Side-chain Substitution Research Articles

Structural and Metal Ion Effects on Human Topoisomerase IIα Inhibition by α-(N)-Heterocyclic Thiosemicarbazones.

Our previous research has shown that α-(N)-heterocyclic thiosemicarbazone (TSC) metal complexes inhibit human topoisomerase IIα (TopoIIα), while the ligands without metals do not. To find out the structural elements of TSC that are important for inhibiting TopoIIα, we have synthesized two series of α-(N)-heterocyclic TSCs with various substrate ring segments, side chain substitutions, and metal ions, and we have examined their activities in TopoIIα-mediated plasmid DNA relaxation and cleavage assays. Our goal is to explore the structure-activity relationship of α-(N)-heterocyclic TSCs and their effect on TopoIIα. Our data suggest that, similar to Cu(II)-TSCs, Pd(II)-TSC complexes inhibit plasmid DNA relaxation mediated by TopoIIα. In TopoIIα-mediated plasmid DNA cleavage assays, the Cu(II)-TSC complexes induce higher levels of DNA cleavage than their Pd(II) counterparts. The Cu(II)-TSC complexes with methyl, ethyl, and tert-butyl substitutions are slightly more effective than those with benzyl and phenyl groups. The α-(N)-heterocyclic ring substrates of the TSCs, including benzoylpyridine, acetylpyridine, and acetylthiazole, do not exhibit a significant difference in TopoIIα-mediated DNA cleavage. Our data suggest that the metal ion of TSC complexes plays a predominant role in inhibition of TopoIIα, the side chain substitution of the terminal nitrogen plays a secondary role, while the substrate ring segment has the least effect. Our molecular modeling data support the biochemical data, which together provide a mechanism by which Cu(II)-TSC complexes stabilize TopoIIα-mediated cleavage complexes.

Antioxidant coumarin and pyrone derivatives from the insect-associated fungus Aspergillus Versicolor

Two new compounds, versicolones A and B (1 and 2), and three known pyrone derivatives (3−5) were isolated from the insect-associated fungus Aspergillus versicolor. Their structures were elucidated through a combination of HRESIMS and NMR spectroscopic analysis. Versicolone A (1) was revealed as a coumarin derivative with the rare 5-alkyl side chain substitution. Compound 5 exhibited significant antioxidant activity with EC50 value of 8.0 μM in the ABTS (2,2-azino-bis-3-ethylbenzothiazoline-6-sulfonic acid) assay, which was more than 2-fold potency of the positive control trolox.

Impact of Polymer Side Chain Modification on OPV Morphology and Performance

Efficiencies of organic photovoltaic (OPV) devices have been steadily climbing, but there is still a prominent gap in understanding the relationship between fabrication and performance. Side chain substitution is one processing parameter that can change OPV device efficiency considerably, primarily because of variations in morphology. In this work, we explain the morphological link between side chain selection and device performance in one polymer to aid in the development of design rules more broadly. We study the morphology of an OPV active layer using a PBDTTPD-backbone polymer with four different side chain configurations, which are shown to change device efficiency by up to 4 times. The optimal device has the smallest domain sizes, the highest degree of crystallinity, and the most face-on character. This is achieved with two branched 2-ethylhexyl (2EH) side chains placed symmetrically on the BDT unit and a linear octyl (C8) side chain on the TPD unit. Substituting either side chain (C14 on BDT and/or 2EH on TPD) makes the orientation less face-on, while the TPD side chain primarily affects domain size. For all side chains, the addition of fullerene increases polymer crystallization compared to the neat film, but the degree of mixing between polymer and fullerene varies with side chain. Interestingly, the optimal device has a negligible amount of mixed phase. The domain sizes present in the optimal system are remarkably unchanged with a changing fullerene ratio between 10 and 90%, hinting that the polymer preferentially self-assembles into 10-20 nm crystallites regardless of concentration. The formation of this crystallite may be the key factor inhibiting mixed phase.

Detailed Structural Characterization of Arabinans and Galactans of 14 Apple Cultivars Before and After Cold Storage.

