Impact Of Side Chains Research Articles

Nucleobase-Functionalized 7-Deazaisoguanine and 7-Deazapurin-2,6-diamine Nucleosides: Halogenation, Cross-Coupling, and Cycloaddition.

The functionalization in position-7 of 7-deazaisoguanine and 7-deazapurin-2,6-diamine ribo- and 2'-deoxyribonucleosides by halogen atoms (chloro, bromo, iodo), and clickable alkynyl and vinyl side chains for copper-catalyzed and copper-free cycloadditions is described. Problems arising during the synthesis of the 7-iodinated isoguanine ribo- and 2'-deoxyribonucleosides were solved by the action of acetone. The impact of side chains and halogen atoms on the pKa values and hydrophobicity of nucleosides was investigated. Halogenated substituents increase the lipophilic character of nucleosides in the order Cl < Br < I and decrease the pK values of protonation. Photophysical properties (fluorescence, solvatochromism, and quantum yields) of azide-alkyne click adducts bearing pyrene as sensor groups were determined. Pyrene fluorescence was solvent-dependent and changed according to the linker lengths. Excimer emission was observed in dioxane for the long linker adduct. Bioorthogonal inverse-electron-demanding Diels-Alder cycloadditions (iEDDA) were conducted on the electron-rich vinyl groups of 7-deazaisoguanine and 7-deazapurin-2,6-diamine nucleosides as dienophiles and 3,6-dipyridyl-1,2,4,5-tetrazine as diene. The initially formed complex reaction mixture of isomers could be easily oxidized with iodine in tetrahydrofuran (THF)/pyridine leading to single aromatic tetrazine adducts within a short time and in excellent yields.

Non-fused ring electron acceptors employing diphenylamine substituted 2,2′-bithiazole cores for organic solar cell applications

The impact of side chains on the performance of 2,2′-bithiazole based non-fused ring electron acceptors is investigated.

Side-chain engineering of organic photothermal agents for boosting further red-shifted absorption and higher photothermal therapeutic effect

Although organic photothermal agents (PTAs) have been extensively studied in preclinical cancer photothermal therapy (PTT), the internal mechanism, particularly the impact of side chains on photothermal performance, remains inadequately investigated. Herein, we conducted a systematic comparison of the photothermal properties between two organic molecules, namely O-IDTBR with four n-octyl chains and EH-IDTBR with four 2-ethylhexyl chains. With the same conjugated main structure, both O-IDTBR and EH-IDTBR exhibited nearly identical absorption properties (with a peak at 629 nm) in their molecular states. Interestingly, after the formation of nanoparticles (NPs), O-IDTBR NPs with linear alkyl chains exhibit a further red-shifted absorption onset (peak at 711 nm) compared to EH-IDTBR NPs (peak at 662 nm) with branched alkyl chains. Additionally, the photothermal conversion efficiency of O-IDTBR NPs was calculated of 33.7%, which is higher than that of EH-IDTBR NPs (27.7%). This can be attributed to the fact that linear alkyl chains of O-IDTBR NPs promote more intramolecular motions at the aggregated state by extending intermolecular distance and distorting molecular conformation. Therefore, the nonradiative thermal deactivation-induced photothermal property can be further enhanced. Through both in vitro and in vivo experiments, O-IDTBR NPs exhibit effective PTT effect and excellent biocompatibility. This study not only introduces a novel PTA but also opens new avenues for exploring organic optical nano-agents through side-chain engineering to adjust intramolecular motions at the aggregated state.

Impact of side-chains in poly(dibenzyl-co-terphenyl piperidinium) copolymers for anion exchange membrane fuel cells

Anion exchange membrane fuel cells (AEMFCs) have experienced rapid advancement in the past few years due to the discovery of high-performance AEMs and ionomers. Here, we report a series of side-chain-type poly(dibenzbeyl-co-terphenyl piperidinium) ( s -PDTP) copolymers as ionomers and membranes for AEMFC applications. The features of aryl ether-free PDTP polymer backbone and pendent ammonium groups endow both high alkaline stability and excellent micromorphology to s -PDTP copolymers. These ion-exchange-capacity (IEC)-controlled s -PDTP membranes possess high OH − conductivity >120 mS cm −1 at 80 °C, reasonable molecular weight (M w = 150–290 kDa), and excellent ex-situ durability in 1 M NaOH at 80 °C for 1000 h (∼90% conductivity remaining). For ionomer research, s -PDTP ionomers with moderate IEC (∼3.0 mmol g −1 ) and rational water uptake (∼200%) exhibit optimal AEMFC performance based on a PDTP membrane compared to high-IEC or low-IEC s -PDTP ionomers (>3.4 mmol g −1 or <2.4 mmol g −1 ). Based on Pt/C, s -PDTP-based AEMFCs reach a peak power density (PPD) of 1.47 W cm −2 in H 2 –O 2 and 1.04 W cm −2 in H 2 -air (CO 2 -free) at 80 °C. • IEC-controlled side-chain-type poly(aryl-co-aryl piperidinium)s is developed. • The effect of IECs on the performance of s-PDTP- x ionomers and AEMs is elucidated. • s-PDTP- x copolymers display excellent durability >1000 h in 1 M NaOH at 80 °C. • s-PDTP-based AEMFCs reach power densities of 1.04 W cm −2 in H 2 -air.

