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1.
J Am Chem Soc ; 146(30): 20636-20648, 2024 Jul 31.
Article in English | MEDLINE | ID: mdl-39018374

ABSTRACT

Current syntheses of CsPbBr3 halide perovskite nanocrystals (NCs) rely on overstoichiometric amounts of Pb2+ precursors, resulting in unreacted lead ions at the end of the process. In our synthesis scheme of CsPbBr3 NCs, we replaced excess Pb2+ with different exogenous metal cations (M) and investigated their effect on the synthesis products. These cations can be divided into two groups: group 1 delivers monodisperse CsPbBr3 cubes capped with oleate species (as for the case when Pb2+ is used in excess) and with a photoluminescence quantum yield (PLQY) as high as 90% with some cations (for example with M = In3+); group 2 yields irregularly shaped CsPbBr3 NCs with broad size distributions. In both cases, the addition of a tertiary ammonium cation (didodecylmethylammonium, DDMA+) during the synthesis, after the nucleation of the NCs, reshapes the NCs to monodisperse truncated cubes. Such NCs feature a mixed oleate/DDMA+ surface termination with PLQY values of up to 97%. For group 1 cations this happens only if the ammonium cation is directly added as a salt (DDMA-Br), while for group 2 cations this happens even if the corresponding tertiary amine (DDMA) is added, instead of DDMA-Br. This is attributed to the fact that only group 2 cations can facilitate the protonation of DDMA by the excess oleic acid present in the reaction environment. In all cases studied, the incorporation of M cations is marginal, and the reshaping of the NCs is only transient: if the reactions are run for a long time, the truncated cubes evolve to cubes.

2.
ACS Appl Mater Interfaces ; 16(9): 11627-11636, 2024 Mar 06.
Article in English | MEDLINE | ID: mdl-38381521

ABSTRACT

Halide perovskite nanocrystals (NCs), specifically CsPbBr3, have attracted considerable interest due to their remarkable optical properties for optoelectronic devices. To achieve high-efficiency light-emitting diodes (LEDs) based on CsPbBr3 nanocrystals (NCs), it is crucial to optimize both their photoluminescence quantum yield (PLQY) and carrier transport properties when they are deposited to form films on substrates. While the exchange of native ligands with didodecyl dimethylammonium bromide (DDAB) ligand pairs has been successful in boosting their PLQY, dense DDAB coverage on the surface of NCs should impede carrier transport and limit device efficiency. Following our previous work, here, we use oleyl phosphonic acid (OLPA) as a selective stripping agent to remove a fraction of DDAB from the NC surface and demonstrate that such stripping enhances carrier transport while maintaining a high PLQY. Through systematic optimization of OLPA dosage, we significantly improve the performance of CsPbBr3 LEDs, achieving a maximum external quantum efficiency (EQE) of 15.1% at 516 nm and a maximum brightness of 5931 cd m-2. These findings underscore the potential of controlled ligand stripping to enhance the performance of CsPbBr3 NC-based optoelectronic devices.

3.
J Am Chem Soc ; 145(33): 18329-18339, 2023 Aug 23.
Article in English | MEDLINE | ID: mdl-37608781

ABSTRACT

We have approached the synthesis of colloidal InAs nanocrystals (NCs) using amino-As and ligands that are different from the commonly employed oleylamine (OA). We found that carboxylic and phosphonic acids led only to oxides, whereas tri-n-octylphosphine, dioctylamine, or trioctylamine (TOA), when employed as the sole ligands, yielded InAs NCs with irregular sizes and a broad size distribution. Instead, various combinations of TOA and OA delivered InAs NCs with good control over the size distribution, and the TOA:OA volume ratio of 4:1 generated InAs tetrapods with arm length of 5-6 nm. Contrary to tetrapods of II-VI materials, which have a zinc-blende core and wurtzite arms, these NCs are entirely zinc-blende, with arms growing along the ⟨111⟩ directions. They feature a narrow excitonic peak at ∼950 nm in absorption and a weak photoluminescence emission at 1050 nm. Our calculations indicated that the bandgap of the InAs tetrapods is mainly governed by the size of their core and not by their arm lengths when these are longer than ∼3 nm. Nuclear magnetic resonance analyses revealed that InAs tetrapods are mostly passivated by OA with only a minor fraction of TOA. Molecular dynamics simulations showed that OA strongly binds to the (111) facets whereas TOA weakly binds to the edges and corners of the NCs and their combined use (at high TOA:OA volume ratios) promotes growth along the ⟨111⟩ directions, eventually forming tetrapods. Our work highlights the use of mixtures of ligands as a means of improving control over InAs NCs size and size distribution.