Physiological and textural properties of apples are greatly influenced by both cultivar and structural composition of their pectic polysaccharides. In previous studies, it was demonstrated that neutral pectic side chains (arabinans and galactans) play a major role during fruit development and postharvest processes. However, these complex polymers have a high structural heterogeneity, and some structural elements such as side chain substituents and substitution of neighboring residues cannot be analyzed by using conventional analytical methods. Therefore, fine structures of arabinans and galactans were analyzed in 14 apple cultivars before and after storage. Besides conventional methods such as methylation analysis, profiling approaches based on enzymatic cleavage were applied to obtain detailed information on the neutral side chains of pectins. Structurally different, highly branched arabinans and linear β-1,4-linked galactans were detected in all cultivars. By using enzymatic profiling approaches, rare structural elements such as β-arabinofuranose and α-arabinopyranose residues were detected. In addition, the combination of all methods indicated structural differences with regard to ramification position or patterns. Cold storage resulted in decreased portions of branched arabinans. It was demonstrated that arabinan decomposition is independent of previously detected structural variations. In addition, analysis of endo-arabinanase hydrolysates demonstrated that β-arabinofuranose containing side chains are enriched after storage and may play a major role in postharvest processes. Analysis of endo-galactanase hydrolysates showed decreased portions of galactan-bound, terminal α-arabinopyranose units after storage. Therefore, these residues are most likely removed during postharvest galactan decomposition. The results of this study demonstrate the high complexity of neutral pectin side chains in apples and that pectic structural elements are differently prone to postharvest modifications.

Probing Backbone Hydrogen Bonds in Proteins by Amide‐to‐Ester Mutations

All proteins contain characteristic backbones formed of consecutive amide bonds, which can engage in hydrogen bonds. However, the importance of these is not easily addressed by conventional technologies that only allow for side-chain substitutions. By contrast, technologies such as nonsense suppression mutagenesis and protein ligation allow for manipulation of the protein backbone. In particular, replacing the backbone amide groups with ester groups, that is, amide-to-ester mutations, is a powerful tool to examine backbone-mediated hydrogen bonds. In this minireview, we showcase examples of how amide-to-ester mutations can be used to uncover pivotal roles of backbone-mediated hydrogen bonds in protein recognition, folding, function, and structure.

Complex Coacervates between a Lactose-Modified Chitosan and Hyaluronic Acid as Radical-Scavenging Drug Carriers.

Complex coacervation of two oppositely charged polysaccharides, namely a lactose-modified chitosan (CTL) and hyaluronan (HA), was investigated in this study. Coacervates of the two polysaccharides were prepared by drop-by-drop injection of HA into CTL. Transmittance and dynamic light scattering (DLS) measurements in combination with TEM analyses demonstrated the formation of spheroidal colloids in the nano-/microsize range showing good homogeneity. Strikingly, the presence of 150 mM supporting NaCl did not hamper the colloid formation. Stability studies on selected formulations demonstrated that HA/CTL coacervates were stable up to 3 weeks at 37 °C and behaved as pH-responsive colloids since transition from entangled to disentangled chains was attained for a proper pH range. The possibility of freeze-drying the coacervates for storage purposes and the ability of encapsulating selected payloads were investigated as well, for two values of the fraction of the lactitol side-chain substitution (FL). Finally, biological tests using human neutrophils were undertaken at acidic pH value (pH = 6.0): under such experimental conditions, akin to those frequently occurring in the inflammatory microenvironment, coacervates scavenged reactive oxygen species (ROS) generated by these cells in basal conditions. Given the well documented bioactivity of CTL with respect to chitosan toward cartilage regeneration, these findings point to a possible application of HA/CTL-based colloids as scavenging and bioactive carriers for the delivery of therapeutic molecules at confined inflamed sites such as knee joints.

First-principles study on vibrationally resolved fluorescence of fused 5,15-(diphenyl)-10,20-(dibromo)porphyrin molecule.

The vibrationally resolved fluorescence spectrum of a narrow-line single-molecule transducer, fused 5,15-(diphenyl)-10,20-(dibromo)porphyrin (fused-H2P) molecule, has been calculated by time-dependent density functional theory with the inclusion of both Franck-Condon and Herzberg-Teller contributions. Analytical transition dipole derivatives are used for the calculations of Herzberg-Teller terms to eliminate the possible errors caused by numerical differentials. The performance of different exchange-correlation functionals including B3LYP, ωB97X-D, and M06-2X has been examined. The comparison with the high-resolution experimental emission spectrum indicates that all three functionals can satisfactorily describe the fluorescence spectral profile, while ωB97X-D and M06-2X give slightly better excitation energy than B3LYP. Detailed analysis shows that the fluorescence spectrum is dominated by the Franck-Condon contribution, while the Herzberg-Teller term contributes mostly to its low energy tail. It is found that the size of the basis set has limited influence on the fluorescence spectrum, and a standard 6-31G(d, p) basis set is adequate for the purpose. The substitution of terthiophene side chains is found to have minor effects on the fluorescence spectrum. Our study provides unambitious assignments for all the vibronic structures in the experimental spectrum.

