How Permanent Are the Permanent Macrodipoles of Anthranilamide Bioinspired Molecular Electrets?

Dipoles are ubiquitous, and their impacts on materials and interfaces affect many aspects of daily life. Despite their importance, dipoles remain underutilized, often because of insufficient knowledge about the structures producing them. As electrostatic analogues of magnets, electrets possess ordered electric dipoles. Here, we characterize the structural dynamics of bioinspired electret oligomers based on anthranilamide motifs. We report dynamics simulations, employing a force field that allows dynamic polarization, in a variety of solvents. The results show a linear increase in macrodipoles with oligomer length that strongly depends on solvent polarity and hydrogen-bonding (HB) propensity, as well as on the anthranilamide side chains. An increase in solvent polarity increases the dipole moments of the electret structures while decreasing the dipole effects on the moieties outside the solvation cavities. The former is due to enhancement of the Onsager reaction field and the latter to screening of the dipole-generated fields. Solvent dynamics hugely contributes to the fluctuations and magnitude of the electret dipoles. HB with the solvent weakens electret macrodipoles without breaking the intramolecular HB that maintains their extended conformation. This study provides design principles for developing a new class of organic materials with controllable electronic properties. An animated version of the TOC graphic showing a sequence of the MD trajectories of short and long molecular electrets in three solvents with different polarities is available in the HTML version of this paper.

Poly(dimethylsiloxane) as a room-temperature solid solvent for photophysics and photochemistry.

Medium viscosity strongly affects the dynamics of solvated species and can drastically alter the deactivation pathways of their excited states. This study demonstrates the utility of poly(dimethylsiloxane) (PDMS) as a room-temperature solid-state medium for optical spectroscopy. As a thermoset elastic polymer, PDMS is transparent in the near ultraviolet, visible, and near infrared spectral regions. It is easy to mould into any shape, forming surfaces with a pronounced smoothness. While PDMS is broadly used for the fabrication of microfluidic devices, it swells in organic solvents, presenting severe limitations for the utility of such devices for applications employing non-aqueous fluids. Nevertheless, this swelling is reversible, which proves immensely beneficial for loading samples into the PDMS solid matrix. Transferring molecular-rotor dyes (used for staining prokaryotic cells and amyloid proteins) from non-viscous solvents into PDMS induces orders-of-magnitude enhancement of their fluorescence quantum yield and excited-state lifetimes, providing mechanistic insights about their deactivation pathways. These findings demonstrate the unexplored potential of PDMS as a solid solvent for optical applications.

Role of intramolecular hydrogen bonds in promoting electron flow through amino acid and oligopeptide conjugates.

Elucidating the factors that control charge transfer rates in relatively flexible conjugates is of importance for understanding energy flows in biology as well as assisting the design and construction of electronic devices. Here, we report ultrafast electron transfer (ET) and hole transfer (HT) between a corrole (Cor) donor linked to a perylene-diimide (PDI) acceptor by a tetrameric alanine (Ala)4 Selective photoexcitation of the donor and acceptor triggers subpicosecond and picosecond ET and HT. Replacement of the (Ala)4 linker with either a single alanine or phenylalanine does not substantially affect the ET and HT kinetics. We infer that electronic coupling in these reactions is not mediated by tetrapeptide backbone nor by direct donor-acceptor interactions. Employing a combination of NMR, circular dichroism, and computational studies, we show that intramolecular hydrogen bonding brings the donor and the acceptor into proximity in a "scorpion-shaped" molecular architecture, thereby accounting for the unusually high ET and HT rates. Photoinduced charge transfer relies on a (Cor)NH…O=C-NH…O=C(PDI) electronic-coupling pathway involving two pivotal hydrogen bonds and a central amide group as a mediator. Our work provides guidelines for construction of effective donor-acceptor assemblies linked by long flexible bridges as well as insights into structural motifs for mediating ET and HT in proteins.

Optical Window to Polarity of Electrolyte Solutions.

Medium polarity plays a crucial role in charge-transfer processes and electrochemistry. The added supporting electrolyte in electrochemical setups, essential for attaining the needed electrical conductivity, sets challenges for estimating medium polarity. Herein, we resort to Lippert-Mataga-Ooshika (LMO) formalism for estimating the Onsager polarity of electrolyte organic solutions pertinent to electrochemical analysis. An amine derivative of 1,8-naphthalimide proves to be an appropriate photoprobe for LMO analysis. An increase in electrolyte concentration enhances the polarity of the solutions. This effect becomes especially pronounced for low-polarity solvents. Adding 100 mM tetrabutylammonium hexafluorophosphate to chloroform results in solution polarity exceeding that of neat dichloromethane and 1,2-dichloroethane. Conversely, the observed polarity enhancement that emerges upon the same electrolyte addition to solvents such as acetonitrile and N,N-dimethylformamide is hardly as dramatic. Measured refractive indices provide a means for converting Onsager to Born polarity, which is essential for analyzing medium effects on electrochemical trends. This study demonstrates a robust optical means, encompassing steady-state spectroscopy and refractometry, for characterizing solution properties important for charge-transfer science and electrochemistry.