4.
ACS Appl Mater Interfaces ; 15(23): 28166-28174, 2023 Jun 14.
Article in English | MEDLINE | ID: mdl-37259773

ABSTRACT

One major concern toward the performance and stability of halide perovskite-based optoelectronic devices is the formation of metallic lead that promotes nonradiative recombination of charge carriers. The origin of metallic lead formation is being disputed whether it occurs during the perovskite synthesis or only after light, electron, or X-ray beam irradiation or thermal annealing. Here, we show that the quantity of metallic lead detected in perovskite crystals depends on the concentration and composition of the precursor solution. Through a controlled crystallization process, we grew black-colored mixed dimethylammonium (DMA)/methylammonium (MA) lead tribromide crystals. The black color is suggested to be due to the presence of small lead clusters. Despite the unexpected black coloring, the crystals show higher crystallinity and less defect density with respect to the standard yellow-colored DMA/MAPbBr3 crystals, as indicated by X-ray rocking curve and dark current measurements, respectively. While the formation of metallic lead could still be induced by external factors, the precursor solution composition and concentration can facilitate the formation of metallic lead during the crystallization process. Our results indicate that additional research is required to fully understand the perovskite precursor solution chemistry.

5.
Nano Lett ; 22(21): 8567-8573, 2022 Nov 09.
Article in English | MEDLINE | ID: mdl-36288498

ABSTRACT

We show how, in the synthesis of yellow-emissive Bi-doped Cs2Ag1-xNaxInCl6 double perovskite nanocrystals (NCs), preventing the transient formation of Ag0 particles increases the photoluminescence quantum yield (PLQY) of the NCs from ∼30% to ∼60%. Calculations indicate that the presence of even a single Ag0 species on the surface of a NC introduces deep trap states. The PL efficiency of these NCs is further increased to ∼70% by partial replacement of Na+ with K+ ions, up to a 7% K content, due to a lattice expansion that promotes a more favorable ligands packing on the NC surface, hence better surface passivation. A further increase in K+ lowers the PLQY, due to both the activation of nonradiative quenching channels and a lower oscillator strength of the BiCl6→AgCl6 transition (through which PL emission occurs). The work indicates how a deeper understanding of parameters influencing carrier trapping/relaxation can boost the PLQY of double perovskites NCs.

6.
Eur J Pharm Biopharm ; 174: 90-100, 2022 May.
Article in English | MEDLINE | ID: mdl-35358697

ABSTRACT

Maximizing loading while modulating the release of therapeutic molecules from nanoparticles and implantable drug delivery systems is the key to successfully address deadly diseases like brain cancer. Here, four different conjugates of the potent chemotherapeutic molecule docetaxel (DTXL)were realized to optimize the pharmacological properties of 1,000 × 400 nmDiscoidal PolymericNanoconstructs(DPNs). DTXL was covalently linked to poly-(ethylene) glycol(PEG)chains of different molecular weights, namely 350, 550 and 1,000 Da, and oleic acid (OA). After extensive physico-chemical and pharmacological characterizations, the conjugate PEG550-DTXL showedan optimal compromise between loading and sustained release out of DPNs, as opposed to the insufficient loading of PEG1000-DTXL and PEG350-DTXL and the excessively slow release of OA-DTXL. Not surprisingly, viability tests conducted on U87-MG cells showed a delay in cytotoxic activity for the DTXL conjugates compared to free DTXL within the first 48 h. However, PEG550-DTXL returned an IC50 value of âˆ¼ 10 nMat 72 h, which is comparable to free DTXL.In mice bearing orthotopically implanted U87-MG cells, the intravenous administration of PEG550-DTXL loaded DPNs doubled the overall animal survival (52.5 days) as compared to temozolomide (27 days) and the untreated controls (32 days). Collectively, these results continue to demonstrate that the therapeutic efficacy of nanoparticles can be boosted by rationally designing drug conjugates-particle complexes for optimal loading and release profiles.


