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1.
Life (Basel) ; 14(3)2024 Feb 22.
Artigo em Inglês | MEDLINE | ID: mdl-38541616

RESUMO

The birth and following growth of social media platforms has influenced a lot. In addition to beneficial features, it has long-been noticed that heavy consumption of social media can have negative effects beyond a simple lack of time for other things. Of particular interest is the idea that consuming short videos lasting only fractions of a minute and watched one after another can lead to deficits in concentration and attention. Completing the existing literature that already reports evidence for attention deficits related to heavy social media use, the present study aims to contribute to this acute topic by adding neurophysiological data to it. In particular, this study made use of a well-known experimental paradigm, which is able to detect attention-related changes on a neurophysiological level. The so-called oddball paradigm was applied and the hypothesis that heavy social media users mainly consuming short videos show a reduced P300 event-related potential (ERP) component was tested, which has been found to reflect attention-related brain functions. For this, we invited twenty-nine participants and designed a visual oddball experiment including a white circle on black background as the low-frequency target stimulus and a white triangle on black background as the high-frequency non-target stimulus. On the basis of their self-reported short-video-based social media usage habits, all participants were grouped into heavy (more than 4 h daily usage) and regular (below 3 h daily usage) users, and finally data from 14 heavy and 15 regular users were further analyzed. It was found that only regular users show a clear P300 ERP component, while this particular brain potential amplitude reflecting attentional processes was significantly reduced in heavy users. This result provides empirical brain imaging evidence that heavy short-video-based social media use indeed affects attentional brain processes in a negative way.

2.
Life (Basel) ; 14(3)2024 Mar 09.
Artigo em Inglês | MEDLINE | ID: mdl-38541687

RESUMO

Trust and distrust are constructs that have provoked and undergone lots of discussion in the fields of sociology and psychology. However, to our knowledge, there is little agreement about how these constructs should be treated in the future. The present study tries to help in this discussion by re-analyzing prior neurophysiological data highlighting differences between trust and distrust by connecting these data with two distinct personality dimensions. Thus, the objective was to analyze the connection between neurophysiological trust/distrust processing and distinct HEXACO personality dimensions. Differences were found in the event-related potentials (ERPs) calculated for visual presentations of political institution words and brand names, which were evaluated with respect to trust and distrust by button presses. Two time points (330 ms and 780 ms) showed brain activity differences between trust and distrust related to the two word categories at frontal electrode locations. For this study, these findings were taken and connected to HEXACO-60 personality inventory results collected from prior participants. Statistical analysis revealed a significant interaction between the ERPs and two HEXACO personality dimensions concerning trusted brands at the later time point (780 ms) at the right frontal electrode location F8. This result is taken as neurophysiological evidence that parameter values of the personality traits honesty-humility and agreeableness have an influence on brain functions related to trusted brands.

3.
Brain Sci ; 13(10)2023 Sep 29.
Artigo em Inglês | MEDLINE | ID: mdl-37891762

RESUMO

The present study addresses the question of whether explicit, survey-type measures of attitude differ in sensitivity when compared to implicit, non-conscious measures of attitude in the context of attitude changes in response to evaluative conditioning (EC). In the frame of a pre-test, participants rated 300 brand names on a Likert-type scale, the results of which were then used to create personalised lists of neutral brands. After this initial online component, the participants were exposed to one, five, and ten rounds of EC (during three separate sessions), during which half of the brands were paired with pleasant audio excerpts (positive EC) and the remainder were paired with unpleasant audio excerpts (negative EC). Following each conditioning round, the participants rated the brand names again, whilst changes in the brain's electrical activity in response to the brands were recorded via electroencephalography (EEG). After having rated the brand names, the participants also completed two implicit association tests (IAT; one for each of the neutral conditions). The results revealed that self-reported, explicit responses of brand names remained unchanged despite having been conditioned. Similarly, the IAT did not reveal any declines in reaction time. In contrast, the EEG data appeared to not only be sensitive to initial brand ratings, but also the conditioning effects of initially neutral brands. Respective neurophysiological effects were found at frontal electrode locations AF3 and AF4 for a 1 s-long time window starting at 400 ms after stimulus onset. Furthermore, the EEG revealed that changes in brand attitude are more susceptible to the effects of negative conditioning than positive conditioning. Given the rather small sample size, any generalizability seems vague, but the present results provide scientific evidence that EEG could indeed be a valuable additional method to investigate EC effects. The results of this study support the notion of utilising a multidimensional approach, inclusive of neuroscience, to understanding consumer attitudes instead of solely relying on self-report measures. In the end, the brain knows more than it admits to consciousness and language, which is why objective methods should always be included in any study.