A sensitive zinc probe operating via enhancement of excited-state intramolecular charge transfer.

Novel highly sensitive fluorescent probes for zinc cations based on the diketopyrrolopyrrole scaffold were designed and synthesized. Large bathochromic shifts (≈80 nm) of fluorescence are observed when the Zn2+-recognition unit (di-(2-picolyl)amine) is bridged with the fluorophore possessing an additional pyridine unit able to participate in the coordination process. This effect originates from the dipolar architecture and the increasing electron-withdrawing properties of the diketopyrrolopyrrole core upon addition of the cation. The new, greenish-yellow emitting probes, which operate via modulation of intramolecular charge transfer, are very sensitive to the presence of Zn2+. Introduction of a morpholine unit in the diketopyrrolopyrrole structure induces a selective six-fold increase of the emission intensity upon zinc coordination. Importantly, the presence of other divalent biologically relevant metal cations has negligible effects and typically even at a 100-fold higher concentration of Mg2+/Zn2+, the effect is comparable. Computational studies rationalize the strong bathochromic shift upon Zn2+-complexation. Decorating the probes with the triphenylphosphonium cation and morpholine unit enables selective localization in the mitochondria and the lysosome of cardiac H9C2 cells, respectively.

How does tautomerization affect the excited-state dynamics of an amino acid-derivatized corrole?

In the first two decades of the XXI century, corroles have emerged as an important class of porphyrinoids for photonics and biomedical photonics. In comparison with porphyrins, corroles have lower molecular symmetry and higher electron density, which leads to uniquely complementary properties. In macrocycles of free-base corroles, for example, three protons are distributed among four pyrrole nitrogens. It results in distinct tautomers that have different thermodynamic energies. Herein, we focus on the excited-state dynamics of a corrole modified with L-phenylalanine. The tautomerization in the singlet-excited state occurs in the timescales of about 10-100 picoseconds and exhibits substantial kinetic isotope effects. It, however, does not discernably affect nanosecond deactivation of the photoexcited corrole and its basic photophysics. Nevertheless, this excited-state tautomerization dynamics can strongly affect photoinduced processes with comparable or shorter timescales, considering the 100-meV energy differences between the tautomers in the excited state. The effects on the kinetics of charge transfer and energy transfer, initiated prior to reaching the equilibrium thermalization of the excited-state tautomer population, can be indeed substantial. Such considerations are crucially important in the design of systems for artificial photosynthesis and other forms of energy conversion and charge transduction.

Correction: Multifaceted aspects of charge transfer.

Correction for 'Multifaceted aspects of charge transfer' by James B. Derr et al., Phys. Chem. Chem. Phys., 2020, 22, 21583-21629, DOI: .

The Synthesis and Photophysical Properties of Weakly Coupled Diketopyrrolopyrroles.

Three centrosymmetric diketopyrrolopyrroles possessing either two 2-(2'-methoxyphenyl)benzothiazole or two 2-(2'-methoxyphenyl)benzoxazolo-thiophene scaffolds were synthesized in a straightforward manner, and their photophysical properties were investigated. Their emission was significantly bathochromically shifted as compared with that of simple DPPs reaching 650 nm. Judging from theoretical calculations performed with time-dependent density functional theory, in all three cases the excited state was localized on the DPP core and there was no significant CT character. Consequently, emission was almost independent of solvents' polarity. DPPs possessing 2,5-thiophene units vicinal to DPP core play a role in electronic transitions, resulting in bathochromically shifted absorption and emission. Interestingly, as judged from transient absorption dynamics, intersystem crossing was responsible for the deactivation of the excited states of DPPs possessing para linkers but not in the case of dye bearing meta linker.

Multifaceted aspects of charge transfer.