Subject(s)
Antineoplastic Agents , Glioblastoma , Nanoparticles , Animals , Docetaxel , Glioblastoma/drug therapy , Mice , Nanoparticles/chemistry , Oleic Acid , Polyethylene Glycols/chemistry , Taxoids/pharmacology
7.
ACS Nano ; 16(1): 1444-1455, 2022 Jan 25.
Article in English | MEDLINE | ID: mdl-35005882

ABSTRACT

The interaction of lead bromide perovskite nanocrystals with charged ligands, such as salts, zwitterions, or acid-base pairs, has been extensively documented over the past few years. On the other hand, little is known about the reactivity of perovskite nanocrystals toward neutral ligands. To fill this gap, in this work we study the interaction of CsPbBr3 nanocrystals passivated with didodecyldimethylammonium bromide (DDABr) toward a series of exogenous acid/base ligands using a combined computational and experimental approach. Our analysis indicates that DDABr-capped nanocrystals are inert toward most ligands, except for carboxylic, phosphonic, and sulfonic acids. In agreement with the calculations, our experimental results indicate that the higher the acidity of the ligands employed in the treatment, the more etching is observed. In detail, dodecylbenzenesulfonic acid (pKa = -1.8) is found to etch the nanocrystals, causing their complete degradation. On the other hand, oleic and oleylphosphonic acids (pKa 9.9 and 2, respectively) interact with surface-bound DDA molecules, causing their displacement as DDABr in various amounts, which can be as high as 40% (achieved with oleylphosphonic acid). Despite the stripping of DDA ligands, the optical properties of the nanocrystals, as well as structure and morphology, remain substantially unaffected, empirically demonstrating the defect tolerance characterizing such materials. Our study provides not only a clear overview on the interaction between perovskite nanocrystals and neutral ligands but also presents an effective ligand stripping strategy.

8.
Adv Mater ; 34(7): e2106160, 2022 Feb.
Article in English | MEDLINE | ID: mdl-34856033

ABSTRACT

The solvent acidolysis crystallization technique is utilized to grow mixed dimethylammonium/methylammonium lead tribromide (DMA/MAPbBr3 ) crystals reaching the highest dimethylammonium incorporation of 44% while maintaining the 3D cubic perovskite phase. These mixed perovskite crystals show suppression of the orthorhombic phase and a lower tetragonal-to-cubic phase-transition temperature compared to MAPbBr3 . A distinct behavior is observed in the temperature-dependent photoluminescence properties of MAPbBr3 and mixed DMA/MAPbBr3 crystals due to the different organic cation dynamics governing the phase transition(s). Furthermore, lateral photodetectors based on these crystals show that, at room temperature, the mixed crystals possess higher detectivity compared to MAPbBr3 crystals caused by structural compression and reduced surface trap density. Remarkably, the mixed-crystal devices exhibit large enhancement in their detectivity below the phase-transition temperature (at 200 K), while for the MAPbBr3 devices only insignificant changes are observed. The high detectivity of the mixed crystals makes them attractive for visible-light communication and for space applications. The results highlight the importance of the synthetic technique for compositional engineering of halide perovskites that governs their structural and optoelectronic properties.

9.
ACS Energy Lett ; 6(8): 2844-2853, 2021 Aug 13.
Article in English | MEDLINE | ID: mdl-34423129

ABSTRACT

We report a one-step synthesis of halide perovskite nanocrystals embedded in amphiphilic polymer (poly(acrylic acid)-block-poly(styrene), PAA-b-PS) micelles, based on injecting a dimethylformamide solution of PAA-b-PS, PbBr2, ABr (A = Cs, formamidinium, or both) and "additive" molecules in toluene. These bifunctional or trifunctional short chain organic molecules improve the nanocrystal-polymer compatibility, increasing the nanocrystal stability against polar solvents and high flux irradiation (the nanocrystals retain almost 80% of their photoluminescence after 1 h of 3.2 w/cm2 irradiation). If the nanocrystals are suspended in toluene, the coil state of the polymer allows the nanocrystals to undergo halide exchange, enabling emission color tunability. If the nanocrystals are suspended in methanol, or dried as powders, the polymer is in the globule state, and they are inert to halide exchange. By mixing three primary colors we could prepare stable, multicolor emissive samples (for example, white emitting powders) and a UV-to-white color converting layer for light-emitting diodes entirely made of perovskite nanocrystals.

10.
Carbohydr Polym ; 271: 118031, 2021 Nov 01.
Article in English | MEDLINE | ID: mdl-34364545

ABSTRACT

Cellulose ester films were prepared by esterification of cellulose with a multibranched fluorinated carboxylic acid, "BRFA" (BRanched Fluorinated Acid), at different anhydroglucose unit:BRFA molar ratios (i.e., 1:0, 10:1, 5:1, and 1:1). Morphological and optical analyses showed that cellulose-BRFA materials at molar ratios 10:1 and 5:1 formed flat and transparent films, while the one at 1:1 M ratio formed rough and translucent films. Degrees of substitution (DS) of 0.06, 0.09, and 0.23 were calculated by NMR for the samples at molar ratios 10:1, 5:1, and 1:1, respectively. ATR-FTIR spectroscopy confirmed the esterification. DSC thermograms showed a single glass transition, typical of amorphous polymers, at -11 °C. The presence of BRFA groups shifted the mechanical behavior from rigid to ductile and soft with increasing DS. Wettability was similar to standard fluoropolymers such as PTFE and PVDF. Finally, breathability and water uptake were characterized and found comparable to materials typically used in textiles.


Subject(s)
Cellulose/analogs & derivatives , Esters/chemistry , Hydrocarbons, Fluorinated/chemistry , Membranes, Artificial , Propionates/chemistry , Cellulose/chemical synthesis , Esterification , Esters/chemical synthesis , Hydrocarbons, Fluorinated/chemical synthesis , Hydrophobic and Hydrophilic Interactions , Propionates/chemical synthesis , Tensile Strength , Wettability
11.
Nano Lett ; 20(12): 8847-8853, 2020 Dec 09.
Article in English | MEDLINE | ID: mdl-33201718

ABSTRACT

We employed oleylphosphonic acid (OLPA) for the synthesis of CsPbBr3 nanocrystals (NCs). Compared to phosphonic acids with linear alkyl chains, OLPA features a higher solubility in apolar solvents, allowing us to work at lower synthesis temperatures (100 °C), which in turn offer a good control over the NCs size. This can be reduced down to 5.0 nm, giving access to the strong quantum confinement regime. OLPA-based NCs form stable colloidal solutions at very low concentrations (∼1 nM), even when exposed to air. Such stability stems from the high solubility of OLPA in apolar solvents, which enables these molecules to reversibly bind/unbind to/from the NCs, preventing the NCs aggregation/precipitation. Small NCs feature efficient, blue-shifted emission and an ultraslow emission kinetics at cryogenic temperature, in striking difference to the fast decay of larger particles, suggesting that size-related exciton structure and/or trapping-detrapping dynamics determine the thermal equilibrium between coexisting radiative processes.

12.
J Med Chem ; 63(19): 11169-11194, 2020 10 08.
Article in English | MEDLINE | ID: mdl-32946228

ABSTRACT

Cystic fibrosis (CF) is a life-threatening autosomal recessive disease, caused by mutations in the CF transmembrane conductance regulator (CFTR) chloride channel. CFTR modulators have been reported to address the basic defects associated with CF-causing mutations, partially restoring the CFTR function in terms of protein processing and/or channel gating. Small-molecule compounds, called potentiators, are known to ameliorate the gating defect. In this study, we describe the identification of the 2,3,4,5-tetrahydro-1H-pyrido[4,3-b]indole core as a novel chemotype of potentiators. In-depth structure-activity relationship studies led to the discovery of enantiomerically pure 39 endowed with a good efficacy in rescuing the gating defect of F508del- and G551D-CFTR and a promising in vitro druglike profile. The in vivo characterization of γ-carboline 39 showed considerable exposure levels and good oral bioavailability, with detectable distribution to the lungs after oral administration to rats. Overall, these findings may represent an encouraging starting point to further expand this chemical class, adding a new chemotype to the existing classes of CFTR potentiators.


Subject(s)
Cystic Fibrosis Transmembrane Conductance Regulator/drug effects , Indoles/pharmacology , Animals , Humans , Indoles/chemistry , Male , Rats , Rats, Sprague-Dawley , Structure-Activity Relationship
13.
Chem Sci ; 11(15): 3986-3995, 2020 Apr 21.
Article in English | MEDLINE | ID: mdl-32884635

ABSTRACT

The preparation of strongly emissive CsPbBr3 perovskite nanocrystals with robust surface passivation is a challenge in the field of lead halide perovskite nanomaterials. We report an approach to prepare polymer-capped CsPbBr3 perovskite nanocrystals by reacting oleylammonium/oleate-capped Cs4PbBr6 nanocrystals with poly(maleic anhydride-alt-1-octadecene) (PMAO). PMAO contains succinic anhydride units that are reactive towards the oleylamine species present on the Cs4PbBr6 nanocrystals' surface and produces polysuccinamic acid, which, in turn, triggers the Cs4PbBr6 to CsPbBr3 conversion. The transformation occurs through the formation of Cs4PbBr6-CsPbBr3 heterostructures as intermediates, which are captured because of the mild reactivity of PMAO and are investigated by high-resolution electron microscopy. The Cs4PbBr6-CsPbBr3 heterostructures demonstrate a dual emission at cryogenic temperature with an indication of the energy transfer from Cs4PbBr6 to CsPbBr3. The fully-transformed CsPbBr3 NCs have high photoluminescence quantum yield and enhanced colloidal stability, which we attribute to the adhesion of polysuccinamic acid to the NC surface through its multiple functional groups in place of oleate and alkylammonium ligands. The PMAO-induced transformation of Cs4PbBr6 NCs opens up a strategy for the chemical modification of metal halide NCs initially passivated with nucleophilic amines.

14.
J Chromatogr A ; 1628: 461434, 2020 Sep 27.
Article in English | MEDLINE | ID: mdl-32822974

ABSTRACT

Differing sensitivity is the main obstacle for a direct combination of HPTLC with NMR spectroscopy. A sufficient amount of the isolated compound zone must be provided by HPTLC for subsequent offline NMR detection (HPTLC//NMR). To fill the gap, a straightforward procedure was developed using the same analytical HPTLC system for both bioprofiling and isolation of bioactive zones from multicomponent mixtures. The HPTLC-effect-directed analysis (EDA) revealed several bioactive compounds in five botanical extracts, i.e. Salvia officinalis, Thymus vulgaris and Origanum vulgare, all Lamiaceae, and peels of red and green apples (Jonagored and Granny Smith, respectively), both Rosaceae. A tricky case study was designed to show how to deal with potentially coeluting bioactive structural isomers, e.g., ursolic (UA), oleanolic (OA) and betulinic acids (all C30H48O3), which are most difficult to identify and assign. A multipotent bioactive HPTLC zone showed the same hRF value and mass signal in HPTLCHRMS, though containing the coeluting structural isomers UA and OA. After zone isolation from the HPTLC plate, first the 1H NMR spectrum allowed to distinguish distinct allylic H-18 protons, i.e. 2.20 ppm for UA and 2.85 ppm for OA, and at the same time, to quantify the two isomers by using the PUlse Length-based CONcentration methodology (HPTLC//1H qNMR-PULCON). In case of a partial overlap of the diagnostic signal with that of the matrix, results were corroborated with those obtained by using the 1H deconvoluted or 2D 1H-13C Heteronuclear Single Quantum Coherence spectra. The comparison of the quantitative results showed a good correlation (R2 = 0.9718) between the two orthogonal methods HPTLC-Vis and HPTLC//1H qNMR-PULCON. A sufficient zone isolation from the HPTLC plate (mean isolation rate of 82%) for both UA and OA (0.27 - 4.67 mM) was achieved for HPTLC//qNMR, comparing the isolated bioactive compound zone with the respective zone in the botanical extract via HPTLC-Vis densitometry. The HPTLC-EDA-Vis//1H qNMR-PULCON procedure for bioprofiling and quantification/identification/confirmation of bioactive compounds in botanical extracts is considered as straightforward, eco-friendly (only 16 mL solvent required), simple (NMR calibration used over weeks) and reliable new alternative to the status quo of bioactivity-guided fractionation.


Subject(s)
Biological Assay/methods , Magnetic Resonance Spectroscopy , Phytochemicals/analysis , Chemical Fractionation , Chromatography, Thin Layer , Lamiaceae/chemistry , Oleanolic Acid/analysis , Oleanolic Acid/chemistry , Pentacyclic Triterpenes , Plant Extracts/chemistry , Reference Standards , Triterpenes/analysis , Triterpenes/chemistry , Betulinic Acid , Ursolic Acid
15.
Talanta ; 214: 120855, 2020 Jul 01.
Article in English | MEDLINE | ID: mdl-32278434

ABSTRACT

Nuclear Magnetic Resonance (NMR) is an analytical technique extensively used in almost every chemical laboratory for structural identification. This technique provides statistically equivalent signals in spite of using spectrometer with different hardware features and is successfully used for the traceability and quantification of analytes in food samples. Nevertheless, to date only a few internationally agreed guidelines have been reported on the use of NMR for quantitative analysis. The main goal of the present study is to provide a methodological pipeline to assess the reproducibility of NMR data produced for a given matrix by spectrometers from different manufacturers, with different magnetic field strengths, age and hardware configurations. The results have been analyzed through a sequence of chemometric tests to generate a community-built calibration system which was used to verify the performance of the spectrometers and the reproducibility of the predicted sample concentrations.


Subject(s)
Fruit and Vegetable Juices/analysis , Vitis/chemistry , Calibration , Magnetic Resonance Spectroscopy
16.
Eur J Med Chem ; 189: 112047, 2020 Mar 01.
Article in English | MEDLINE | ID: mdl-31982652

ABSTRACT

The LIBRA compound library is a collection of 522 non-commercial molecules contributed by various Italian academic laboratories. These compounds have been designed and synthesized during different medicinal chemistry programs and are hosted by the Italian Institute of Technology. We report the screening of the LIBRA compound library against Trypanosoma brucei and Leishmania major pteridine reductase 1, TbPTR1 and LmPTR1. Nine compounds were active against parasitic PTR1 and were selected for cell-based parasite screening, as single agents and in combination with methotrexate (MTX). The most interesting TbPTR1 inhibitor identified was 4-(benzyloxy)pyrimidine-2,6-diamine (LIB_66). Subsequently, six new LIB_66 derivatives were synthesized to explore its Structure-Activity-Relationship (SAR) and absorption, distribution, metabolism, excretion and toxicity (ADMET) properties. The results indicate that PTR1 has a preference to bind inhibitors, which resemble its biopterin/folic acid substrates, such as the 2,4-diaminopyrimidine derivatives.


Subject(s)
Antineoplastic Agents/pharmacology , Enzyme Inhibitors/pharmacology , High-Throughput Screening Assays/methods , Macrophages/drug effects , Oxidoreductases/antagonists & inhibitors , Pyrimidines/chemistry , Trypanosoma brucei brucei/enzymology , A549 Cells , Antimetabolites, Antineoplastic/pharmacology , Antineoplastic Agents/chemistry , Cell Proliferation , Drug Synergism , Enzyme Inhibitors/chemistry , Humans , Methotrexate/pharmacology , Models, Molecular , Molecular Structure , Structure-Activity Relationship
17.
ACS Mater Lett ; 2(11): 1442-1449, 2020 Nov 02.
Article in English | MEDLINE | ID: mdl-33644762

ABSTRACT

Understanding and tuning the ligand shell composition in colloidal halide perovskite nanocrystals (NCs) has been done systematically only for Pb-based perovskites, while much less is known on the surface of Pb-free perovskite systems. Here, we reveal the ligand shell architecture of Bi-doped Cs2Ag1-x Na x InCl6NCs via nuclear magnetic resonance analysis. This material, in its bulk form, was found to have a photoluminescence quantum yield (PLQY) as high as 86%, a record value for halide double perovskites. Our results show that both amines and carboxylic acids are present and homogeneously distributed over the surface of the NCs. Notably, even for an optimized surface ligand coating, achieved by combining dodecanoic acid and decylamine, a maximum PLQY value of only 37% is reached, with no further improvements observed when exploiting post-synthesis ligand exchange procedures (involving Cs-oleate, different ammonium halides, thiocyanates and sulfonic acids). Our density functional theory calculations indicate that, even with the best ligands combination, a small fraction of unpassivated surface sites, namely undercoordinated Cl ions, is sufficient to create deep trap states, opposite to the case of Pb-based perovskites that exhibit much higher defect tolerance. This was corroborated by our transient absorption measurements, which showed that an ultrafast trapping of holes (most likely mediated by surface Cl-trap states) competes with their localization at the AgCl6 octahedra, from where, instead, they can undergo an optically active recombination yielding the observed PL emission. Our results highlight that alternative surface passivation strategies should be devised to further optimize the PLQY of double perovskite NCs, which might include their incorporation inside inorganic shells.

18.
Chem Mater ; 32(24): 10641-10652, 2020 Dec 22.
Article in English | MEDLINE | ID: mdl-33384476

ABSTRACT

Various strategies have been proposed to engineer the band gap of metal halide perovskite nanocrystals (NCs) while preserving their structure and composition and thus ensuring spectral stability of the emission color. An aspect that has only been marginally investigated is how the type of surface passivation influences the structural/color stability of AMX3 perovskite NCs composed of two different M2+ cations. Here, we report the synthesis of blue-emitting Cs-oleate capped CsCd x Pb1-x Br3 NCs, which exhibit a cubic perovskite phase containing Cd-rich domains of Ruddlesden-Popper phases (RP phases). The RP domains spontaneously transform into pure orthorhombic perovskite ones upon NC aging, and the emission color of the NCs shifts from blue to green over days. On the other hand, postsynthesis ligand exchange with various Cs-carboxylate or ammonium bromide salts, right after NC synthesis, provides monocrystalline NCs with cubic phase, highlighting the metastability of RP domains. When NCs are treated with Cs-carboxylates (including Cs-oleate), most of the Cd2+ ions are expelled from NCs upon aging, and the NCs phase evolves from cubic to orthorhombic and their emission color changes from blue to green. Instead, when NCs are coated with ammonium bromides, the loss of Cd2+ ions is suppressed and the NCs tend to retain their blue emission (both in colloidal dispersions and in electroluminescent devices), as well as their cubic phase, over time. The improved compositional and structural stability in the latter cases is ascribed to the saturation of surface vacancies, which may act as channels for the expulsion of Cd2+ ions from NCs.

20.
PLoS One ; 14(4): e0214956, 2019.
Article in English | MEDLINE | ID: mdl-30958838

ABSTRACT

ε-caprolactone-p-coumaric acid copolymers at different mole ratios (ε-caprolactone:p-coumaric acid 1:0, 10:1, 8:1, 6:1, 4:1, and 2:1) were synthesized by melt-polycondensation and using 4-dodecylbenzene sulfonic acid as catalyst. Chemical analysis by NMR and GPC showed that copolyesters were formed with decreasing molecular weight as p-coumaric acid content was increased. Physical characteristics, such as thermal and mechanical properties, as well as water uptake and water permeability, depended on the mole fraction of p-coumaric acid. The p-coumarate repetitive units increased the antioxidant capacity of the copolymers, showing antibacterial activity against the common pathogen Escherichia coli. In addition, all the synthesized copolyesters, except the one with the highest concentration of the phenolic acid, were cytocompatible and hemocompatible, thus becoming potentially useful for skin regeneration applications.


Subject(s)
Anti-Bacterial Agents , