Properties Of Donor Research Articles

Neutral donors confined in semiconductor coupled quantum dot-rings: Position-dependent properties and optical transparency phenomenon

Electronic properties of a neutral donor confined in a GaAs coupled quantum dot-ring covered by a Al0.3Ga0.7As matrix were calculated using the finite element method under the effective mass and the envelope function approximations. The proposed model is set up to fit a realistic coupled quantum dot-ring geometry revealed by atomic force microscopy images. The results show that the energy levels and the transition energies in the presence of an electric field strongly depend on the donor center’s angular position. Furthermore, the total optical absorption coefficient is calculated within the two-level approximation and the matrix density formalism. The absorption spectrum shows that the system can be tuned between 5 and 30meV. Also, an optical transparency effect for different configurations characterized by specific donor center’s angular positions and electric field values is seen. Finally, a novel redshift is observed when the sample temperature increases.

Illuminating the Performance of Electron Withdrawing Groups in Halogen Bonding.

Throughout the halogen bonding literature, electron withdrawing groups are relied upon heavily for tuning the in- teraction strength between the halogen bond donor and acceptor; however, the interplay of electronic effects associated with various substituents is less of a focus. This work utilizes computational techniques to study the degree ofσ- andπ- electron donating/accepting character of electron withdrawing groups in a prescribed set of halo-alkyne, halo-benzene, and halo-ethynyl benzene halogen bond donors. We examine how these factors affect theσ-hole magnitude of the donors as well as the binding strength of the corresponding complexes with an ammonia acceptor. Statistical analyses aid the interpretation of how these substituents influence the properties of the halogen bond donors and complexes, and show that the electron withdrawing groups that are bothσ- andπ-electron accepting form the strongest halogen bond complexes.

Photophysical properties of donor (D)-acceptor (A)-donor (D) diketopyrrolopyrrole (A) systems as donors for applications to organic electronic devices.

Fourteen substituted diketopyrrolopyrrole (DPP) molecules in a donor (D)-acceptor (DPP)-donor (D) arrangement were designed. We employed density functional theory, time-dependent DFT, DFT-MRCI and the ab initio wave function second-order algebraic diagrammatic construction (ADC(2)) methods to investigate theoretically these systems. The examined aromatic substituents have one, two, or three hetero- and non-hetero rings. We comprehensively investigated their optical, electronic, and charge transport properties to evaluate potential applications in organic electronic devices. We found that the donor substituents based on one, two, or three aromatic rings bonded to the DPP core can improve the efficiency of an organic solar cell by fine-tuning the highest occupied molecular orbital/lowest unoccupied molecular orbital levels to match acceptors in typical bulk heterojunctions acceptors. Several properties of interest for organic photovoltaic devices were computed. We show that the investigated molecules are promising for applications as donor materials when combined with typical acceptors in bulk heterojunctions because they have appreciable energy conversion efficiencies resulting from their low ionization potentials and high electron affinities. This scenario allows a more effective charge separation and reduces the recombination rates. A comprehensive charge transfer analysis shows that D-A (DDP)-D systems have significant intramolecular charge transfer, further confirming their promise as candidates for donor materials in solar cells. The significant photophysical properties of DPP derivatives, including the high fluorescence emission, also allow these materials to be used in organic light-emitting diodes.

Aryl-Substituted Acridine Donor Derivatives Modulate the Transition Dipole Moment Orientation and Exciton Harvesting Properties of Donor-Acceptor TADF Emitters.

Thermally activated delayed fluorescence (TADF) compounds are highly attractive as sensitizing and emitting materials for organic light-emitting diodes (OLEDs). The efficiency of the OLED depends on multiple parameters, most of which rely on the properties of the emitter including those that govern the internal quantum and outcoupling efficiencies. Herein, we investigate a series of aryl substituted acridine donor derivatives of the donor-acceptor TADF emitter DMAC-TRZ, with the objective of correlating their properties, such as triplet harvesting efficiency and transition dipole moment orientation, with their corresponding device efficiency. The decoration of the DMAC donor with substituted aryl groups not only modifies the molecular weight and length of the emitter but also affects the emission color and the capacity for the emitters to efficiently harvest triplet excitons. The presence of electron-withdrawing 4-cyanophenyl and 4-trifluoromethylphenyl groups in, respectively, CNPh-DMAC-TRZ and CF3Ph-DMAC-TRZ, blue-shifts the emission spectrum but slows down the reverse intersystem crossing rate constant (k RISC), while the opposite occurs in the presence of electron-donating groups in t BuPh-DMAC-TRZ and OMePh-DMAC-TRZ (red-shifted emission spectrum and faster k RISC). In contrast to our expectations, the OLED performance of the five DMAC-TRZ derivatives does not scale with their degree of horizontal emitter orientation but follows the k RISC rates. This, in turn, demonstrates that triplet harvesting (and not horizontal emitter orientation) is the dominant effect for device efficiency using this family of emitters. Nonetheless, highly efficient OLEDs were fabricated with t BuPh-DMAC-TRZ and OMePh-DMAC-TRZ as emitters, with improved EQEmax (∼28%) compared to the reference DMAC-TRZ devices.