Side-chain effect in ethenylene fused thiophene-vinylene-thiophene (ETVT) based photovoltaic polymers

To investigate side chain effect of ETVT based photovoltaic polymers, we designed and synthesized the polymers with different solubilizing substituents. The impact of side chains on the solubility, planarity, optical and electronic properties of these ETVT based conjugated polymers was systematically studied. Extending the intrinsic alkyl group or adding new alkyl substituent to the polymer obviously increased the solubility of the resulting polymers. Thus, the polymerization reaction yield was improved to 88% and 81%, for PETVT-TBT24 and PETVT8-TBT, compared to that of 39% for PETVT-TBT. PETVT8-TBT showed blue-shifted absorption spectrum, reduced hole mobility and consequently inferior photovoltaic performance, owing to the steric hindrance caused by redundant octyl group on ETVT unit. However, the introduction of alkyl substitutes in ETVT remarkably increases the open-circuit voltage of PETVT8-TBT based PSCs to 1.03 V, by both decreasing HOMO of the polymer and reducing the energy losses. Extending the intrinsic alkyl group resolved the problem of low solubility of PETVT-TBT, and furthermore, was benefit to improve charge carrier mobility in the resulting polymer based solar cells. As a result, PETVT-TBT24 basically maintained the advantages of ETVT based photovoltaic polymers, realizing a moderate PCE of 7.8% when paired with the non-fullerene acceptor of ITIC.

Dithienopyrrole-benzodithiophene based donor materials for small molecular BHJSCs: Impact of side chain and annealing treatment on their photovoltaic properties

Two small molecular organic materials denoted as ICT1 and ICT2 with A-D1-D2-D1-A architecture have been synthesized and their thermal, photo-physical, electrochemical and photovoltaic properties are explored. Synthesized materials have n-butylrhodanine acceptor (A), dithienopyrrole (DTP) (D1) and benzodithiophene (BDT) (D2) (Alkoxy BDT and alkylthiophene BDT, respectively for ICT1 and ICT2) donor moieties. Both the materials have good solubility (up to 25 mg/mL) in most common organic solvents and have excellent thermal stability with the decomposition temperature (Td) as 348 and 382 °C, respectively for ICT1 and ICT2. Both ICT1 and ICT2 have broad and intense visible region absorption (molar excitation coefficient is 1.71 × 105 and 1.65 × 105 mol−1 cm−1, respectively for ICT1 and ICT2) and have suitable HOMO and LUMO energy levels for PC71BM acceptor. Bulk heterojunction solar cells with ITO/PEDOT:PSS/blend/Al structure are fabricated using these materials. The BHJSCs fabricated by spin cast of ICT1:PC71BM and ICT2:PC71BM (1:2 wt ratio) blend from chloroform showed power conversion efficiency (PCE) of 2.77% (Jsc = 6.84 mA/cm2, Voc = 0.92 V and FF = 0.44) and 3.27% (Jsc = 7.26 mA/cm2, Voc = 0.96 V and FF = 0.47), respectively. Annealing the active layer significantly improved the PCE of these BHJSCs to 5.12% (Jsc = 10.15 mA/cm2, Voc = 0.87 V and FF = 0.58) and 5.90% (Jsc = 10.68 mA/cm2, Voc = 0.92 V and FF = 0.60), respectively for ICT1 and ICT2 donors. The enhancement in the PCE is due to higher light harvesting ability of the active layer, better nanoscale morphology for efficient and balanced charge transport and effective exciton dissociation at the donor-acceptor interface.

Solubility of non-ionic poly(fluorooxetane)-block-(ethylene oxide)-block-(fluorooxetane) surfactants in carbon dioxide

The impact of side chain and midblock length on the solubility of ABA triblock copolymers of fluorooxetane-(ethylene oxide)-fluorooxetane in carbon dioxide is examined. The use of short fluorinated side chains instead of long fluorinated chains prevents issues with bioaccumulation of the degradation products of the surfactant. At 40 °C for the same degree of polymerization, increasing the number of perfluoro-units from one to four results in a non-monotonic change in the cloud point pressure; the cloud point pressure decreases as the side chain is increased from perfluoromethyl to perfluoroethyl. However, further increasing the fluorinated side chain to perfluorobutyl results in a significant increase in the cloud point. However when the temperature is increased to 60 °C, the cloud point pressure for the surfactants with perfluoroethyl and perfluorobutyl side chains is statistically similar, while the perfluoromethyloxetane based surfactant requires a substantially larger pressure to obtain comparable solubility. An increase in cloud point pressure is observed when increasing the hydrophilic ethylene oxide segment. These results illustrate that commercially available fluorooxetane-(ethylene oxide)-fluorooxetane surfactants are highly soluble in CO 2.

Relationship between supramolecular assembly and charge-carrier mobility in perylenediimide derivatives: The impact of side chains

Discotic mesophases are known for their ability to self-assemble into columnar structures which serve as semiconducting molecular wires. Charge-carrier mobility along these wires strongly depends on molecular packing which is controlled by intermolecular interactions. Using solid-state NMR and molecular dynamics simulations we relate how conformations of alkyl and glycol side chains affect helical pitch and angular distribution of molecules within the columnar structures of perylenediimide derivatives. Using the high-temperature limit of Marcus theory we then establish a link between the secondary structure and charge-carrier mobility. Simulation results are compared to pulse-radiolysis time-resolved microwave conductivity measurements. We conclude that for achieving high charge-carrier mobilities in discotics, side chains with specific interactions are required in order to minimize the translational and orientational molecular disorder in the columns.