Charge transfer and charge transport are by far among the most important processes for sustaining life on Earth and for making our modern ways of living possible. Involving multiple electron-transfer steps, photosynthesis and cellular respiration have been principally responsible for managing the energy flow in the biosphere of our planet since the Great Oxygen Event. It is impossible to imagine living organisms without charge transport mediated by ion channels, or electron and proton transfer mediated by redox enzymes. Concurrently, transfer and transport of electrons and holes drive the functionalities of electronic and photonic devices that are intricate for our lives. While fueling advances in engineering, charge-transfer science has established itself as an important independent field, originating from physical chemistry and chemical physics, focusing on paradigms from biology, and gaining momentum from solar-energy research. Here, we review the fundamental concepts of charge transfer, and outline its core role in a broad range of unrelated fields, such as medicine, environmental science, catalysis, electronics and photonics. The ubiquitous nature of dipoles, for example, sets demands on deepening the understanding of how localized electric fields affect charge transfer. Charge-transfer electrets, thus, prove important for advancing the field and for interfacing fundamental science with engineering. Synergy between the vastly different aspects of charge-transfer science sets the stage for the broad global impacts that the advances in this field have.

meso-Modified Cobalamins: Synthesis, Structure, and Properties.

Vitamin B12 and its derivatives present excellent paradigms for bioinspired catalysis. The inherent challenges for derivatizing cobalamins, such as vitamin B12 , to incorporate them in supramolecular designs and materials, limit the range of their utility and applications. Herein, we present a synthetic approach toward derivatives of vitamin B12 possessing electron-donating and -withdrawing substituents at the meso position (C10). Spectroscopic and cyclic voltammetry studies reveal that changes in the substitution pattern on the equatorial ligand have a significant impact on the electronic and optical properties of the cobalamin. These synthetic methods, therefore, provide invaluable routes not only for covalent linking to other structures, but also for attaining a wide range of functionalities for the derivatives of vitamin B12 .

Dipole Effects on Electron Transfer are Enormous.

Molecular dipoles present important, but underutilized, methods for guiding electron transfer (ET) processes. While dipoles generate fields of Gigavolts per meter in their vicinity, reported differences between rates of ET along versus against dipoles are often small or undetectable. Herein we show unprecedentedly large dipole effects on ET. Depending on their orientation, dipoles either ensure picosecond ET, or turn ET completely off. Furthermore, favorable dipole orientation makes ET possible even in lipophilic medium, which appears counterintuitive for non-charged donor-acceptor systems. Our analysis reveals that dipoles can substantially alter the ET driving force for low solvent polarity, which accounts for these unique trends. This discovery opens doors for guiding forward ET processes while suppressing undesired backward electron transduction, which is one of the holy grails of photophysics and energy science.

Fluorinated aminoanthranilamides: non-native amino acids for bringing proteomic approaches to charge-transfer systems.

The ability to control charge transfer at molecular and nanometer scales represents the ultimate level of electronic mastery, and its impacts cannot be overstated. As electrostatic analogues of magnets, electrets possess ordered electric dipoles that present key paradigms for directing transduction of electrons and holes. Herein we describe the design and development of fluorinated aminoanthranilamides, derivatives of non-native aromatic beta-amino acids, as building blocks for hole-transfer molecular electrets. A highly regio-selective nucleophilic aromatic substitution of difluorinated nitrobenzoic acid provides the underpinnings for an array of unprecedented anthranilamide structures. Spin density distribution and electrochemical analyses reveal that fluorine induces about 200 mV positive shifts in reduction potentials without compromising the stability of the oxidized residues, making them invaluable building blocks for hole-transfer systems. These findings open unexplored routes to novel amino-acid structures, setting a foundation for bringing principles of proteomics to designs of charge-transfer systems.

Gating That Suppresses Charge Recombination-The Role of Mono-N-Arylated Diketopyrrolopyrrole.

Suppressing the charge recombination (CR) that follows an efficient charge separation (CS) is of key importance for energy, electronics, and photonics applications. We focus on the role of dynamic gating for impeding CR in a molecular rotor, comprising an electron donor and acceptor directly linked via a single bond. The media viscosity has an unusual dual effect on the dynamics of CS and CR in this dyad. For solvents with intermediate viscosity, CR is 1.5-3 times slower than CS. Lowering the viscosity below ∼0.6 mPa s or increasing it above ∼10 mPa s makes CR 10-30 times slower than CS. Ring rotation around the donor-acceptor bond can account only for the trends observed for nonviscous solvents. Media viscosity, however, affects not only torsional but also vibrational modes. Suppressing predominantly slow vibrational modes by viscous solvents can impact the rates of CS and CR to a different extent. That is, an increase in the viscosity can plausibly suppress modes that are involved in the transition from the charge-transfer (CT) to the ground state, i.e., CR, but at the same time are not important for the transition from the locally excited to the CT state, i.e., CS. These results provide a unique example of synergy between torsional and vibronic modes and their drastic effects on charge-transfer dynamics, thus setting paradigms for controlling CS and CR.

