Herein, we report for the first time on a full-fledged investigation of water-soluble CdTe quantum dots (QD) that are immobilized onto exfoliated graphite (EG) and/or nanographene (NG). Particular emphasis was placed on a top-down preparation of stable aqueous dispersions-starting from natural graphite rather than graphene oxide-while preserving the intrinsic properties of graphene. To this end, we circumvented the harsh conditions commonly employed for the pre-exfoliation (i.e., Hummers method). First, a hydrophobic-hydrophobic/π-π stacking motif was tested between EG and pyrene, to which QDs are covalently attached (QD-pyrene). Second, we employed the combination of hydrophobic-hydrophobic/π-π stacking and electrostatic interactions to build up hierarchical structures composed of NG, positively charged pyrene (pyrene(+)), and negatively charged QDs. The novel nanohybrids-QD-pyrene/EG and QD/pyrene(+)/NG-were characterized with specific emphasis on electron-transfer chemistry. In fact, both assays provide kinetic and spectroscopic evidence that support electron transfer dynamics that vary, however, between EG and NG as a reflection of the different degree of graphite exfoliation.
The impact of Förster resonant energy transfer (FRET) in CdTe quantum dot (QD) based photoelectrochemical cells is investigated. By deposition of different CdTe QD sizes onto indium on oxide electrodes, FRET across the photoactive film could be obtained, resulting in a 25% enhancement of the photon‐to‐current efficiency when compared to reference systems that lack FRET.
Inorganic meets organic: Covalent bonds (peptide condensation) and noncovalent interactions (π–π stacking) have been employed en route toward versatile donor–acceptor inorganic–organic nanohybrids, QD‐pyrene/SWNT. A charge‐transfer event within the hybrid transforms the excitonic state of the quantum dot into a charge‐transfer state that has a lifetime of several nanoseconds.
The novelty of the current work lies in the versatile synthesis of highly luminescent water-soluble CdTe quantum rods (QR) which to the best of our knowledge are the first known water-soluble QR carrying positively charged stabilizer.
Newly prepared CdTe quantum dots ( QD) bearing shells of water solubility providing capping agents (i.e., thioglycolic acid ( TGA) and 2-(dimethylamino)ethanethiol hydrochloride (DMAET) were subjected to electrostatic assays with several proteins (i.e., cytochrome c (cyt c) and human serum albumin (HSA). In particular, we employed absorption, emission, transient absorption and time-resolved emission spectroscopic means to test their response to light. Only for negatively capped QDs spectroscopic and kinetic evidence were gathered that corroborate the successful bioconjugation of QDs with cyt c to yield QD- cyt c bioconjugates. In fact, photoexcitation of QD-cyt c leads to a fast deactivation of the QD band gap emission and of the QD excited state. Notably, these interactions depend on the size of the QDs. Repulsive forces, on the other hand, are operative between the positively capped QDs and cyt c, hampering any bioconjugation.
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