4.
Small ; 19(52): e2304380, 2023 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-37649193

RESUMO

Using colloidal particles as models to understand processes on a smaller scale is a precious approach. Compared to molecules, particles are less defined, but their architecture can be more complex and so is their long-range interaction. One can observe phenomena that are unknown or much more difficult to realize on the molecular level. The current paper focuses on particle-based surfactants and reports on numerous unexpected properties. The main goal is creating an amphiphilic system with responsiveness in surface activity and associated self-organization phenomena depending on applying an external trigger, preferably a physical field. A key step is the creation of a Janus-type particle characterized by two types of dipoles (electric and magnetic) which geometrically stand orthogonal to each other. In a field, one can control which contribution and direction dominate the interparticle interactions. As a result, one can drastically change the system's properties. The features of ferrite-core organosilica-shell particles with grain-like morphology modified by click chemistry are studied in response to spatially isotropic and anisotropic triggers. A highly unusual aggregation-dissolution-reaggregation sequence w as discovered. Using a magnetic field, one can even switch off the amphiphilic properties and use this for the field-triggered breaking of multiphase systems such as emulsions.

5.
Brain Sci ; 13(5)2023 May 21.
Artigo em Inglês | MEDLINE | ID: mdl-37239305

RESUMO

Especially for young people, influencers and other celebrities followed on social media evoke affective closeness that in their young minds seems real even though it is fake. Such fake friendships are potentially problematic because of their felt reality on the consumer side while lacking any inversely felt true closeness. The question arises if the unilateral friendship of a social media user is equal or at least similar to real reciprocal friendship. Instead of asking social media users for explicit responses (conscious deliberation), the present exploratory study aimed to answer this question with the help of brain imaging technology. Thirty young participants were first invited to provide individual lists including (i) twenty names of their most followed and loved influencers or other celebrities (fake friend names), (ii) twenty names of loved real friends and relatives (real friend names) as well as (iii) twenty names they do not feel any closeness to (no friend names). They then came to the Freud CanBeLab (Cognitive and Affective Neuroscience and Behavior Lab) where they were shown their selected names in a random sequence (two rounds), while their brain activities were recorded via electroencephalography (EEG) and later calculated into event-related potentials (ERPs). We found short (ca. 100 ms) left frontal brain activity starting at around 250 ms post-stimulus to process real friend and no friend names similarly, while both ERPs differed from those elicited by fake friend names. This is followed by a longer effect (ca. 400 ms), where left and right frontal and temporoparietal ERPs also differed between fake and real friend names, but at this later processing stage, no friend names elicited similar brain activities to fake friend names in those regions. In general, real friend names elicited the most negative going brain potentials (interpreted as highest brain activation levels). These exploratory findings represent objective empirical evidence that the human brain clearly distinguishes between influencers or other celebrities and close people out of real life even though subjective feelings of closeness and trust can be similar. In summary, brain imaging shows there is nothing like a real friend. The findings of this study might be seen as a starting point for future studies using ERPs to investigate social media impact and topics such as fake friendship.