Nonplanar Butterfly-Shaped π-Expanded Pyrrolopyrroles.

Large aza-analogues of curved polycyclic aromatic hydrocarbons with a double-helicene structure present unique features for molecular photonics. We present the preparation and characterization of three such structures. The synthesis of these heterocyclic nanographenes involves only a few high-yield steps that use readily available starting materials. X-ray analysis revealed that each of these new dyes has three conformational isomers: one diastereoisomer in a meso form and two enantiomers in twisted forms [(P,P)] and [(M,M)]. The low energy barriers between the conformers, however, prevent their separation by using chiral HPLC, and the NMR spectra show only one set of signals for each of these curved compounds. Density functional theory (DFT) calculations quantify the small energy difference and the small energy barriers between the chiral and meso forms, which fully supports the experimental results. Their optical absorption lacks any sensitivity to the solvent environment, whereas their fluorescence features exhibit pronounced solvatochromism. This rarely observed solvatofluorochromism of centrosymmetric molecules without either electron-withdrawing groups or -donating substituents was probed by using time-resolved spectroscopy. These studies suggest that, similar to 9,9'-bianthryl, the nonpolar locally excited state shows negligible solvatochromism, whereas the charge-transfer state is sensitive to solvent polarity.

How To Reach Intense Luminescence for Compounds Capable of Excited-State Intramolecular Proton Transfer?

Photoinduced intramolecular direct arylation allows structurally unique compounds containing phenanthro[9',10':4,5]imidazo[1,2-f]phenanthridine and imidazo[1,2-f]phenanthridine skeletons, which mediate excited-state intramolecular proton transfer (ESIPT), to be efficiently synthesized. The developed polycyclic aromatics demonstrate that the combination of five-membered ring structures with a rigid arrangement between a proton donor and a proton acceptor provides a means for attaining large fluorescence quantum yields, exceeding 0.5, even in protic solvents. Steady-state and time-resolved UV/Vis spectroscopy reveals that, upon photoexcitation, the prepared protic heteroaromatics undergo ESIPT, converting them efficiently into their excited-state keto tautomers, which have lifetimes ranging from about 5 to 10 ns. The rigidity of their structures, which suppresses nonradiative decay pathways, is believed to be the underlying reason for the nanosecond lifetimes of these singlet excited states and the observed high fluorescence quantum yields. Hydrogen bonding with protic solvents does not interfere with the excited-state dynamics and, as a result, there is no difference between the occurrences of ESIPT processes in MeOH versus cyclohexane. Acidic media has a more dramatic effect on suppressing ESIPT by protonating the proton acceptor. As a result, in the presence of an acid, a larger proportion of the fluorescence of ESIPT-capable compounds originates from their enol excited states.

Virus-resembling nano-structures for near infrared fluorescence imaging of ovarian cancer HER2 receptors.

Ovarian cancer remains the dominant cause of death due to malignancies of the female reproductive system. The capability to identify and remove all tumors during intraoperative procedures may ultimately reduce cancer recurrence, and lead to increased patient survival. The objective of this study is to investigate the effectiveness of an optical nano-structured system for targeted near infrared (NIR) imaging of ovarian cancer cells that over-express the human epidermal growth factor receptor 2 (HER2), an important biomarker associated with ovarian cancer. The nano-structured system is comprised of genome-depleted plant-infecting brome mosaic virus doped with NIR chromophore, indocyanine green, and functionalized at the surface by covalent attachment of monoclonal antibodies against the HER2 receptor. We use absorption and fluorescence spectroscopy, and dynamic light scattering to characterize the physical properties of the constructs. Using fluorescence imaging and flow cytometry, we demonstrate the effectiveness of these nano-structures for targeted NIR imaging of HER2 receptors in vitro. These functionalized nano-materials may provide a platform for NIR imaging of ovarian cancer.

Dipole-mediated rectification of intramolecular photoinduced charge separation and charge recombination.