Understanding the Intrinsic Carrier Transport in Highly Oriented Poly(3-hexylthiophene): Effect of Side Chain Regioregularity.

The fundamental understanding of the influence of molecular structure on the carrier transport properties in the field of organic thermoelectrics (OTEs) is a big challenge since the carrier transport behavior in conducting polymers reveals average properties contributed from all carrier transport channels, including those through intra-chain, inter-chain, inter-grain, and hopping between disordered localized sites. Here, combining molecular dynamics simulations and experiments, we investigated the carrier transport properties of doped highly oriented poly(3-hexylthiophene) (P3HT) films with different side-chain regioregularity. It is demonstrated that the substitution of side chains can not only take effect on the carrier transport edge, but also on the dimensionality of the transport paths and as a result, on the carrier mobility. Conductive atomic force microscopy (C-AFM) study as well as temperature-dependent measurements of the electrical conductivity clearly showed ordered local current paths in the regular side chain P3HT films, while random paths prevailed in the irregular sample. Regular side chain substitution can be activated more easily and favors one-dimensional transport along the backbone chain direction, while the irregular sample presents the three-dimensional electron hopping behavior. As a consequence, the regular side chain P3HT samples demonstrated high carrier mobility of 2.9 ± 0.3 cm2/V·s, which is more than one order of magnitude higher than that in irregular side chain P3HT films, resulting in a maximum thermoelectric (TE) power factor of 39.1 ± 2.5 μW/mK2 at room temperature. These findings would formulate design rules for organic semiconductors based on these complex systems, and especially assist in the design of high performance OTE polymers.

Electron-Transporting Bis(heterotetracenes) with Tunable Helical Packing.

A novel kind of electron-deficient bis(heterotetracenes) namely perylenotetrathiophenediimides (PTTIs) involving double S-hetero[5]helicene diimides, is developed by a fourfold thienannulation route via ortho-functionalization of perylene diimides (PDIs). PTTIs exhibit significantly red-shifted absorption capacity with lowest-energy transition maxima beyond 700 nm and narrowed HOMO-LUMO energy gaps. Through delicately tuning the side-chain substitution, the distorted propeller-like framework could self-assemble into unprecedented 1D helical π-stacking structures with short π-π contacts and rich nonbonding interactions from alternating arrangements of P/M enantiomeric couples or tetrads. Excellent electron transporting efficiency in racemate PTTI crystals with 0.40 cm2 V-1 s-1 for 5 a and 0.90 cm2 V-1 s-1 for 5 b, was witnessed in single-crystalline transistors, signifying the prospects of the chiral π-helix in optoelectronic applications.

Dissecting the conformational determinants of chitosan and chitlac oligomers.

Chitosan and its highly hydrophilic 1-deoxy-lactit-1-yl derivative (Chitlac) are polysaccharides with increasing biomedical applications. Aimed to unravel their conformational properties we have performed a series of molecular dynamics simulations of Chitosan/Chitlac decamers, exploring different degrees of substitution (DS) of lactitol side chains. At low DS, two conformational regions with different populations are visited, while for DS ≥ 20% the oligomers remain mostly linear and only one main region of the glycosidic angles is sampled. These conformers are (locally) characterized by extended helical "propensities". Helical conformations 32 and 21, by far the most abundant, only develop in the main region. The accessible conformational space is clearly enlarged at high ionic strength, evidencing also a new region accessible to the glycosidic angles, with short and frequent interchange between regions. Simulations of neutral decamers share these features, pointing to a central role of electrostatic repulsion between charged moieties. These interactions seem to determine the conformational behavior of the chitosan backbone, with no evident influence of H-bond interactions. Finally, it is also shown that increasing temperature only slightly enlarges the available conformational space, but certainly without signs of a temperature-induced conformational transition.

Structurally Well-Defined Anion Conductive Aromatic Copolymers: Effect of the Side-Chain Length

For improving the alkaline stability and other properties of aromatic semiblock copolymer [QPE-bl-11a(C1)] membranes containing benzyltrimethylammonium groups, several novel hydrophilic monomers with different side-chain lengths and substitution positions were designed and synthesized for the polymerization. The pendant-type preaminated copolymers PE-bl-11s were quaternized using iodomethane to obtain the target QPE-bl-11s with well-defined chemical structure. In TEM analyses, QPE-bl-11a(C3) and QPE-bl-11a(C5) membranes with propyl and pentyl side-chains, respectively, showed more developed phase-separated morphology with greater hydrophilic domains (ca. 10–20 nm in width) than that of the C1 equivalent. The phase separation was more distinct and larger for the QPE-bl-11a membranes linked with p-phenylene groups in the hydrophilic part than for the QPE-bl-11b membranes with m-phenylene groups. In particular, QPE-bl-11b(C5) membrane exhibited considerably smaller hydrophilic/hydrophobic domains compared to...