Photophysical properties of donor–acceptor antiaromatic organoboron compounds based on dithienodiborinines

Abstract Boron-containing antiaromatics, such as diborinines and boroles, have sparked interest in materials chemists owing to their exciting optical properties and high Lewis acidity. In this study, we synthesized donor–acceptor (D–A) type diborinines fused with thiophene rings by introducing electron-donating amino-substituted aryl groups onto boron and elucidated their properties. The D–A type dithienodiborinines exhibited long-wavelength absorption arising from their D–A interactions and antiaromaticity. In addition, their fluorescence intensity increased under oxygen-free conditions, indicating thermally activated delayed fluorescence.

High-resolution Cell Transplantation in Embryonic and Larval Zebrafish.

Development and regeneration occur by a process of genetically encoded spatiotemporally dynamic cellular interactions. The use of cell transplantation between animals to track cell fate and to induce mismatches in the genetic, spatial, or temporal properties of donor and host cells is a powerful means of examining the nature of these interactions. Organisms such as chick and amphibians have made crucial contributions to our understanding of development and regeneration, respectively, in large part because of their amenability to transplantation. The power of these models, however, has been limited by low genetic tractability. Likewise, the major genetic model organisms have lower amenability to transplantation. The zebrafish is a major genetic model for development and regeneration, and while cell transplantation is common in zebrafish, it is generally limited to the transfer of undifferentiated cells at the early blastula and gastrula stages of development. In this article, we present a simple and robust method that extends the zebrafish transplantation window to any embryonic or larval stage between at least 1 and 7 days post fertilization. The precision of this approach allows for the transplantation of as little as one cell with near-perfect spatial and temporal resolution in both donor and host animals. While we highlight here the transplantation of embryonic and larval neurons for the study of nerve development and regeneration, respectively, this approach is applicable to a wide range of progenitor and differentiated cell types and research questions.

Electronic Control of Polyproline II Helix Stability via the Identity of Acyl Capping Groups: the Pivaloyl Group Particularly Promotes PPII.

The type II polyproline helix (PPII) is a fundamental secondary structure of proteins, important in globular proteins, in intrinsically disordered proteins, and at protein-protein interfaces. PPII is stabilized in part by n→π* interactions between consecutive carbonyls, via electron delocalization between an electron-donor carbonyl lone pair (n) and an electron-acceptor carbonyl (π*) on the subsequent residue. We previously demonstrated that changes to the electronic properties of the acyl donor can predictably modulate the strength of n→π* interactions, with data from model compounds, in solution in chloroform, in the solid state, and computationally. Herein, we examined whether the electronic properties of acyl capping groups could modulate the stability of PPII in peptides in water. In X-PPGY-NH2 peptides (X=10 acyl capping groups), the effect of acyl group identity on PPII was quantified by circular dichroism and NMR spectroscopy. Electron-rich acyl groups promoted PPII relative to the standard acetyl (Ac-) group, with the pivaloyl and iso-butyryl groups most significantly increasing PPII. In contrast, acyl derivatives with electron-withdrawing substituents and the formyl group relatively disfavored PPII. Similar results, though lesser in magnitude, were also observed in X-APPGY-NH2 peptides, indicating that the capping group can impact PPII conformation at both proline and non-proline residues. The pivaloyl group was particularly favorable in promoting PPII. The effects of acyl capping groups were further analyzed in X-DfpPGY-NH2 and X-ADfpPGY-NH2 peptides, Dfp=4,4-difluoroproline. Data on these peptides indicated that acyl groups induced order Piv- > Ac- > For-. These results suggest that greater consideration should be given to the identity of acyl capping groups in inducing structure in peptides.