6.
Life (Basel) ; 13(2)2023 Feb 20.
Artigo em Inglês | MEDLINE | ID: mdl-36836942

RESUMO

This study represents a follow-up event-related potential (ERP) analysis of a prior investigation. The previous results showed that participants had most negative-tending ERPs in the mid-frontal brain region during exposure to neutral emotion pictures (compared to negative and positive pictures) while being accompanied by a significant other person (social presence condition). The present analysis aimed at investigating potential sex differences related to this phenomenon. Female and male participants' brain activity data from the previous study were analyzed separately for one representative mid-frontal electrode location selected on the basis of having the highest significance level. As a result, only female participants showed significantly more negative-tending potentials in response to neutral pictures, compared to both other emotion categories (positive and negative) in the social presence condition. This was not found in male participants. The respective ERP effect was most dominant at 838 ms post stimulus onset, which is slightly later than the effect found in the prior study. However, this result is interpreted as evidence that the general effect from the prior study can be understood as a largely female phenomenon. In line with the prior study, the present results are interpreted as a predominantly female activation in the mid-frontal brain region in response to neutral picture stimuli while being accompanied by a significant other person (social presence condition). Although only speculative, this would align with previous studies demonstrating sex-related hormonal and structural differences in the anterior cingulate cortex (ACC). In general, ACC activation has been associated with an integrative weighting function in ambiguous social settings, which makes sense given the ambiguous nature of neutral pictures in combination with a social presence condition.

8.
Nat Commun ; 13(1): 5501, 2022 09 20.
Artigo em Inglês | MEDLINE | ID: mdl-36127376

RESUMO

Rhodopsins had long been considered non-fluorescent until a peculiar voltage-sensitive fluorescence was reported for archaerhodopsin-3 (Arch3) derivatives. These proteins named QuasArs have been used for imaging membrane voltage changes in cell cultures and small animals, but they could not be applied in living rodents. To develop the next generation of sensors, it is indispensable to first understand the molecular basis of the fluorescence and its modulation by the membrane voltage. Based on spectroscopic studies of fluorescent Arch3 derivatives, we propose a unique photo-reaction scheme with extended excited-state lifetimes and inefficient photoisomerization. Molecular dynamics simulations of Arch3, of the Arch3 fluorescent derivative Archon1, and of several its mutants have revealed different voltage-dependent changes of the hydrogen-bonding networks including the protonated retinal Schiff-base and adjacent residues. Experimental observations suggest that under negative voltage, these changes modulate retinal Schiff base deprotonation and promote a decrease in the populations of fluorescent species. Finally, we identified molecular constraints that further improve fluorescence quantum yield and voltage sensitivity.


Assuntos
Rodopsinas Microbianas , Bases de Schiff , Animais , Hidrogênio , Ligação de Hidrogênio , Rodopsinas Microbianas/química , Rodopsinas Microbianas/genética , Bases de Schiff/química , Análise Espectral
9.
J Chem Phys ; 156(19): 191103, 2022 May 21.
Artigo em Inglês | MEDLINE | ID: mdl-35597651

RESUMO

Transitions into the first excited state of carotenoids, Car S1, are optically forbidden in conventional one-photon excitation (OPE) but are possible via two-photon excitation (TPE). This can be used to quantify the amount of Car S1 to Chlorophyll (Chl) energy transfer in pigment-protein complexes and plants by observing the chlorophyll fluorescence intensity after TPE in comparison to the intensity observed after direct chlorophyll OPE. A parameter, ΦCoupling Car S1-Chl, can be derived that directly reflects relative differences or changes in the Car S1 → Chl energy transfer of different pigment-protein complexes and even living plants. However, very careful calibrations are necessary to ensure similar OPE and TPE excitation probabilities and transition energies. In plants, the exact same sample spot must be observed at the same time. All this is experimentally quite demanding. ΦCoupling Car S1-Chl also corrects intrinsically for direct chlorophyll TPE caused by larger chlorophyll excesses in the complexes, but recently it turned out that in certain TPE wavelengths ranges, its contribution can be quite large. Fortunately, this finding opens also the possibility of determining ΦCoupling Car S1-Chl in a much easier way by directly comparing values in TPE spectra observed at wavelengths that are either more dominated by Cars or Chls. This avoids tedious comparisons of OPE and TPE experiments and potentially allows measurement at even only two TPE wavelengths. Here, we explored this new approach to determine ΦCoupling Car S1-Chl directly from single TPE spectra and present first examples using known experimental spectra from Cars, Chl a, Chl b, LHC II, and PS 1.