Variation in Hemicellulose Structure and Assembly in the Cell Wall Associated with the Transition from Earlywood to Latewood in Cryptomeria japonica

The size of cellulose microfibril (CMF) bundles varies to interact with glucomannan/galactoglucomannan (GM/GGM). Arabino-4-O-methylglucuronoxylan (AGX) bonded CMF bundles coated with GM/GGM also have important roles in elaborating the distance between these components. Since the precise roles of GM/GGM and AGX are not clear, the elution analysis to evaluate the strength of the interaction between the cell wall were tried. Earlywood (EW) and latewood (LW) were separated in a Japanese cedar. The chemical components of cellulose, hemicellulose including GM/GGM and AGX, and lignin were almost the same in EW and LW. Slight differences in GM/GGM, the side-chain substitution in AGX and the ionic bond characteristics of glucuronic acid side chains were observed. Based on measurements of GM/GGM and AGX adhering to CMFs, there were more hemicelluloses forming strong hydrogen bonds in LW than in EW. The results showed that the highly assembled hemicellulose in LW produced a strong cell wall framework.

Insights into the Structural Determinants of Substrate Binding to Human Cytochromes P450 2C9 and 2C18

Xenobiotic metabolizing cytochrome P450 (CYP) enzymes constitute the major enzyme family in drug metabolism with increasing importance in pharmacogenetics, and more recently to pharmacogenomics. The highly polymorphic CYP2C9 metabolizes over 15% of clinical drugs that include ibuprofen, diclofenac, warfarin, losartan, tolbutamide, and glimepiride. Whereas CYP2C18 represents the least characterized enzyme with little information regarding substrates, the active site and the overall structure, despite the high sequence identity (more than 80%) with other human CYP2C subfamily of enzymes. Sequence alignment of CYP2C9 and 2C18 revealed interesting differences in amino acid substitutions, which allowed analysis of the active site of two enzymes of the same subfamily with distinct information regarding substrate specificity. A homology model of CYP2C18 created using the most recent crystal structure of CYP2C9‐losartan complex revealed key residue substitutions that significantly reduced the volume of the active site. In particular, the larger side chain substitutions L113, F201, F237 and N365 in CYP2C18 protrude the active site and play an important role in ligand interaction. Molecular docking studies using a diverse range of CYP2C9 substrates demonstrated remarkably altered orientation in the CYP2C18 active site indicative of differences in substrate preference compared to CYP2C9. The results suggest the active site architecture of CYP2C18 may not allow binding of larger or bulkier substrates as seen with other human CYP2C enzymes. Overall, the analysis of amino acid differences in the active site, the access channel and the recently identified potential substrate recognition site at the periphery provide important insights into the role of distinct side chain substitutions among related CYP enzymes.This abstract is from the Experimental Biology 2018 Meeting. There is no full text article associated with this abstract published in The FASEB Journal.

Effects of Side-Chain Topology on Aggregation of Conjugated Polymers

Controlling interchain interactions in conjugated polymers is critical to the development of high performance materials. These interchain interactions are dictated by the aggregation and self-assembly of conjugated polymers in solution and from processing steps, such as thermal annealing, in the solid state. Herein, a macrocyclic benzodithiophene building block for conjugated polymers is developed, and the properties of the resulting polymers are compared to analogous acyclic derivatives. The properties of small molecule macrocyclic BDT compounds show the influence of the side-chain substitution on the thermodynamic forces of self-assembly. Comparison of the optical properties of conjugated polymers with macrocyclic and acyclic side-chains in solution and the solid state reveals the ability of the macrocyclic side-chain to modify the structure of aggregates. Grazing incidence wide-angle X-ray scattering shows that the macrocyclic polymers can remain ordered in the solid state while having higher photolumi...