Understanding the impact of thiazole unit sequence in π-bridge on the performance of small molecule donor materials

Energy level regulation and crystallization optimization of materials are the key ideas to improve the performance of organic solar cells. In this work, based on clarifying small molecule structure, we introduce thiazole into different positions of π-bridge and investigate its effect on the properties of small molecule donors (SMDs) and related device performance. As thiazole gradually moves towards BDT, the electron clouds of these three SMDs (BTTTzR, BTTzTR and BTzTTR) tend to be divided on the framework, gradually deepened the energy level, and enlarged band gaps. In terms of device performance, the BTTzTR:Y6 device shows good inhibition of charge recombination and phase separation performance, and the efficiency of the related OSCs is 7.87 %. Morphological analysis shows that BTTTzR is prone to form nanoscale microcrystals after thermal annealing treatment, with slightly decreased performance of 6.79 %. BTzTTR is affected by difficult intramolecular charge transfer and weak intermolecular interactions, shows the worst performance of 5.77 %. This work is conducive to a deeper understanding of the electron-deficient substitution of the π-bridge in SMDs.

Efficient doping of functionalized graphene and h-BN by molecular adsorption

In this work, we investigate the structural and electronic properties of molecular acceptors and donors adsorbed on H/F-functionalized graphene and h-BN by using first principles calculation. Graphane adsorbed with acceptors show p-type doping features, and fluorographene with donors are n-type doping. On the other hand, both H- and F-functionalized BN adsorbed systems exhibit n-type doping. The different doping characteristics depend on the relative energy level alignment of the molecules and substrates, which determines the electron transfer direction. In addition, the bands of adatoms are close to the band edges of substrates near Fermi level (0.0004–0.113 eV), denoting the efficient doping for H/F-functionalized graphene and h-BN. These results provide important indications for designing novel two-dimensional materials with suitable doped characteristics for opto-electronics applications.

Tuning the adsorptive and photocatalytic properties of donor–acceptor covalent organic polymers with varying hydroxyl ratios

Covalent organic polymers and frameworks have excellent potential to degrade and eliminate organic pollutants in industrial wastewater. Herein, a family of donor–acceptor covalent organic polymers (D–A COPs) that contain thiazole units and varying amounts of hydroxyl groups from 0 to 100 %, have been designed and synthesized for improved adsorption and photocatalytic performance. Compared with COPs containing hydroxyl groups, NXCOP-3000 without a hydroxyl group is more effective in the adsorption of organic dye pollutants, and the maximum adsorption capacity was 122.5 mg g−1, which is also supported by the theoretical simulation. The more the hydroxyl group content is, the narrower the band gap is in this case. Interestingly, NXCOP-3075 with a 75 % hydroxyl group has demonstrated superior photocatalytic activity, where the dye removal efficiency reaches 98.87 %, which suggests that these COPs create efficient carrier pathways to separate photogenerated holes and electrons efficiently. Therefore, introducing hydroxyl groups into COP can be used as a strategy to enhance photocatalytic activity.

Elucidating the Role of Electron-Donating Groups in Halogen Bonding.

Computational quantum chemical techniques were utilized to systematically examine how electron-donating groups affect the electronic and spectroscopic properties of halogen bond donors and their corresponding complexes. Unlike the majority of studies on halogen bonding, where electron-withdrawing groups are utilized, this work investigates the influence of electron-donating substituents within the halogen bond donors. Statistical analyses were performed on the descriptors of halogen bond donors in a prescribed set of archetype, halo-alkyne, halo-benzene, and halo-ethynyl benzene halogen bond systems. The σ-hole magnitude, binding and interaction energies, and the vibrational X···N local force constant (where X = Cl, Br, I, and At) were found to correlate very well in a monotonic and linear manner with all other properties studied. In addition, enhanced halogen bonds were found when the systems contained electron-donating groups that could form intramolecular hydrogen bonds with the electronegative belt of the halogen atom and adjacent linker features.

Fluorinated Polymer Donors for Nonfullerene Organic Solar Cells.

The rapid development of narrow-bandgap nonfullerene acceptors (NFAs) has boosted the efficiency of organic solar cells (OSCs) over 19 %. The new features of high-performance NFAs, such as visible-NIR light absorption, moderate the highest occupied molecular orbitals (HOMO), and high crystallinity, require polymer donors with matching physical properties. This emphasizes the importance of methods that can effectively tune the physical properties of polymers. Owning to very small atom size and strongest electronegativity, the fluorination has been proved the most efficient strategy to regulate the physical properties of polymer donors, including frontier energy level, absorption coefficient, dielectric constant, crystallinity and charge transport. Owing to the success of fluorination strategy, the vast majority of high-performance polymer donors possess one or more fluorine atoms. In this review, the fluorination synthetic methods, the synthetic route of well-known fluorinated building blocks, the fluorinated polymers which are categorized by the type of donor or acceptor units, and the relationships between the polymer structures, properties, and photovoltaic performances are comprehensively surveyed. We hope this review could provide the readers a deeper insight into fluorination strategy and lay a strong foundation for future innovation of fluorinated polymers.

