Abstract:Targeting the DNA
of tumor cells with small molecules may offer effective clinical strategies
for transcriptional inhibition. We unveil synthesis and characterization
of ∼20 nm chiral carbon nanoparticles for enantiospecific recognition
of DNA. Our approach inculcates chirality in carbon nanoparticles
by controlled tethering of minor groove binders, i.e., Tröger’s
base (TB). The chiral particles positively enriched the cellular nucleus
in MCF-7 breast cancer cells, irrespective of the TB asymmetry tethered
on… Show more
“…47 The N1s band can be deconvoluted into three peaks, pyridinic N (~399.6 eV), amino N (~400.5 eV), and pyrrolic N (401.6 eV). 48 However, for CD-A 5 , the pyrrolic peak was absent. The elemental composition of the CDs as well as a detailed analysis of O1s, C1s, and N1s of different CDs have been summarized in Table S3-Table S6.…”
Carbon dots (CDs) are extensively studied to investigate their unique optical properties such as undergoing electron transfer in different scenarios. This study presents an in-depth investigation to study the ensemble-averaged state/bulk state and single-particle level photophysical properties of CDs that have been passivated with electron-accepting (CD-A) and electron-donating molecules (CD-D) on their surface. Our ensemble-averaged state experiments including UV-Vis absorbance titrations, time-resolved photoluminescence (PL) spectra, and 2D emission studies depicted that both CD-A or CD-D had a blue-shift in emission, with a drastic increase in emission intensity, and consequently higher quantum yields, and that acceptor populations (CD-A) dominate overall photophysical properties. Interestingly, transmission electron microscopy and atomic force microscopy revealed that the mixing of donor and acceptor particles (CD-A+ CD-D) leads to a formation of at least two associated geometries, which was dependent on time, concentration, intramolecular electron/charge transfer and hydrogen bonding. On the other hand, single-particle studies revealed that the instantaneous intensity of CDs was comparable, but that CD-A and CD-D have a larger on-time duty cycle, attributed to an increase of blinking frequency. On-and off-time power-law analysis further revealed that CD-A has a larger off-time distribution slope than bare CDs, This article is protected by copyright. All rights reserved. 3 while their on-time distribution is similar. CD-D exhibits an increase in both on-and off-time distribution slope compared to bare CDs. These results indicate that the electron donor provides additional bright and dark states, while the electron acceptor primarily provides bright states, which can explain the increased blinking frequency in CD-A and CD-D at the single-particle level. Singleparticle studies, however, did not reveal an "acceptor-dominating" scenario based on analysis of instantaneous intensity, bleaching kinetics, and photoblinking, indicating that the direct interaction of CD-A and CD-D may affect their photophysical properties in the bulk state due to formation of hierarchical structural assemblies. We anticipate that these fundamental results will further provide insights towards our understanding of the complex mechanism associated with CD emission, which is one of the key contributors to their successful application. As an immediate application of these CDs, we have shown that they can be used as a sensing array for metal ions and can serve as a powerful toolbox for the technological application of CDs.
“…47 The N1s band can be deconvoluted into three peaks, pyridinic N (~399.6 eV), amino N (~400.5 eV), and pyrrolic N (401.6 eV). 48 However, for CD-A 5 , the pyrrolic peak was absent. The elemental composition of the CDs as well as a detailed analysis of O1s, C1s, and N1s of different CDs have been summarized in Table S3-Table S6.…”
Carbon dots (CDs) are extensively studied to investigate their unique optical properties such as undergoing electron transfer in different scenarios. This study presents an in-depth investigation to study the ensemble-averaged state/bulk state and single-particle level photophysical properties of CDs that have been passivated with electron-accepting (CD-A) and electron-donating molecules (CD-D) on their surface. Our ensemble-averaged state experiments including UV-Vis absorbance titrations, time-resolved photoluminescence (PL) spectra, and 2D emission studies depicted that both CD-A or CD-D had a blue-shift in emission, with a drastic increase in emission intensity, and consequently higher quantum yields, and that acceptor populations (CD-A) dominate overall photophysical properties. Interestingly, transmission electron microscopy and atomic force microscopy revealed that the mixing of donor and acceptor particles (CD-A+ CD-D) leads to a formation of at least two associated geometries, which was dependent on time, concentration, intramolecular electron/charge transfer and hydrogen bonding. On the other hand, single-particle studies revealed that the instantaneous intensity of CDs was comparable, but that CD-A and CD-D have a larger on-time duty cycle, attributed to an increase of blinking frequency. On-and off-time power-law analysis further revealed that CD-A has a larger off-time distribution slope than bare CDs, This article is protected by copyright. All rights reserved. 3 while their on-time distribution is similar. CD-D exhibits an increase in both on-and off-time distribution slope compared to bare CDs. These results indicate that the electron donor provides additional bright and dark states, while the electron acceptor primarily provides bright states, which can explain the increased blinking frequency in CD-A and CD-D at the single-particle level. Singleparticle studies, however, did not reveal an "acceptor-dominating" scenario based on analysis of instantaneous intensity, bleaching kinetics, and photoblinking, indicating that the direct interaction of CD-A and CD-D may affect their photophysical properties in the bulk state due to formation of hierarchical structural assemblies. We anticipate that these fundamental results will further provide insights towards our understanding of the complex mechanism associated with CD emission, which is one of the key contributors to their successful application. As an immediate application of these CDs, we have shown that they can be used as a sensing array for metal ions and can serve as a powerful toolbox for the technological application of CDs.