Controlling charge transfer at a molecular scale is critical for efficient light harvesting, energy conversion, and nanoelectronics. Dipole-polarization electrets, the electrostatic analogue of magnets, provide a means for "steering" electron transduction via the local electric fields generated by their permanent electric dipoles. Here, we describe the first demonstration of the utility of anthranilamides, moieties with ordered dipoles, for controlling intramolecular charge transfer. Donor-acceptor dyads, each containing a single anthranilamide moiety, distinctly rectify both the forward photoinduced electron transfer and the subsequent charge recombination. Changes in the observed charge-transfer kinetics as a function of media polarity were consistent with the anticipated effects of the anthranilamide molecular dipoles on the rectification. The regioselectivity of electron transfer and the molecular dynamics of the dyads further modulated the observed kinetics, particularly for charge recombination. These findings reveal the underlying complexity of dipole-induced effects on electron transfer and demonstrate unexplored paradigms for molecular rectifiers.

Functionalized polymeric nanoparticles loaded with indocyanine green as theranostic materials for targeted molecular near infrared fluorescence imaging and photothermal destruction of ovarian cancer cells.

BACKGROUND AND OBJECTIVES: Ovarian cancer remains the deadliest malignancy of the female reproductive system. The ability to identify and destroy all ovarian tumor nodules may have a termendous impact on preventing tumor recurrence, and patient survival. The objective of this study is to investigate the effectiveness of a nano-structured system for combined near infrared (NIR) fluorescence imaging of human epidermal growth factor receptor-2 (HER2) over-expression, as a biomarker of ovarian cancer cells, and photothermal destruction of these cells in vitro. MATERIALS AND METHODS: The nano-structured system consists of the near infrared dye, indocyanine green (ICG), encapsulated within poly(allylamine) hydrochloride chains cross-linked ionically with sodium phosphate. The surface of the construct is functionalized by covalently attached polyethylene glycol, and monoclonal antibodies against HER2 using reducitve amination methods. We use dynamic light scattering, and absorption and fluorescence spectroscopy for phyiscal characterization of the constructs. Flow cytometry and fluorescence microscopy are used to investigate molecular targeting and imaging capabilities of the constructs against SKOV3 and OVCAR3 ovarian cancer cell lines, which have relatively high and low expression levels of the HER2 receptor, respectively. Continuous NIR laser irradiation at 808 nm is used to investigating the utility of the constructs in mediating photothermal destruction of SKOV3 cells. RESULTS: Flow cytometry results indicate that the functionalized nano-constructs are more effective in targeting the HER2 receptor than non-encapsulated ICG and non-functionlaized constructs (P < 0.005). Fluorescence microscopic images show the capaiblity of the functionalized constructs in NIR imaging of HER2 overexpression. The functionalized nano-constructs are also capable of inducing a significantly greater increase in photothermal destruction of SKOV3 cells than free ICG and non-functionalized constructs (P < 0.005). CONCLUSION: We have demonstrated the efficacy of polymeric nano-structured constructs loaded with ICG, and functionalized with the monoclonal antibodies, as thernaostic materials for targted molecular NIR imaging of the HER2 receptor overexpression on ovarian cancer cells, and photothermal destruction of these cells. These nanoparticles may prove useful towards intraoperative detection, imaging, and phototherapy of small ovarian cancer nodules.

Quadrupolar, Highly Polarized Dyes: Emission Dependence on Viscosity and Selective Mitochondria Staining.

Quadrupolar A-D-A-type 1,4-dihydropyrrolo[3,2-b]pyrroles (DHPPs) bearing pyridinium and quinolinium substituents emit in the 500-600 nm region. The enhancement of electronic communication between the electron-rich heterocyclic core and electron-deficient peripheral substituents turned out to be crucial for achieving emission enhancement in viscous media. DHPP bearing two 4-pyridinium substituents has optical brightness 34,000 in glycerol and only 700 in MeOH, as evidenced by measurements of the emission intensity and fluorescence lifetimes in a series of polar solvents. Such behavior makes it an excellent candidate for viscosity probes in fluorescence microscopy, as demonstrated by the fluorescence imaging of H9C2 cardiomyocytes.

Microfluidic space-domain time-resolved emission spectroscopy of terbium(III) and europium(III) chelates with pyridine-2,6-dicarboxylate.

This article describes the utilization of laminar microflows for time-resolved emission measurements with steady-state excitation and detection. Passing a laminar flow through a short illuminated section of a microchannel provided a means for pulsed-like photoexcitation of the moieties carried by the fluid. Imaging the microchannel flows carrying thus photoexcited chelates of lanthanide ions allowed us to extract their excited-state lifetimes from the spatial distribution of the changes in the emission intensity. The lifetime values obtained using this space-domain approach agreed well with the lifetimes from time-domain measurements. This validated space-domain microfluidic approach reveals a means for miniaturization of time-resolved emission spectroscopy.