Functional Side Chains Research Articles

Optical Detection of Stereoselective Interactions with DNA-Wrapped Single-Wall Carbon Nanotubes.

DNA-wrapped carbon nanotubes have been explored increasingly as sensitive near-infrared fluorescence probes for biomolecules. However, notably missing in previous studies is an inquiry on stereoselective interactions between DNA-wrapped carbon nanotubes and biomolecules. Here, enantiopure (+) and (-)(6,5), and (-)(8,3) as well as achiral (11,0) carbon nanotubes wrapped with specific resolving DNA sequences are used to demonstrate their stereoselective detection of amino acid enantiomers. Furthermore, stereoselective sensing abilities are found to be retained by dispersions containing a multitude of chiral nanotube structures. The fluorescence response profiles of six different DNA-wrapped carbon nanotube dispersions to nine standard amino acids, and their enantiomers, demonstrate that DNA-wrapped carbon nanotubes are exquisitely sensitive to the stereoconfiguration and side-chain functionality of amino acids in a manner that is dependent on both DNA sequence and nanotube chirality. Implications of our findings are discussed in the context of developing a machine learning-aided multiplexed biosensing scheme called a molecular perceptron.

A Guideline for the Synthesis of Amino-Acid-Functionalized Monomers and Their Polymerizations.

Amino acids have emerged as a sustainable source for the design of functional polymers. Besides their wide availability, especially their high degree of biocompatibility makes them appealing for a broad range of applications in the biomedical research field. In addition to these favorable characteristics, the versatility of reactive functional groups in amino acids (i.e., carboxylic acids, amines, thiols, and hydroxyl groups) makes them suitable starting materials for various polymerization approaches, which include step- and chain-growth reactions. This review aims to provide an overview of strategies to incorporate amino acids into polymers. To this end, it focuses on the preparation of polymerizable monomers from amino acids, which yield main chain or side chain-functionalized polymers. Furthermore, postpolymerization modification approaches for polymer side chain functionalization are discussed. Amino acids are presented as a versatile platform for the development of polymers with tailored properties.

Resilient Poly(α-hydroxy acids) with Improved Strength and Ductility via Scalable Stereosequence-Controlled Polymerization.

Despite the degradability and biocompatibility of poly(α-hydroxy acids), their utility remains limited because their thermal and mechanical properties are inferior to those of commodity polyolefins, which can be attributed to the lack of side-chain functionality on the polyester backbone. Attempts to synthesize high-molecular-weight functionalized poly(α-hydroxy acids) from O-carboxyanhydrides have been hampered by scalability problems arising from the need for an external energy source such as light or electricity. Herein, we report an operationally simple, scalable method for the synthesis of stereoregular, high-molecular-weight (>200 kDa) functionalized poly(α-hydroxy acids) by means of controlled ring-opening polymerization of O-carboxyanhydrides mediated by a highly redox reactive manganese complex and a zinc-alkoxide. Mechanistic studies indicated that the ring-opening process likely proceeded via the Mn-mediated decarboxylation with alkoxy radical formation. Gradient copolymers produced directly by this method from mixtures of two O-carboxyanhydrides exhibited better ductility and toughness than their corresponding homopolymers and block copolymers, therefore highlighting the potential feasibility of functionalized poly(α-hydroxy acids) as ductile and resilient polymeric materials.

Defect Passivation for Perovskite Solar Cells: from Molecule Design to Device Performance.

Perovskite solar cells (PSCs) are a promising third-generation photovoltaic (PV) technology developed rapidly in recent years. Further improvement of their power conversion efficiency is focusing on reducing the non-radiative charge recombination induced by the defects in metal halide perovskites. So far, defect passivation by the organic small molecule has been considered as a promising approach for boosting the PSC performance owing to their large structure flexibility adapting to passivating variable kinds of defect states and perovskite compositions. Here, the recent progress of defect passivation toward efficient and stable PSCs was reviewed from the viewpoint of molecular structure design and device performance. To comprehensively reveal the structure-performance correlation of passivation molecules, it was separately discussed how the functional groups, organic frameworks, and side chains affect the corresponding PV parameters of PSCs. Finally, a guideline was provided for researchers to select more suitable passivation agents, and a perspective was given on future trends in development of passivation strategies.

