Phase-Stable and Highly Luminescent CsPbI3 Perovskite Nanocrystals with Suppressed Photoluminescence Blinking.

Despite their low band gap, the utility of CsPbI3 nanocrystals (NCs) in solar photovoltaic and optoelectronic applications is rather limited because of their phase instability and photoluminescence (PL) intermittency. Herein we show that phase-pure, monodispersed, stable and highly luminescent CsPbI3 NCs can be obtained by tweaking the conventional hot-injection method employing NH4I as an additional precursor. Single-particle studies show a significant suppression of PL blinking. Among all NCs studied, 60% exhibit only high-intensity ON states with a narrow distribution of intensity. The remaining 40% of NCs exhibit a much wider distribution of PL intensity with a significant contribution of low-intensity OFF states. Excellent characteristics of these CsPbI3 NCs are shown to be the result of NH4+ replacing some surface Cs+ of an iodide-rich surface of the NCs. These phase-stable and highly luminescent CsPbI3 NCs with significantly suppressed PL blinking can be useful single-photon emitters and promising materials for optoelectronic and solar photovoltaic applications.

Low-pH Molten Globule-Like Form of CIA17, a Chitooligosaccharide-Specific Lectin from the Phloem Exudate of Coccinia indica, Retains Carbohydrate-Binding Ability.

pH-induced changes in the conformation, structural dynamics, and carbohydrate-binding activity of Coccinia indica agglutinin (CIA17), a PP2-type lectin, were investigated employing biophysical approaches. The secondary structure of CIA17 remains nearly unaltered over a wide pH range (2.0-8.5), while the tertiary structure of the protein exhibits considerable changes. A decrease in the fluorescence intensity and excited-state lifetime at low pH indicated perturbation in the local conformation (near Trp residues) of CIA17, which was further supported by enhancement in the Trp accessibility toward charged quenchers under acidic conditions. Fluorescence correlation spectroscopic studies indicated that at pH 2.0, CIA17 exists as a monomer over the concentration range of 10-200 nM and forms dimers at higher concentrations (KD ∼ 387 nM) but could not form higher oligomers even at ∼150-fold higher concentrations, unlike under native conditions at pH 7.4. Thermal unfolding of the low pH intermediate involves two distinct steps: dissociation of a dimer to a monomer, followed by the unfolding of the monomer. These results strongly suggest that the acid-induced unfolding pathway of CIA17 involves the formation of a monomeric molten globule-like intermediate, which retains appreciable carbohydrate-binding ability. These observations are of great physiological significance since the PP2 proteins are involved in plant defense responses.

DSC and FCS Studies Reveal the Mechanism of Thermal and Chemical Unfolding of CIA17, a Polydisperse Oligomeric Protein from Coccinia Indica.

The mechanism of thermal and chemical unfolding of Coccinia indica agglutinin (CIA17), a chitooligosacharide-specific phloem exudate lectin, was investigated by biophysical approaches. DSC studies revealed that the unfolding thermogram of CIA17 consists of three components (Tm ∼ 98, 106, and 109 °C), which could be attributed to the dissociation of protein oligomers into constituent dimers, dissociation of the dimers into monomers, and unfolding of the monomers. Intrinsic fluorescence studies on the chemical denaturation by guanidinium thiocyanate and guanidinium chloride indicated the presence of two distinct steps in the unfolding pathway, which could be assigned to dissociation of the dimeric protein into monomers and unfolding of the monomers. Results of fluorescence correlation spectroscopic studies could be interpreted in terms of the following model: CIA17 forms oligomeric structures in a concentration dependent manner, with the protein existing as a monomer below 1 nM concentration but associating to form dimers at higher concentrations (KD ≈ 2.9 nM). The dimers associate to yield tetramers with a KD of ∼50 µM, which further associate to form higher oligomers with further increase in concentration. These results are consistent with the proposed role of CIA17 as a key player in the defense response of the plant against microbes and insects.

Ultrafast carrier dynamics of metal halide perovskite nanocrystals and perovskite-composites.

Perovskite nanocrystals (NCs), especially those based on cesium lead halides, have emerged in recent years as highly promising materials for efficient solar cells and photonic applications. The key to realization of full potential of these materials lies however in the molecular level understanding of the processes triggered by light. Herein we highlight the knowledge gained from photophysical investigations on these NCs of various sizes and compositions employing primarily the femtosecond pump-probe technique. We show how spectral and temporal characterization of the photo-induced transients provide insight into the mechanism and dynamics of relaxation of hot and thermalized charge carriers through their recombination and trapping. We discuss how the multiple excitons including the charged ones (trions), generated using high pump fluence or photon energy, recombine through the Auger-assisted process. We discussed the harvesting of hot carriers prior to their cooling and band-edge carriers from these perovskite NCs to wide band-gap metal oxides, metal chalcogenide NCs and molecular acceptors. How perovskites can influence the charge carrier dynamics in composites of organic and inorganic semiconductors is also discussed.