Decarboxylation involving a ferryl, propionate, and a tyrosyl group in a radical relay yields heme b

The H2O2-dependent oxidative decarboxylation of coproheme III is the final step in the biosynthesis of heme b in many microbes. However, the coproheme decarboxylase reaction mechanism is unclear. The structure of the decarboxylase in complex with coproheme III suggested that the substrate iron, reactive propionates, and an active-site tyrosine convey a net 2e-/2H+ from each propionate to an activated form of H2O2 Time-resolved EPR spectroscopy revealed that Tyr-145 formed a radical species within 30 s of the reaction of the enzyme-coproheme complex with H2O2 This radical disappeared over the next 270 s, consistent with a catalytic intermediate. Use of the harderoheme III intermediate as substrate or substitutions of redox-active side chains (W198F, W157F, or Y113S) did not strongly affect the appearance or intensity of the radical spectrum measured 30 s after initiating the reaction with H2O2, nor did it change the ∼270 s required for the radical signal to recede to ≤10% of its initial intensity. These results suggested Tyr-145 as the site of a catalytic radical involved in decarboxylating both propionates. Tyr-145• was accompanied by partial loss of the initially present Fe(III) EPR signal intensity, consistent with the possible formation of Fe(IV)=O. Site-specifically deuterated coproheme gave rise to a kinetic isotope effect of ∼2 on the decarboxylation rate constant, indicating that cleavage of the propionate Cβ-H bond was partly rate-limiting. The inferred mechanism requires two consecutive hydrogen atom transfers, first from Tyr-145 to the substrate Fe/H2O2 intermediate and then from the propionate Cβ-H to Tyr-145•.

The isotope effect on charge transport for bithiophene and di(n-hexyl)-bithiophene: impacts of deuteration position, deuteration number and side chain substitution position

The isotope effect on charge transport had been proposed to judge the transport mechanism in organic semiconductors. By using quantum nuclear tunneling model, we found that isotopic substitution could reduce mobility. For deeply understanding the impacts of the isotopic substitution position, substitution number and even molecular structure on the isotope effect, we take 2,2′-bithiophene and its dihexyl substitutions as examples to study the deuteration effect on hole transport. For deuterated–bithiophene, the isotope effect is linearly increasing with deuteration number. However, when the number is identical, deuteration on 5(5′)-position of thiophene will lead to stronger isotope effect than 3(3′)- or 4(4′)-position, since the reorganization energy contributed by 5-position hydrogen atoms is larger. For di(n-hexyl)-bithiophene isomers, 5,5′-dihexyl substitution also exhibits the strongest isotope effect after hexyl-deuteration or all-deuteration, due to the larger reorganization energy contributed by hexyl group in 5(5′)-position rather than 3(3′)- and 4(4′)-positions. Our calculation indicates that for identical system, the isotope effect is closely related to the number and position of isotopic atoms, while for isomers, the isotope effect is also related to the molecular configuration, such as the position of side chain substitution.

GH30 Glucuronoxylan-Specific Xylanase from Streptomyces turgidiscabies C56.

