Gold nanomaterials have received great interest for their use in cancer theranostic applications over the past two decades. Many gold nanoparticle-based drug delivery system designs rely on adsorbed ligands such as DNA or cleavable linkers to load therapeutic cargo. The heightened research interest was recently demonstrated in the simple design of nanoparticle-drug conjugates wherein drug molecules are directly adsorbed onto the as-synthesized nanoparticle surface. The potent chemotherapeutic, doxorubicin often serves as a model drug for gold nanoparticle-based delivery platforms; however, the specific interaction facilitating adsorption in this system remains understudied. Here, for the first time, we propose empirical and theoretical evidence suggestive of the main adsorption process where (1) hydrophobic forces drive doxorubicin towards the gold nanoparticle surface before (2) cation-π interactions and gold-carbonyl coordination between the drug molecule and the cations on AuNP surface facilitate DOX adsorption. In addition, biologically relevant compounds, such as serum albumin and glutathione, were shown to enhance desorption of loaded drug molecules from AuNP at physiologically relevant concentrations, providing insight into the drug release and in vivo stability of such drug conjugates.

Isolation of specific rare cell subtypes from whole blood is critical in cellular analysis and important in basic and clinical research. Traditional immunomagnetic cell capture suffers from suboptimal sensitivity, specificity, and time- and cost-effectiveness. Mimicking the features of octopuses, a device termed a “NanoOctopus” was developed for cancer cell isolation in whole blood. The device consists of long multimerized aptamer DNA strands, or tentacle DNA, immobilized on magnetic microparticle surfaces. Their ultrahigh sensitivity and specificity are attributed to multivalent binding of the tentacle DNA to cell receptors without steric hindrance. The simple, quick, and noninvasive capture and release of the target cells allows for extensive downstream cellular and molecular analysis, and the time- and cost-effectiveness of fabrication and regeneration of the devices makes them attractive for industrial manufacture.

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This paper studies the excitonic factor in the excited state energy transfer of phycobilisome (PBS) by using a polarized time-resolved pump-probe and by changing the ionic strength of the cofactors’ medium in the PBS of Acaryochloris marina (A. marina). As a result, the interplay between the surrounding medium and the closely excited adjacent cofactors is shown to be a negligible factor of the excitonic decay kinetics at 618 nm of the phycocyanin (PC), while it appears as a driving factor of an increase in excitonic delocalization at 630 nm. The obtained anisotropy values are consistent with the contribution of ionic strength in the excitonic mechanism in PBS. These values were 0.38 in high ionic strength and 0.4 in low ionic strength at 618 nm, and 0.52 in high ionic strength and 0.4 in low ionic strength at 630–635 nm. The anisotropy value of 0.52 in high phosphate is similar at 630 nm and 635 nm, which is consistent with an excitonic delocalization band at 635 nm. The 635 nm band is suggested to show the true low energy level of PC in A. marina PBS. The anisotropy decay kinetic at 630 nm suggests that the excited state population of PC is not all equilibrated in 3 ps because of the existence of the 10 ps decay kinetic component. The presence of the slow kinetic decay component in high, and low ionic strength, is consistent with a 10 and 14 ps energy transfer pathway, while the 450 fs kinetic decay component is consistent with the presence of an additional excitation energy transfer pathway between adjacent α84 and β84. Furthermore, the 450 fs decay kinetic is suggested to be trapped in the trimer, while the 400 fs decay kinetic rules out an excitonic flow from low energy level PC to allophycoyanin. This excitonic flow may occur between β84 in adjacent trimers, towards the low energy state of the PBS rod.

We applied a femtosecond flash method, using induced transient absorption changes, to obtain a time-resolved view of excitation energy transfer in intact phycobilisomes of Thermosynechococcus vulcanus at room temperature. Our measurement of an excitation energy transfer rate of 888 fs in phycobilisomes shows the existence of ultrafast kinetics along the phycocyanin rod subcomplex to the allophycocyanin core that is faster than expected for previous excitation energy transfer based on Förster theory in phycobilisomes. Allophycocyanin in the core further transfers energy to the terminal emitter(s) in 17 ps. In the phycobilisome, rod doublets composed of hexameric phycocyanin discs and internal linker proteins are arranged in a parallel fashion, facilitating direct rod-rod interactions. Excitonic splitting likely drives rod absorption at 635 nm as a result of strong coupling between β84 chromophores (20 ± 1 Å) in adjacent hexamers. In comparison to the absorbance of the phycobilisome antenna system of the cyanobacterium Acaryochloris marina, which possesses a single rod structure, the linkers in T. vulcanus rods induce a 17 nm red shift in the absorbance spectrum. Furthermore, the kinetics of 888 fs indicates that the presence of the linker protein induces ultrafast excitation energy transfer between phycocyanin and allophycocyanin inside the phycobilisome, which is faster than all previous excitation energy transfer in phycobilisome subunits or sub-complexes reported to date.