Assuntos
Carotenoides , Complexo de Proteínas do Centro de Reação Fotossintética , Clorofila , Transferência de Energia , Complexos de Proteínas Captadores de Luz , Fótons
10.
Brain Sci ; 12(4)2022 Mar 30.
Artigo em Inglês | MEDLINE | ID: mdl-35447996

RESUMO

The present electroencephalography (EEG) study observed how the brain processes visual stimuli (words and shapes) displayed with four different duration times (17 ms, 33 ms, 67 ms, and 100 ms). All stimuli had to be classified into "I saw nothing", "I saw a blur", "I saw a word," or "I saw a shape" via distinct button presses while brain potentials were being measured. The neurophysiological correlates of word and shape processing were subsequently analysed and compared for two distinct time points at the occipito-parietal area in both hemispheres (P7 and P8). In a further step, word and shape identification rates were also analysed. Identification rates revealed that participants recognized words and shapes when presented for 17 ms at a rate of only 6% and 7%, which is poor enough to assume an overall lack of conscious recognition. Analysis of EEG data revealed two time points of interest, one at 210 ms and the other at 280 ms post stimulus onset. Brain potentials at the earlier time point reflect modulations in presentation duration with increased amplitudes elicited by longer presentations. At this time point, no differences were seen between words and shapes in both hemispheres. The later time point, though, clearly distinguished between word and shape processing with totally missing amplitudes (i.e., brain activity) in the case of shapes in general in both hemispheres. Crucially, words presented for only 17 ms still elicited an average brain potential amplitude significantly different from the corresponding 17 ms presentations of shapes at this time point at electrode location P7, even though both stimuli categories were basically not seen (i.e., not consciously recognized). This later word-specific brain potential for the shortest presentation duration is interpreted as neurophysiological evidence of subliminal word processing. Strikingly, this difference was not found in the right hemisphere at P8.

11.
Polymers (Basel) ; 14(3)2022 Jan 28.
Artigo em Inglês | MEDLINE | ID: mdl-35160519

RESUMO

Light-harvesting concentrators have a high potential to make highly efficient but precious energy converters, such as multijunction photovoltaics, more affordable for everyday applications. They collect sunlight, including diffusively scattered light, on large areas and redirect it to much smaller areas of the highly efficiency solar cells. Among the best current concepts are pools of randomly oriented light-collecting donor molecules that transfer all excitons to few aligned acceptors reemitting the light in the direction of the photovoltaics. So far, this system has only been realized for the 350-550 nm wavelength range, suitable for AlGaInP photovoltaics. This was achieved by using acceptor molecules that aligned during mechanical stretching of polymers together with donors, that stay random in that very same material and procedure. However, until recently, very little was known about the factors that are responsible for the alignability of molecules in stretched polymers and therefore it was difficult to find suitable donors and acceptors, as well as for other spectral ranges. Recently, a structural parameter was introduced with a high predictivity for the alignability of molecules that contain rigid band-like structures or linear aromatic π-systems. However, for light concentrators in more red spectral ranges, molecular systems often contain larger and extended, planar-like π-systems for which the previously reported parameter is not directly applicable. Here, we present a refined prediction parameter also suitable for larger plane-like structures. The new parameter depends on the number of in-plane atoms divided by out-of-plane atoms as determined by computational geometry optimization and additionally the planar aspect ratio for molecules that contain only in-plane atoms. With the help of this parameter, we found a new system that can efficiently collect and redirect light for the second 500-700 nm AlGaAs layer of current world-record multijunction photovoltaics. Similarly, as the previously reported system for the blue-green layer, it has also overall absorption and re-directioning quantum efficiencies close to 80-100%. Both layers, together, already cover about 75% of the energy in the solar spectrum.

12.
Methods Mol Biol ; 2417: 147-166, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-35099798

RESUMO

Fluorescence Cross-Correlation Spectroscopy (FCCS) is a well-established and useful tool in physics and chemistry. Furthermore, due to its hybrid character of being a bulk assay at a single molecular level, it found many applications in biophysics and molecular biochemistry. Examples may be investigating kinetics and dynamics of chemical and biochemical reactions such as protein-ligand-, protein-protein-binding, fast conformational changes, and intracellular transportation. Also, it was utilized to characterize larger structures such as lipid vesicles and multi-protein complexes. A two-photon excitation source makes FCCS relatively easy-to-use and easy-to-maintain. Combining this technique with fluorescence lifetime analysis results in a versatile biophysical tool that can be used to solve many biological problems, as even small changes in the local environment, like pH or salt concentration, can be monitored if appropriate fluorophores are used. An example of its use for membrane docking and fusion assays is described in Chap. 13 . In this chapter, we want to give the reader a simple, detailed step-by-step guide of how to set up such a tool.


Assuntos
Corantes Fluorescentes , Fótons , Fluorescência , Corantes Fluorescentes/química , Cinética , Ligação Proteica , Espectrometria de Fluorescência/métodos
13.
Methods Mol Biol ; 2417: 167-180, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-35099799

RESUMO

Watching events of membrane fusion in real time and distinguishing between intermediate steps of these events is useful for mechanistic insights but at the same time a challenging task. In this chapter, we describe how to use fluorescence cross-correlation spectroscopy and Förster-resonance energy transfer to resolve the tethering and fusion of membranes by SNARE proteins (syntaxin-1, SNAP-25, and synaptobrevin-2) as an example. The given protocols can easily be adapted to other membrane proteins to investigate their ability to tether or even fuse vesicular membrane.


Assuntos
Lipossomos , Fusão de Membrana , Transferência Ressonante de Energia de Fluorescência , Lipossomos/química , Proteínas SNARE/metabolismo , Espectrometria de Fluorescência , Sintaxina 1
14.
Plant Commun ; 2(5): 100212, 2021 09 13.
Artigo em Inglês | MEDLINE | ID: mdl-34746759

RESUMO

An ever-increasing number of intracellular multi-protein networks have been identified in plant cells. Split-GFP-based protein-protein interaction assays combine the advantages of in vivo interaction studies in a native environment with additional visualization of protein complex localization. Because of their simple protocols, they have become some of the most frequently used methods. However, standard fluorescent proteins present several drawbacks for sophisticated microscopy. With the HaloTag system, these drawbacks can be overcome, as this reporter forms covalent irreversible bonds with synthetic photostable fluorescent ligands. Dyes can be used in adjustable concentrations and are suitable for advanced microscopy methods. Therefore, we have established the Split-HaloTag imaging assay in plants, which is based on the reconstitution of a functional HaloTag protein upon protein-protein interaction and the subsequent covalent binding of an added fluorescent ligand. Its suitability and robustness were demonstrated using a well-characterized interaction as an example of protein-protein interaction at cellular structures: the anchoring of the molybdenum cofactor biosynthesis complex to filamentous actin. In addition, a specific interaction was visualized in a more distinctive manner with subdiffractional polarization microscopy, Airyscan, and structured illumination microscopy to provide examples of sophisticated imaging. Split-GFP and Split-HaloTag can complement one another, as Split-HaloTag represents an alternative option and an addition to the large toolbox of in vivo methods. Therefore, this promising new Split-HaloTag imaging assay provides a unique and sensitive approach for more detailed characterization of protein-protein interactions using specific microscopy techniques, such as 3D imaging, single-molecule tracking, and super-resolution microscopy.


