intestinal health in the food and pharmaceutical industries.

Influence of Backbone Curvature on the Organic Electrochemical Transistor Performance of Glycolated Donor–Acceptor Conjugated Polymers

AbstractTwo new glycolated semiconducting polymers PgBT(F)2gT and PgBT(F)2gTT of differing backbone curvatures were designed and synthesised for application as p‐type accumulation mode organic electrochemical transistor (OECT) materials. Both polymers demonstrated stable and reversible oxidation, accessible within the aqueous electrochemical window, to generate polaronic charge carriers. OECTs fabricated from PgBT(F)2gT featuring a curved backbone geometry attained a higher volumetric capacitance of 170 F cm−3. However, PgBT(F)2gTT with a linear backbone displayed overall superior OECT performance with a normalised peak transconductance of 3.00×104 mS cm−1, owing to its enhanced order, expediting the charge mobility to 0.931 cm2 V−1 s−1.

Influence of Backbone Curvature on the Organic Electrochemical Transistor Performance of Glycolated Donor-Acceptor Conjugated Polymers.

Two new glycolated semiconducting polymers PgBT(F)2gT and PgBT(F)2gTT of differing backbone curvatures were designed and synthesised for application as p‐type accumulation mode organic electrochemical transistor (OECT) materials. Both polymers demonstrated stable and reversible oxidation, accessible within the aqueous electrochemical window, to generate polaronic charge carriers. OECTs fabricated from PgBT(F)2gT featuring a curved backbone geometry attained a higher volumetric capacitance of 170 F cm−3. However, PgBT(F)2gTT with a linear backbone displayed overall superior OECT performance with a normalised peak transconductance of 3.00×104 mS cm−1, owing to its enhanced order, expediting the charge mobility to 0.931 cm2 V−1 s−1.

Structure elucidation of the novel carotenoid gemmatoxanthin from the photosynthetic complex of Gemmatimonas phototrophica AP64

Gemmatimonas phototrophica AP64 is the first phototrophic representative of the bacterial phylum Gemmatimonadetes. The cells contain photosynthetic complexes with bacteriochlorophyll a as the main light-harvesting pigment and an unknown carotenoid with a single broad absorption band at 490 nm in methanol. The carotenoid was extracted from isolated photosynthetic complexes, and purified by liquid chromatography. A combination of nuclear magnetic resonance (1H NMR, COSY, 1H-13C HSQC, 1H-13C HMBC, J-resolved, and ROESY), high-resolution mass spectroscopy, Fourier-transformed infra-red, and Raman spectroscopy was used to determine its chemical structure. The novel linear carotenoid, that we have named gemmatoxanthin, contains 11 conjugated double bonds and is further substituted by methoxy, carboxyl and aldehyde groups. Its IUPAC-IUBMB semi-systematic name is 1′-Methoxy-19′-oxo-3′,4′-didehydro-7,8,1′,2′-tetrahydro- Ψ, Ψ carotene-16-oic acid. To our best knowledge, the presence of the carboxyl, methoxy and aldehyde groups on a linear C40 carotenoid backbone is reported here for the first time.

Distributed Algorithms for Multiple Path Backbone Discovery in Thick Linear Sensor Networks

Continued advancements in microprocessors, electronics, and communication technology have led to the design and development of sensing devices with increased functionalities, smaller sizes, larger processing, storage, and communication capabilities, and decreased cost. A large number of these sensor nodes are used in many environmental, infrastructure, commercial, and military monitoring applications. Due to the linearity of a good number of the monitored structures such as oil, gas, and water pipelines, borders, rivers, and roads, the wireless sensor networks (WSNs) that are used to monitor them have a linear topology. This type of WSN is called a linear sensor network (LSN). In this paper, two distributed algorithms for topology discovery in thick LSNs are presented: the linear backbone discovery algorithm (LBD) and the linear backbone discovery algorithm with x backbone paths (LBDx). Both of them try to construct a linear backbone for efficient routing in LSNs. However, the LBD algorithm has the objective of minimizing the number of messages used during the backbone discovery process. On the other hand, the LBDx algorithm focuses on reducing the number of hops of the data messages transmitted from the nodes to the sink. LBD and LBDx exhibit good properties and efficient performance, which are confirmed by extensive simulations.

Exploiting diol reactivity for the access to unprecedented low molecular weight curdlan sulfate polysaccharides

Curdlan is a bacterial sourced polysaccharide, consisting of a linear backbone of β-1 → 3-linked glucose (Glc) units. The high interest in pharmaceutical applications of curdlan and derivatives thereof is fueling the study of multi-step sequences for regioselective modifications of its structure. Here we have developed semi-synthetic sequences based on a regioselective protection-sulfation-deprotection approach, allowing the access to some, new, low molecular weight curdlan polysaccharide derivatives with unprecedented sulfation patterns. Three different semi-synthetic schemes were investigated, all relying upon the installation of a cyclic benzylidene protecting group on Glc O-4,6-diols, followed by either direct sulfation and deprotection, or some additional steps – including a hydrolytic or oxidative cleavage of the benzylidene rings – prior to sulfation and deprotection. The six obtained polysaccharides were subjected to a detailed structural characterization by 2D-NMR analysis, revealing that some of them showed the majority of Glc units along the polymeric backbone decorated by unprecedented sulfation motifs.

Mechanical and scratch behaviors of polyrotaxane‐modified poly(methyl methacrylate)

AbstractThe mechanical and scratch behaviors of polyrotaxane (PR) modified poly(methyl methacrylate) (PMMA) were investigated. PR is a necklace‐like supramolecule with rings threaded onto a linear backbone chain that is capped by bulky end groups. Cyclodextrin (CD) serves as the ring structure and can be functionalized to induce specific interactions with the hosting polymer matrix. To systematically investigate the effect of CD functionalization on the mechanical properties of PMMA, PR with polycaprolactone (PCL) grafted chains on CD, and PR with methacrylate functional groups at the terminal of the PCL grafted chains on CD were chosen for this study. Tensile and compressive true stress–strain tests, ASTM scratch test, and coefficient of friction measurements were conducted to fundamentally understand how PR influences the mechanical and scratch behaviors of PMMA. Additionally, dielectric relaxation spectroscopy and dynamic mechanical analysis were conducted to explore how PR influences the relaxation dynamics of PMMA. The above findings suggest that the methacrylate functional group on PR induces favorable molecular interactions with PMMA matrix, leading to enhanced molecular cooperativity during deformation, which in turn improves tensile and compressive properties and achieves greatly improved scratch resistance.

Partial Order–Disorder Transformation of Interpenetrated Porous Coordination Polymers

Controlling interpenetration and flexibility behaviors is intriguing and fundamental for porous coordination polymers. We report exceptional interpenetration behaviors involving controllable partia...

Absolute Configuration of In Situ Crystallized (+)-γ-Decalactone

Knowledge about the absolute configuration of small bioactive organic molecules is essential in pharmaceutical research because enantiomers can exhibit considerably different effects on living organisms. X-ray crystallography enables chemists to determine the absolute configuration of an enantiopure compound due to anomalous dispersion. Here, we present the determination of the absolute configuration of the flavoring agent (+)-γ-decalactone, which is liquid under ambient conditions. Single crystals were grown from the liquid in a glass capillary by in situ cryo-crystallization. Diffraction data collection was performed using Cu-Kα radiation. The absolute configuration was confirmed. The molecule consists of a linear aliphatic non-polar backbone and a polar lactone head. In the solid state, layers of polar and non-polar sections of the molecule alternating along the c-axis of the unit cell are observed. In favorable cases, this method of absolute configuration determination of pure liquid (bioactive) agents or liquid products from asymmetric catalysis is a convenient alternative to conventional methods of absolute structure determination, such as optical rotatory dispersion, vibrational circular dichroism, ultraviolet-visible spectroscopy, use of chiral shift reagents in proton NMR and Coulomb explosion imaging.

Implicit Side-Chain Model and Experimental Characterization of Bottlebrush Block Copolymer Solution Assembly

Bottlebrush polymers are a class of macromolecules with linear backbones and densely grafted side chains, possessing unique physical properties due to strong steric interactions between the side ch...