Organometallic reagents primed for peptide modification

In this issue of Chem Catalysis , Walczak and co-workers introduce a carbastannatrane alanine derivative that facilitates amino acid side-chain functionalizations via C–C, C–S, and C–Se bond formation using Stille cross-coupling reactions. Applications in late-stage peptide modifications and macrocyclizations further exemplify the value of this novel building block. In this issue of Chem Catalysis , Walczak and co-workers introduce a carbastannatrane alanine derivative that facilitates amino acid side-chain functionalizations via C–C, C–S, and C–Se bond formation using Stille cross-coupling reactions. Applications in late-stage peptide modifications and macrocyclizations further exemplify the value of this novel building block.

Apical Membrane Expression of Distinct Sulfated Glycans Is a Characteristic Feature of Ductules and Their Reactive and Neoplastic Counterparts.

Intrahepatic bile ducts transport bile between bile canaliculi and the extrahepatic bile duct. The luminal surface of this tract is lined by a layer of biliary epithelial cells, or cholangiocytes, which secrete mucins consisting of scaffold proteins and O-glycosidically linked carbohydrate side chains. Although mucin core proteins have been extensively investigated, the structure and function of carbohydrate side chains have not. Here, we demonstrate that distinct sulfated glycans positive for MECA-79, R-10G, and 297-11A, but not 5D4, monoclonal antibodies are expressed in the cytoplasm of cells of large-sized ducts and in the apical membrane of cells in ductules, and that R-10G immunolabeling is partially eliminated by endo-β-galactosidase digestion, supporting the presence of N-acetylglucosamine-6-O-sulfated N-acetyllactosamine structures. We observed comparable apical membrane-predominant staining in ductular reactions seen during regeneration that occurs in various liver diseases and in cholangiolocarcinoma, a subtype of small duct-type intrahepatic cholangiocarcinoma (iCCA). Apical membrane expression of distinct sulfated glycans in large duct-type iCCA was negligible. Intriguingly, under pathological conditions, endo-β-galactosidase digestion almost completely eliminated R-10G immunoreactivity. These findings suggest that apical membrane expression of distinct sulfated glycans is a characteristic feature of ductules and their reactive and neoplastic counterparts.

Analysis of non-derivatized bacteriohopanepolyols using UHPLC-HRMS reveals great structural diversity in environmental lipid assemblages

Bacteriohopanepolyols (BHPs) are lipids with great chemotaxonomic potential for microbial populations and biogeochemical processes in the environment. The most commonly used methods for BHP analysis are chemical degradation followed by gas chromatography-mass spectrometry (MS) or derivatization followed by high performance liquid chromatography (HPLC)-atmospheric pressure chemical ionization/MS. Here we report on significant advances in the analysis of non-derivatized BHPs using U(ltra)HPLC-electrospray ionization-high resolution MS2. Fragmentation mass spectra provided information on the BHP core, functionalized side chain, as well as the conjugated moiety of composite BHPs. We successfully identified the common bacteriohopanepolyols and their (di)methylated and (di)unsaturated homologues, aminoBHPs, and composite BHPs (e.g., cyclitol ethers and methylcarbamate-aminoBHPs) in biomass of several known BHP-producing bacteria. To show how the method can be exploited to reveal the diversity of BHPs in the environment, we investigated a soil from an active methane seep, in which we detected ca. 130 individual BHPs, including a complex distribution of adenosylhopanes. We identified the nucleoside base moiety of both adenosylhopane type-2 and type-3. Adenosyl hopane type-3 contains a methylated adenine as its nucleobase, while type-2 appears to contain a deaminated and methylated adenine, or N1-methylinosine. In addition, we detected novel adenosylhopanes. Furthermore, we identified a series of novel composite BHPs comprising of bacteriohopanepolyols conjugated to an ethenolamine moiety. The novel ethenolamineBHPs as well as aminoBHPs were also detected acylated to fatty acids. The analytical approach described allows for simultaneous analysis of the full suite of IPLs, now including BHPs, and represents a further step towards environmental lipidomics.