Assuntos
Botânica/instrumentação , Plantas/metabolismo , Domínios e Motivos de Interação entre Proteínas
15.
Life (Basel) ; 11(7)2021 Jun 24.
Artigo em Inglês | MEDLINE | ID: mdl-34202700

RESUMO

The self is an increasingly central topic in current neuroscience. Understanding the neural processes that are involved in self-referential processing and functioning may also be crucial to understanding consciousness. The current short communication goes beyond the typical concept that the self is singular, as has been assumed from neuroanatomical descriptions of the self by fMRI and PET studies. Long ago, theoretically, the idea of multiple aspects of the human self-arose, highlighting a dynamic organizational structure, but an increasing number of electrophysiological brain imaging studies, searching for the temporal dynamics of self-referential brain processes, now has empirical evidence supporting their existence. This short communication focuses on the theoretical idea of a dynamic self and provides first preliminary empirical evidence, including results from own studies of the authors, in support of, and highlights the serial dynamics of the human self, suggesting a primitive Me1 and an elaborate Me2 (a non-personal and a personal self). By focusing on the temporal dimension of the self, we propose that multiple aspects of the self can be distinguished based on their temporal sequence. A multiple aspects Self Theory (MAST) is proposed. This model is meant as a theoretical framework for future studies providing further support.

16.
Brain Sci ; 11(6)2021 May 31.
Artigo em Inglês | MEDLINE | ID: mdl-34072811

RESUMO

It remains an unsolved conundrum how social presence affects the neural processes involved in adaptive situation-specific decision-making mechanisms. To investigate this question, brain potential changes via electroencephalography (EEG) and skin conductance responses (SCR) were taken within this study, while participants were exposed to pre-rated pleasant, neutral, and unpleasant pictures, which they had to rate in terms of their perceived arousal. Crucially, they had to-in respective runs-do this alone and in the presence of a significant other. Contrasting respective event-related potentials (ERPs) revealed significantly more negative going potentials peaking at 708 ms post stimulus onset at mid-frontal electrode locations (around FPz and AFz), when participants were exposed to neutral pictures while in the presence of a significant other. SCR results demonstrate higher states of arousal in the presence of a significant other regardless of picture emotion category. Self-reported arousal turned out to be highest in response to neutral pictures within the significant other condition, whereas in the alone condition in response to the pleasant pictures. In light of existing literature on social aspects and the anterior cingulate cortex (ACC), the ERP finding in the significant other condition, while rating emotionally neutral pictures, is interpreted as reflecting heightened ACC activation, which is supported by electrode locations showing significant brain activity differences as well as by source localization results. Neutral pictures are inherently ambiguous, and the current results indicate the presence of another person to change the way one processes, perceives, and acts on them. This is in support for theories proposing the ACC to be part of a larger signal-specification network that gauges relevant stimuli for adequate execution of control.

17.
Phys Chem Chem Phys ; 23(14): 8731-8738, 2021 Apr 14.
Artigo em Inglês | MEDLINE | ID: mdl-33876032

RESUMO

In addition to (bacterio)chlorophylls, (B)Chls, photosynthetic pigment-protein complexes bind carotenoids (Cars) that fulfil various important functions which are not fully understood, yet. However, certain excited states of Cars are optically one-photon forbidden ("dark") and can potentially undergo excitation energy transfer (EET) to (B)Chls following two-photon absorption (TPA). The amount of EET is reflected by the differences in TPA and two-photon excitation (TPE) spectra of a complex (multi-pigment) system. Since it is technically and analytically demanding to resolve optically forbidden states, different studies reported varying contributions of Cars and Chls to TPE/TPA spectra. In a study using well-defined 1 : 1 Car-tetrapyrrole dyads TPE contributions of tetrapyrrole molecules, including Chls, and Cars were measured. In these experiments, TPE of Cars dominated over Chl a TPE in a broad wavelength range. Another study suggested only minor contributions of Cars to TPE spectra of pigment-protein complexes such as the plant main light-harvesting complex (LHCII), in particular for wavelengths longer than ∼600/1200 nm. By joining forces and a combined analysis of all available data by both teams, we try to resolve this apparent contradiction. Here, we demonstrate that reconstruction of a wide spectral range of TPE for LHCII and photosystem I (PSI) requires both, significant Car and Chl contributions. Direct comparison of TPE spectra obtained in both studies demonstrates a good agreement of the primary data. We conclude that in TPE spectra of LHCII and PSI, the contribution of Chls is dominating above 600/1200 nm, whereas the contributions of forbidden Car states increase particularly at wavelengths shorter than 600/1200 nm. Estimates of Car contributions to TPA as well as TPE spectra are given for various wavelengths.