Effect of Seleno-Thiophene π-Linkers on Electronic and Photovoltaic Properties of Boro-Phenothiazine Donors for DSSCs Application: TD-DFT and DFT Methods

Effect of Seleno-Thiophene π-Linkers on Electronic and Photovoltaic Properties of Boro-Phenothiazine Donors for DSSCs Application: TD-DFT and DFT Methods

Candidate molecules as alternative nitric oxide donors with better antibacterial property against Escherichia coli and Staphylococcus aureus.

Four nitric oxide (NO) donors, S-nitrosoglutathione (GSNO), S-nitrosocysteine (CySNO), S-nitroso-N-acetylcysteine (SNAC), and 2-(2-S-nitroso propionamide) acetic acid (GAS) were prepared and their physicochemical characteristics were analyzed. Besides, the antibacterial properties of NO donors were investigated against Escherichia coli and Staphylococcus aureus. UV-visible absorption spectrum and Fourier transform infrared spectrum verified the successful preparation of RSNOs. All NO donors (10mmol l-1) could release NO continuously, and the amount of NO release was from 80.22 μmol l-1 to 706.63 μmol l-1, in which the release of NO from SNAC was the highest, and the release of NO from NaNO2 was the least. The inhibition zone indicated that all NO donors showed stronger antibacterial activity against E. coli and S. aureus, and the antibacterial ability was in the order of SNAC>GSNO>CySNO>GAS>NaNO2 for both E. coli and S. aureus (P<0.05). Scanning electron microscopy(SEM) showed that all NO donors could result in varying degrees of damage to cell wall and membrane of both E. coli and S. aureus and the damage of E. coli was more severe. Four alternative NO donors were successfully synthesized. All alternative NO donors showed better antibacterial properties against E. coli and S. aureus than NaNO2.

Theoretical study of the effect of D-A type polymer donors on the performance of Y6-based organic solar cells

Non-fullerene organic solar cells (OSCs) based on Y6 molecule have developed rapidly in recent years, and the power conversion efficiency (PCE) varies greatly when the OSC device constructed by Y6 and donor molecules with small structural difference. In this work, the influence of six donor-acceptor (D-A) polymer donors on Y6-based OSCs were focused. The ground-state properties (planarity, frontier molecular orbital energy levels, driving force), excited-state properties of donors (primary indicators, Coulomb attraction) and donor/acceptor interfaces (Frenkel excitation (FE) and charge transfer (CT) states, electron coupling and charge separation rates) were discussed. The results show that symmetrical alkyl chains in the acceptor unit is favorable for maintaining planarity of molecule, while fluorination induces twisting in the thiophene bridge and acceptor unit. And the investigated high-performance molecules have desirable driving force, smaller Coulomb attraction and significant degree of holes and electrons delocalization. Also, the highest-performance system has multiple charge transfer pathways, which can improve charge separation efficiency. At the same time, high-performance systems often have better planarity and more favorable substituent positions. The high-performance donor/Y6 systems have more advantage in charge separation than the low-performance systems. This work provides a fundamental understanding of the impact of D-A type donor materials on the cell performance and theoretical guidance for further optimization of polymer donor materials in Y6-based OSCs.

Origin of high comprehensive electromechanical properties of novel donor and acceptor–codoped PMN–30PT ceramics

Donor and acceptor–codoped PMN–30PT ceramics with 1–3 mol% Sm and 1 mol% Mn were fabricated via a two-step solid-state reaction. The crystal structure and electrical properties were investigated in detail. Donor Sm and acceptor Mn codoping substantially enhances the electromechanical, piezoelectric, and dielectric properties with a high piezoelectric coefficient d33 = 483–680 pC/N, a high mechanical quality factor Qm = 518–642, a high field-induced strain = 0.20%–0.24 %, and a low dielectric loss tan δ = 0.54%–0.69 %. X-ray diffraction and Raman spectra reveal the coexisting triple phase composition of the rhombohedral phase, tetragonal phase, and monoclinic polar nanoregions. Thermally stimulated depolarization current verifies the formation of various defect dipole clusters such as (MnTi″–VO··)×. With enhanced local structure heterogeneity induced by Sm, the phase composition and defect chemistry are regarded as the origin of such high comprehensive performance.

Enabling artificial photosynthesis systems with molecular recycling: A review of photo- and electrochemical methods for regenerating organic sacrificial electron donors.

This review surveys advances in the literature that impact organic sacrificial electron donor recycling in artificial photosynthesis. Systems for photocatalytic carbon dioxide reduction are optimized using sacrificial electron donors. One strategy for coupling carbon dioxide reduction and water oxidation to achieve artificial photosynthesis is to use a redox mediator, or recyclable electron donor. This review highlights photo- and electrochemical methods for recycling amines and NADH analogues that can be used as electron donors in artificial photosynthesis. Important properties of sacrificial donors and recycling strategies are also discussed. Compounds from other fields, such as redox flow batteries and decoupled water splitting research, are introduced as alternative recyclable sacrificial electron donors and their oxidation potentials are compared to the redox potentials of some model photosensitizers. The aim of this review is to act as a reference for researchers developing photocatalytic systems with sacrificial electron donors, and for researchers interested in designing new redox mediator and recyclable electron donor species.

N-X⋅⋅⋅O-N Halogen Bonds in Complexes of N-Haloimides and Pyridine-N-oxides: A Large Data Set Study.

N-X⋅⋅⋅- O-N+ halogen-bonded systems formed by 27 pyridine N-oxides (PyNOs) as halogen-bond (XB) acceptors and two N-halosuccinimides, two N-halophthalimides, and two N-halosaccharins as XB donors are studied in silico, in solution, and in the solid state. This large set of data (132 DFT optimized structures, 75 crystal structures, and 168 1 H NMR titrations) provides a unique view to structural and bonding properties. In the computational part, a simple electrostatic model (SiElMo) for predicting XB energies using only the properties of halogen donors and oxygen acceptors is developed. The SiElMo energies are in perfect accord with energies calculated from XB complexes optimized with two high-level DFT approaches. Data from in silico bond energies and single-crystal X-ray structures correlate; however, data from solution do not. The polydentate bonding characteristic of the PyNOs' oxygen atom in solution, as revealed by solid-state structures, is attributed to the lack of correlation between DFT/solid-state and solution data. XB strength is only slightly affected by the PyNO oxygen properties [(atomic charge (Q), ionization energy (Is,min ) and local negative minima (Vs,min )], as the σ-hole (Vs,max ) of the donor halogen is the key determinant leading to the sequence N-halosaccharin>N-halosuccinimide>N-halophthalimide on the XB strength.

N−X⋅⋅⋅O−N Halogen Bonds in Complexes of N‐Haloimides and Pyridine‐N‐oxides: A Large Data Set Study

AbstractN−X⋅⋅⋅−O−N+ halogen‐bonded systems formed by 27 pyridine N‐oxides (PyNOs) as halogen‐bond (XB) acceptors and two N‐halosuccinimides, two N‐halophthalimides, and two N‐halosaccharins as XB donors are studied in silico, in solution, and in the solid state. This large set of data (132 DFT optimized structures, 75 crystal structures, and 168 1H NMR titrations) provides a unique view to structural and bonding properties. In the computational part, a simple electrostatic model (SiElMo) for predicting XB energies using only the properties of halogen donors and oxygen acceptors is developed. The SiElMo energies are in perfect accord with energies calculated from XB complexes optimized with two high‐level DFT approaches. Data from in silico bond energies and single‐crystal X‐ray structures correlate; however, data from solution do not. The polydentate bonding characteristic of the PyNOs’ oxygen atom in solution, as revealed by solid‐state structures, is attributed to the lack of correlation between DFT/solid‐state and solution data. XB strength is only slightly affected by the PyNO oxygen properties [(atomic charge (Q), ionization energy (Is,min) and local negative minima (Vs,min)], as the σ‐hole (Vs,max) of the donor halogen is the key determinant leading to the sequence N‐halosaccharin&gt;N‐halosuccinimide&gt;N‐halophthalimide on the XB strength.

N-acyl homoserine lactone mediating initial adhesion of microalgal biofilm formation

While pioneering methods have demonstrated that bacterial N-acyl homoserine lactone (AHL) signaling molecules can influence the growth and self-aggregation of suspended microalgae, whether AHLs can affect the initial adhesion to a carrier has remained an open question. Here we revealed that the microalgae exhibited different adhesion potential under AHL mediation, where the performance was affiliated to both AHL types and concentrations. The result can be well explained by the interaction energy theory, where the energy barrier between the carriers and the cells varied due to AHL mediation. Depth analyses revealed that AHL acted through modifying the properties of the surface electron donor of the cells, which were dependent upon three major components, i.e., extracellular protein (PN) secretion, the PN secondary structure, and the PN amino acid composition. These findings expand the known diversity of AHLs mediation on microalgal initial adhesion and metabolisms, which may interface with other major cycles and become helpful to theoretically guide the application of AHLs in microalgal culture and harvesting.