Design and Self-Assembling Behaviour of Calamitic Reactive Mesogens with Lateral Methyl and Methoxy Substituents and Vinyl Terminal Group.

Smart self-organising systems attract considerable attention in the scientific community. In order to control and stabilise the liquid crystalline behaviour, and hence the self-organisation, the polymerisation process can be effectively used. Mesogenic units incorporated into the backbones as functional side chains of weakly cross-linked macromolecules can become orientationally ordered. Several new calamitic reactive mesogens possessing the vinyl terminal group with varying flexible chain lengths and with/without lateral substitution by the methyl (methoxy) groups have been designed and studied. Depending on the molecular structure, namely, the type and position of the lateral substituents, the resulting materials form the nematic, the orthogonal SmA and the tilted SmC phases in a reasonably broad temperature range, and the structure of the mesophases was confirmed by X-ray diffraction experiments. The main objective of this work is to contribute to better understanding of the molecular structure–mesomorphic property relationship for new functional reactive mesogens, aiming at further design of smart self-assembling macromolecular materials for novel sensor systems.

Non-Covalent Carrier Hydrophobicity as a Universal Predictor of Intracellular Protein Activity.

Over the past decade, extensive optimization of polymeric cell-penetrating peptide (CPP) mimics (CPPMs) by our group has generated a substantial library of broadly effective carriers which circumvent the need for covalent conjugation often required by CPPs. In this study, design rules learned from CPPM development were applied to reverse-engineer the first library of simple amphiphilic block copolypeptides for non-covalent protein delivery, namely, poly(alanine-block-arginine), poly(phenylalanine-block-arginine), and poly(tryptophan-block-arginine). This new CPP library was screened for enhanced green fluorescent protein and Cre recombinase delivery alongside a library of CPPMs featuring equivalent side-chain configurations. Due to the added hydrophobicity imparted by the polymer backbone as compared to the polypeptide backbone, side-chain functionality was not a universal predictor of carrier performance. Rather, overall carrier hydrophobicity predicted the top performers for both internalization and activity of protein cargoes, regardless of backbone identity. Furthermore, comparison of protein uptake and function revealed carriers which facilitated high gene recombination despite remarkably low Cre internalization, leading us to formalize the concept of intracellular availability (IA) of the delivered cargo. IA, a measure of cargo activity per quantity of cargo internalized, provides valuable insight into the physical relationship between cellular internalization and bioavailability, which can be affected by bottlenecks such as endosomal escape and cargo release. Importantly, carriers with maximal IA existed within a narrow hydrophobicity window, more hydrophilic than those exhibiting maximal cargo uptake. Hydrophobicity may be used as a scaffold-independent predictor of protein uptake, function, and IA, enabling identification of new, effective carriers which would be overlooked by uptake-based screening methods.

Capacity for increased surface area in the hydrophobic core of β-sheet peptide bilayer nanoribbons.

Amphipathic peptides with amino acids arranged in alternating patterns of hydrophobic and hydrophilic residues efficiently self‐assemble into β‐sheet bilayer nanoribbons. Hydrophobic side chain functionality is effectively buried in the interior of the putative bilayer of these nanoribbons. This study investigates consequences on self‐assembly of increasing the surface area of aromatic side chain groups that reside in the hydrophobic core of nanoribbons derived from Ac‐(XKXE)2‐NH2 peptides (X = hydrophobic residue). A series of Ac‐(XKXE)2‐NH2 peptides incorporating aromatic amino acids of increasing molecular volume and steric profile (X = phenylalanine [Phe], homophenylalanine [Hph], tryptophan [Trp], 1‐naphthylalanine [1‐Nal], 2‐naphthylalanine [2‐Nal], or biphenylalanine [Bip]) were assessed to determine substitution effects on self‐assembly propensity and on morphology of the resulting nanoribbon structures. Additional studies were conducted to determine the effects of incorporating amino acids of differing steric profile in the hydrophobic core (Ac‐X1KFEFKFE‐NH2 and Ac‐(X1,5KFE)‐NH2 peptides, X = Trp or Bip). Spectroscopic analysis by circular dichroism (CD) and Fourier transform infrared (FT‐IR) spectroscopy indicated β‐sheet formation for all variants. Self‐assembly rate increased with peptide hydrophobicity; increased molecular volume of the hydrophobic side chain groups did not appear to induce kinetic penalties on self‐assembly rates. Transmission electron microscopy (TEM) imaging indicated variation in fibril morphology as a function of amino acid in the X positions. This study confirms that hydrophobicity of amphipathic Ac‐(XKXE)2‐NH2 peptides correlates to self‐assembly propensity and that the hydrophobic core of the resulting nanoribbon bilayers has a significant capacity to accommodate sterically demanding functional groups. These findings provide insight that may be used to guide the exploitation of self‐assembled amphipathic peptides as functional biomaterials.

Structure-Property Relation of Trimethyl Ammonium Ionic Liquids for Battery Applications

Ionic liquids are attractive and safe electrolytes for diverse electrochemical applications such as advanced rechargeable batteries with high energy densities. Their properties that are beneficial for energy storage and conversion include negligible vapor-pressure, intrinsic conductivity as well as high stability. To explore the suitability of a series of ionic liquids with small ammonium cations for potential battery applications, we investigated their thermal and transport properties. We studied the influence of the symmetrical imide-type anions bis(trifluoromethanesulfonyl)imide ([TFSI]−) and bis(fluorosulfonyl)imide ([FSI]−), side chain length and functionalization, as well as lithium salt content on the properties of the electrolytes. Many of the samples are liquid at ambient temperature, but their solidification temperatures show disparate behavior. The transport properties showed clear trends: the dynamics are accelerated for samples with the [FSI]− anion, shorter side chains, ether functionalization and lower amounts of lithium salts. Detailed insight was obtained from the diffusion coefficients of the different ions in the electrolytes, which revealed the formation of aggregates of lithium cations coordinated by anions. The ionic liquid electrolytes exhibit sufficient stability in NMC/Li half-cells at elevated temperatures with small current rates without the need of additional liquid electrolytes, although Li-plating was observed. Electrolytes containing [TFSI]− anions showed superior stability compared to those with [FSI]− anions in battery tests.

Xylan Structure and Dynamics in Native Brachypodium Grass Cell Walls Investigated by Solid-State NMR Spectroscopy.

The polysaccharide composition and dynamics of the intact stem and leaf cell walls of the model grass Brachypodium distachyon are investigated to understand how developmental stage affects the polysaccharide structure of grass cell walls. 13C enrichment of the entire plant allowed detailed analysis of the xylan structure, side-chain functionalization, dynamics, and interaction with cellulose using magic-angle-spinning solid-state NMR spectroscopy. Quantitative one-dimensional 13C NMR spectra and two-dimensional 13C–13C correlation spectra indicate that stem and leaf cell walls contain less pectic polysaccharides compared to previously studied seedling primary cell walls. Between the stem and the leaf, the secondary cell wall-rich stem contains more xylan and more cellulose compared to the leaf. Moreover, the xylan chains are about twofold more acetylated and about 60% more ferulated in the stem. These highly acetylated and ferulated xylan chains adopt a twofold conformation more prevalently and interact more extensively with cellulose. These results support the notion that acetylated xylan is found more in the twofold screw conformation, which preferentially binds cellulose. This in turn promotes cellulose–lignin interactions that are essential for the formation of the secondary cell wall.

Solid-Phase Synthesis of Gly-Ψ[CH(CF3)NH]-Peptides.

The solid-phase synthesis of Gly-Ψ[CH(CF3)NH]-peptides is presented. In order to achieve this goal, the synthesis of Gly-Ψ[CH(CF3)NH]-dipeptides having the C-terminus unprotected, the N-terminus protected as Fmoc- or Teoc-, and possibly side chain functionalities protected with acid-labile protecting groups has been developed. A selected small library of six peptidomimetics, encompassing analogues of biological relevant peptides, have been obtained in high purity.

Improving the performance of quaternized SEBS based anion exchange membranes by adjusting the functional group and side chain structure

Polystyrene-b-poly(ethylene-co-butylene)-b-polystyrene (SEBS) has attracted more and more attention recently for using as the matrix of anion exchange membranes (AEMs) in fuel cells due to its low cost, superior mechanical properties and ether-free total C-C bond backbone. In this work, the short side chain of chloromethyl and long side chain of bromohexanoyl groups are grafted into the SEBS copolymer via the chloromethylation and Friedel-Crafts acylation reactions. After quaternized by different nitrogen heterocyclic compounds including 1-methylimidazole (Im), 1-methylpyrrolidine (Mpy), N-methylpiperidine (Pip) and 2-methyl-1-pyrroline (Mpyl), various SEBSCn-x AEMs are prepared. Combing with small molecule model experiment results, Mpy and Pip cations grafted SEBS membranes are confirmed to possess good alkali resistance, while SEBSC1-x membranes with Im and Mpyl cations are not suitable for AEMs due to their poor alkaline stability. Meanwhile, long side-chain cation grafted SEBSC6-x AEMs with lower ion exchange capacity (IEC) values exhibit higher water uptake, ionic conductivity and mechanical strength simultaneously comparing with short side-chain cation grafted SEBSC1-x AEMs. As an example, the SEBSC6-Pip membrane with an IEC of 0.48 mmol g−1 exhibits a water uptake of 47% at 80 °C, an OH− conductivity of 57.7 mS cm−1 at 80 °C, a tensile strength of 52 MPa at room temperature, and a conductivity retention percent of 75% after 600 h in 1 M KOH at 80 °C, demonstrating a big potential for the AEM fuel cell application.

Polypeptides-Drug Conjugates for Anticancer Therapy.

Polypeptides are an important class of biodegradable polymers that have been widely used in drug delivery field. Owing to the controllable synthesis and robust side chain-functionalization ability, polypeptides have long been ideal candidates for conjugation with anticancer drugs. The chemical conjugation of anticancer drugs with polypeptides, termed polypeptides-drug conjugates, has demonstrated several advantages in improving pharmacokinetics, enhancing drug targeting, and controlling drug release, thereby leading to enhanced therapeutic outcomes with reduced side toxicities. This review focuses on the recent advances in the design and preparation of polypeptides-drug conjugates for enhanced anticancer therapy. Strategies for conjugation of different types of drugs, including small-molecule chemotherapeutic drugs, proteins, vascular disrupting agents, and gas molecules, onto polypeptides backbone are summarized. Finally, the challenges and future perspectives on the development of innovative polypeptides-drug conjugates for clinical cancer treatment are also presented.

Twisted Alkylthiothien‐2‐yl Flanks and Extended Conjugation Length Synergistically Enhanced Photovoltaic Performance by Boosting Dielectric Constant and Carriers Kinetic Characteristics

AbstractAlternating conjugated polymers (CPs), derived from 2‐ethylhexylthiothiophen‐2‐yl (TS) or 2‐ethylhexylthiophen‐2‐yl (T) flanked dithieno[3,2‐d:3,2‐d′]benzo[1,2‐b:4,5‐b′]dithiophene (DTBDT) and diketopyrrolo‐pyrrole (DPP) termed as PDTBDT‐TS‐DPP and PDTBDT‐T‐DPP, are prepared and characterized. It is found that the PDTBDT‐TS‐DPP not only exhibits slightly deepening the highest occupied molecular orbital energy levels, and similar absorption, etc., but also presents higher dielectric constant (εr) of 6.7 at 1 kHz in contrast to 3.2 for PDTBDT‐T‐DPP, which are even higher than those of 4.3 and 3.0 for PBDT‐TS‐DPP/PBDT‐T‐DPP generated from TS and T flanked benzo[1,2‐b:4,5‐bʹ]dithiophene and DPP. Beyond that, the power conversion efficiency of 8.17% for the inverted photovoltaic devices from DPP‐based CPs, is achieved from PDTBDT‐TS‐DPP. The alkylthio side chains are used in the DTBDT of the larger twisting angles of TS flanks and longer conjugation length, synergistically contribute to the highest dipole moments, and then lead to the enhancement of εr, thus devoted the modification exciton dissociation and charge carriers kinetic characteristics. To the authors’ knowledge, it is the first time to report that εr of the CPs is connected with the twisting angle of flanks and conjugation length of the building blocks, besides the use of functional side chains and atoms.

Decorating sdAbs with Chelators: Effect of Conjugation on Biodistribution and Functionality

Single domain antibodies (sdAbs) have proven to be valuable probes for molecular imaging. In order to produce such probes, one strategy is the functionalization of the reactive amine side chain of lysines with a chelator, resulting in a mixture of compounds with a different degree of conjugation. In this study, we implemented anion exchange chromatography (AEX) to separate the different compounds or fractions that were further characterized and evaluated to study the impact of the conjugation degree on pharmacokinetic properties and functionality. Anti-HER2 and anti-MMR sdAbs were functionalized with NOTA or DTPA chelator. Anion exchange chromatography was performed using 0.02 mol/L Tris pH 7.5 as the first solvent and 0.25 M or 0.4 M NaCl (in case of NOTA chelator or DTPA chelator, respectively) as the second solvent applied as a gradient. The fractions were characterized via mass spectrometry (MS), surface plasmon resonance (SPR), and isoelectric focusing gel electrophoresis (IEF), while in vivo studies were performed after radiolabeling with either 68Ga (NOTA) or 111In (DTPA) to assess the impact of the conjugation degree on pharmacokinetics. AEX could successfully be applied to separate fractions of (chelator)n-anti-HER2 and (chelator)n-anti-MMR sdAb constructs. MS confirmed the identity of different peaks obtained in the separation process. SPR measurement suggests a small loss of affinity for (chelator)3-anti-sdAb, while IEF revealed a correlated decrease in isoelectric point (pI) with the number of conjugated chelators. Interestingly, both the reduction in affinity and in pI was stronger with the DTPA chelator than with NOTA for both sdAbs. In vivo data showed no significant differences in organ uptake for any construct, except for (DTPA)n-anti-MMR, which showed a significantly higher liver uptake for (DTPA)1-anti-MMR compared to (DTPA)2-anti-MMR and (DTPA)3-anti-MMR. For all constructs in general, high kidney uptake was observed, due to the typical renal clearance of sdAb-based tracers. The kidney uptake showed significant differences between fractions of a same construct and indicates that a higher conjugation degree improves kidney clearance. AEX allows the separation of sdAbs with a different degree of conjugation and provides the opportunity to further characterize individual fractions. The conjugation of a chelator to sdAbs can alter some properties of the tracers, such as pI; however, the impact on the general biodistribution profile and tumor targeting was minimal.

A molecular dynamics study of the effect of functional groups and side chain on adsorption of alcoholic surfactant and interfacial thermal transport

In the present study, we investigated the effect of the number and position of functional groups, and the length of the main chain and side chain in organic surfactant on adsorption behavior and interfacial heat transfer between silica surface and alkane solvent by non-equilibrium molecular dynamics simulation, where the surfactants were primary/secondary alcohol, monohydric/dihydric alcohol, and linear/branched alcohol. The results showed a similar adsorption behavior for all the surfactant types, where hydroxyl functional (OH) groups adsorbed onto the silica surface and alkyl chain was in contact with the solvent, which produced a heat path from silica via surfactant to solvent. The number of adsorbed OH groups did not directly translate to significantly decreased thermal boundary resistance due to the adsorption structure. Coulomb interaction enabled the closer distance between primary terminal OH groups in surfactant and silica surface, which enhanced the solid-surfactant intermolecular heat transfer. However, Coulomb interaction contributed less to shorten the molecular distances between secondary OH groups in surfactant and silica surface, which was connected to less efficient heat transfer from silica to surfactant and thereby did not enhance the interfacial heat transfer as much as surfactants with terminal OH. The increase in terminal OH groups in the surfactant molecules could not significantly reduce thermal boundary resistance, although the adsorption amount of OH was distinctly greater than that of surfactants with single OH. The side chain in surfactant enabled the efficient surfactant-solvent intermolecular heat transfer but related to the desorption of surfactant when decreasing the temperature. Thus branched-chain dihydric alcohol performed better than other surfactants on reducing thermal boundary resistance when the interfacial temperature was high enough to maintain the sufficient adsorption amount. We considered such reverse temperature-sensitive surfactant has a great potential application to fulfill multiple needs for heat dissipation of electronic devices, especially the high temperature operation. The new insights obtained in the present study were a step towards a molecular structure design of surfactant enhancing solid–liquid interfacial heat transfer.

Investigating the effect of diverse structural variation of conjugated polymer electrolytes as the interlayer on photovoltaic properties

The effect of the diverse structural variation of conjugated polymer electrolytes (CPEs) as an interlayer on the photovoltaic properties was investigated. We found that the CPE with a strong electronegative BT group in the backbone and OH salt group in the side chain offers the highest PCEs among CPEs. • Diverse structural variation of conjugated polymer electrolytes (CPEs). • Step-by-step improvement in efficiency of solar cells based on diverse CPEs as interlayer. • Optical simulations of solar cells using transfer matrix formalism. A series of conjugated polymer electrolytes (CPEs) based on dimethylamino propyl fluorene (FN), thiophene (T), benzothiadiazole (BT), and dithienyl benzothiadiazole (TBT) were synthesized by the Suzuki coupling reaction. Quaternarized polyelectrolytes were obtained from the post-polymerization treatment of the amino-terminal group. The incorporation of electron-rich (T), electron-deficient moiety (BT), and their combination (TBT) in the polymer backbone represent the different effects of polarity. Conjugated backbones are substantially strengthened by varying their electron affinity and conjugated planarity. We systematically investigated the effect of applying CPEs with different backbones and functionalities in the side chain. Different backbones produce different molecular dipoles, and the side chain functionality induces an interfacial dipole. Inverted polymer solar cells (iPSCs) based on a bulk heterojunction (BHJ) were fabricated with the ITO/ZnO/CPE/PTB7-Th:PC 71 BM/MoO 3 /Ag structure. The device performance enhancement was achieved by inserting CPEs as the interlayer. Modifying the polymer backbone leads to improved efficiency and modifying the side chain functionality improves the performance compared with that of the interlayered neutral polymer.

Easily Functionalized and Readable Sequence-Defined Polytriazoles.

Developing sequence-defined skeletons that could be conveniently characterized and functionalized with diverse side groups is attractive but challenging. Here we report one novel sequence-defined polytriazole structure bearing side groups at its triazole rings. Its construction was facilely accessed by the iterative employments of azidation and iridium-catalyzed cycloaddition of azide with internal 1-thioalkyne (IrAAC) in solution phase. The easy preparation of 1-thioalkyne monomers and the excellent tolerance of IrAAC enable the introduction of diverse functional side chains to this architecture. The obtained sequence was effectively characterized by tandem mass spectrometry owing to the efficient fractures of both of the Csp3-S and Csp3-N bonds in its backbone, indicating its potential utilization in high-capacity digital polymer developments. Further successful application of this structure in building monodisperse macromolecules exhibiting aggregation-induced emission (AIE) characteristics demonstrates its expected application in functional material fabrications.