Assuntos
Carotenoides/química , Clorofila/química , Complexos de Proteínas Captadores de Luz/química , Fótons , Análise Espectral/métodos
18.
Eur Biophys J ; 50(2): 211-222, 2021 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-33787948

RESUMO

In the past decade, we developed various fluorescence-based methods for monitoring membrane fusion, membrane docking, distances between membranes, and membrane curvature. These tools were mainly developed using liposomes as model systems, which allows for the dissection of specific interactions mediated by, for example, fusion proteins. Here, we provide an overview of these methods, including two-photon fluorescence cross-correlation spectroscopy and intramembrane Förster energy transfer, with asymmetric labelling of inner and outer membrane leaflets and the calibrated use of transmembrane energy transfer to determine membrane distances below 10 nm. We discuss their application range and their limitations using examples from our work on protein-mediated vesicle docking and fusion.


Assuntos
Fusão de Membrana , Fluorescência , Lipossomos
19.
Chemistry ; 27(6): 2212-2218, 2021 Jan 26.
Artigo em Inglês | MEDLINE | ID: mdl-32955154

RESUMO

We developed three bathochromic, green-light activatable, photolabile protecting groups based on a nitrodibenzofuran (NDBF) core with D-π-A push-pull structures. Variation of donor substituents (D) at the favored ring position enabled us to observe their impact on the photolysis quantum yields. Comparing our new azetidinyl-NDBF (Az-NDBF) photolabile protecting group with our earlier published DMA-NDBF, we obtained insight into its excitation-specific photochemistry. While the "two-photon-only" cage DMA-NDBF was inert against one-photon excitation (1PE) in the visible spectral range, we were able to efficiently release glutamic acid from azetidinyl-NDBF with irradiation at 420 and 530 nm. Thus, a minimal change (a cyclization adding only one carbon atom) resulted in a drastically changed photochemical behavior, which enables photolysis in the green part of the spectrum.

20.
Proc Natl Acad Sci U S A ; 117(52): 32929-32938, 2020 Dec 29.
Artigo em Inglês | MEDLINE | ID: mdl-33318220

RESUMO

There is no theoretical limit in using molecular networks to harvest diffusive sun photons on large areas and funnel them onto much smaller areas of highly efficient but also precious energy-converting materials. The most effective concept reported so far is based on a pool of randomly oriented, light-harvesting donor molecules that funnel all excitation quanta by ultrafast energy transfer to individual light-redirecting acceptor molecules oriented parallel to the energy converters. However, the best practical light-harvesting system could only be discovered by empirical screening of molecules that either align or not within stretched polymers and the maximum absorption wavelength of the empirical system was far away from the solar maximum. No molecular property was known explaining why certain molecules would align very effectively whereas similar molecules did not. Here, we first explore what molecular properties are responsible for a molecule to be aligned. We found a parameter derived directly from the molecular structure with a high predictive power for the alignability. In addition, we found a set of ultrafast funneling molecules that harvest three times more energy in the solar's spectrum peak for GaInP photovoltaics. A detailed study on the ultrafast dipole moment reorientation dynamics demonstrates that refocusing of the diffusive light is based on ∼15-ps initial dipole moment depolarization followed by ∼50-ps repolarization into desired directions. This provides a detailed understanding of the molecular depolarization/repolarization processes responsible for refocusing diffusively scattered photons without violating the second law of thermodynamics.

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