Endoxylanases are important enzymes in bioenergy research because they specifically hydrolyze xylan, the predominant polysaccharide in the hemicellulose fraction of lignocellulosic biomass. For effective biomass utilization, it is important to understand the mechanism of substrate recognition by these enzymes. Recent studies have shown that the substrate specificities of bacterial and fungal endoxylanases classified into glycoside hydrolase family 30 (GH30) were quite different. While the functional differences have been described, the mechanism of substrate recognition is still unknown. Therefore, a gene encoding a putative GH30 endoxylanase was cloned from Streptomyces turgidiscabies C56, and the recombinant enzyme was purified and characterized. GH30 glucuronoxylan-specific xylanase A of Streptomyces turgidiscabies (StXyn30A) showed hydrolytic activity with xylans containing both glucuronic acid and the more common 4-O-methyl-glucuronic acid side-chain substitutions but not on linear xylooligosaccharides, suggesting that this enzyme requires the recognition of glucuronic acid side chains for hydrolysis. The StXyn30A limit product structure was analyzed following a secondary β-xylosidase treatment by thin-layer chromatography and mass spectrometry analysis. The hydrolysis products from both glucuronoxylan and 4-O-methylglucuronoxylan by StXyn30A have these main-chain substitutions on the second xylopyranosyl residue from the reducing end. Because previous structural studies of bacterial GH30 enzymes and molecular modeling of StXyn30A suggested that a conserved arginine residue (Arg296) interacts with the glucuronic acid side-chain carboxyl group, we focused on this residue, which is conserved at subsite -2 of bacterial but not fungal GH30 endoxylanases. To help gain an understanding of the mechanism of how StXyn30A recognizes glucuronic acid substitutions, Arg296 mutant enzymes were studied. The glucuronoxylan hydrolytic activities of Arg296 mutants were significantly reduced in comparison to those of the wild-type enzyme. Furthermore, limit products other than aldotriouronic acid were observed for these Arg296 mutants upon secondary β-xylosidase treatment. These results indicate that a disruption of the highly conserved Arg296 interaction leads to a decrease of functional specificity in StXyn30A, as indicated by the detection of alternative hydrolysis products. Our studies allow a better understanding of the mechanism of glucuronoxylan recognition and enzyme specificity by bacterial GH30 endoxylanases and provide further definition of these unique enzymes for their potential application in industry.IMPORTANCE Hemicellulases are important enzymes that hydrolyze hemicellulosic polysaccharides to smaller sugars for eventual microbial assimilation and metabolism. These hemicellulases include endoxylanases that cleave the β-1,4-xylose main chain of xylan, the predominant form of hemicellulose in lignocellulosic biomass. Endoxylanases play an important role in the utilization of plant biomass because in addition to their general utility in xylan degradation, they can also be used to create defined compositions of xylooligosaccharides. For this, it is important to understand the mechanism of substrate recognition. Recent studies have shown that the substrate specificities of bacterial and fungal endoxylanases that are classified into glycoside hydrolase family 30 (GH30) were distinct, but the difference in the mechanisms of substrate recognition is still unknown. We performed characterization and mutagenesis analyses of a new bacterial GH30 endoxylanase for comparison with previously reported fungal GH30 endoxylanases. Our study results in a better understanding of the mechanism of substrate specificity and recognition for bacterial GH30 endoxylanases. The experimental approach and resulting data support the conclusions and provide further definition of the structure and function of GH30 endoxylanases for their application in bioenergy research.

Water and hydrophobic gates in ion channels and nanopores.

Ion channel proteins form nanopores in biological membranes which allow the passage of ions and water molecules. Hydrophobic constrictions in such pores can form gates, i.e. energetic barriers to water and ion permeation. Molecular dynamics simulations of water in ion channels may be used to assess whether a hydrophobic gate is closed (i.e. impermeable to ions) or open. If there is an energetic barrier to water permeation then it is likely that a gate will also be impermeable to ions. Simulations of water behaviour have been used to probe hydrophobic gates in two recently reported ion channel structures: BEST1 and TMEM175. In each of these channels a narrow region is formed by three consecutive rings of hydrophobic sidechains and in both cases such analysis demonstrates that the crystal structures correspond to a closed state of the channel. In silico mutations of BEST1 have also been used to explore the effect of changes in the hydrophobicity of the gating constriction, demonstrating that substitution of hydrophobic sidechains with more polar sidechains results in an open gate which allows water permeation. A possible open state of the TMEM175 channel was modelled by the in silico expansion of the hydrophobic gate resulting in the wetting of the pore and free permeation of potassium ions through the channel. Finally, a preliminary study suggests that a hydrophobic gate motif can be transplanted in silico from the BEST1 channel into a simple β-barrel pore template. Overall, these results suggest that simulations of the behaviour of water in hydrophobic gates can reveal important design principles for the engineering of gates in novel biomimetic nanopores.

The effect of side-chain substitution on the aggregation and photovoltaic performance of diketopyrrolopyrrole-alt-dicarboxylic ester bithiophene polymers

Alternating donor–acceptor polymers of diketopyrrolopyrrole and quaterthiophene with electron-withdrawing ester groups are studied to reduce the photon energy loss in solar cells.

Optical properties and structural morphology of one-dimensional perylenediimide derivatives

Three derivatives of perylene diimide, namely N,N′-ditridecylperylene-3,4,9,10-tetracarboxylic diimide (DT-PDI), N,N′-dipentylperylene-3,4,9,10-tetracarboxylic diimide (DP-PDI) and N,N′-bis(1-hexylheptyl)perylene-3,4,9,10-tetracarboxylic diimide (DH-PDI) differ in their side-chain substitution have been examined to study the effect of side-chain substituents on their optical properties and structural morphology. Due to the different side-chain, the self-assembly of these molecules results in totally different optical properties and structural morphologies, as confirmed from the steady-state absorption and fluorescence, time resolved fluorescence, and scanning electron microscopy (SEM) techniques. The collected results confirmed the formation of one-dimensional (1D) nanowires in the case of short linear side chain, chunky aggregates in the case of long linear substituted side chain, and zero-dimensional (0D) nanospheres with the branched substituted side chain.