“…are composed of chiral small‐molecules. Hence, a good deal of biological and physiological activities such as proteins adhesion, [ 5‐6 ] genetic expression [ 7‐8 ] and cell adsorption, [ 9‐10 ] are highly affected by chiral molecules, which usually occur on chiral surface and are essential in maintaining the normal function of life body. [ 11‐13 ] The exploration of the interaction between these molecules and chiral surface not only may conduce to enhance people's comprehension from the perspective of chemistry and biochemistry, but also can provide some helpful inspiration for practical application of chiral surface.…”
Section: Background and Originality Contentmentioning
Comprehensive Summary
Chiral properties of biological surface is of importance as they dominate interactions with biomolecules (such as proteins, nucleic acids, hormones) in a living system. Inspired by this phenomenon, we designed and constructed a L‐/D‐N‐acetyl‐cysteine‐pillar[6]arene functionalized Si surface (L‐/D‐NACP surface) for studying the influence of superficial chirality on selective adsorption of R‐adrenaline. The fabricated chiral L‐/D‐NACP surface with consistency in hydrophilia and elementary composition exhibited a strong mirror‐symmetric circular dichroism signal. In the adsorption study, the contact‐angle of R‐adrenaline droplet on D‐NACP surface was more hydrophilic from macroscopical view, and the size and quantity of R‐adrenaline aggregation on D‐NACP surface was larger than L‐NACP surface, implying selective adsorption of R‐adrenaline appeared on the D‐NACP surface. The possible mechanism was due to the stronger host‐guest interaction between D‐NACP and R‐adrenaline, which facilitated the selective adsorption. Besides, the D‐NACP surface with good selectivity can be used for chiral separation of racemic adrenaline. The results enhance the understanding of hormones adsorption affected by surface chirality, and may provide some helpful inspiration for practical application of chiral surface.
“…It was found that chiral particles present groove-binding agents at the nanometer level, which can be positively enriching the cellular nucleus in MCF-7 breast cancer cells and give DNA enantiomer-specific recognition and help induce the apoptotic cascade of cancer cells. However, the negatively induced chiral carbon nanoparticles showed higher efficiency in inhibiting cell growth [ 72 ]. Schematic showing cancer cell apoptosis caused by the interaction between chiral carbon NPs and DNA (Fig.…”
Section: Chiral Nanomaterials That Induce Apoptosis In Tumor Cellsmentioning
confidence: 99%
“…Reprinted with permission from ref. [ 72 ]. Copyright (2018) Wiley–VCH Verlag GmbH & Co. KGaA, Weinheim Fig.…”
Section: Chiral Nanomaterials That Induce Apoptosis In Tumor Cellsmentioning
confidence: 99%
“…In addition, the D-chirality matches that of the L-phospholipid molecular layer on the surface of the cancer cell, leading to more efficient binding between them, and D-NPs are not easily degraded by natural proteases and coenzymes in the cellular environment, Both of these make D-NPs better absorbed by cancer cells and induce their apoptosis.Moreover, the efficacy of the negatively induced chiral carbon NPs in cancer treatment may due to the low intracellular PH value, the negatively induced chiral carbon NPs can more easily enter in nucleus by lipid-flipping thereby interacting with DNA in a grooved manner [ 72 ].…”
Section: Chiral Nanomaterials That Induce Apoptosis In Tumor Cellsmentioning
Chirality is a fundamental characteristic of natural molecules and a crucial factor in the biochemical reactions of living cells and organisms. Recently, researchers have successfully introduced chiral molecules to the surfaces of nanomaterials, creating chiral nanomaterials that exhibit an upscaling of chiral behavior from the molecular scale to the nanoscale. These chiral nanomaterials can selectively induce autophagy, apoptosis, and photothermal ablation in tumor cells based on their chirality, making them promising for application in anti-tumor therapy. However, these interesting and important phenomena have hitherto received little attention. Accordingly, we herein present a review of recent research progress in the field of chiral nanomaterials for tumor therapy along with brief looks at the mechanistic details of their actions. Finally, the current challenges and future perspectives of chiral nanomaterials in terms of maximizing their potential in tumor therapy are discussed. Thus, this review provides a helpful introduction to the design of chiral nanomaterials and will hopefully highlight the importance of chirality in tumor therapy.
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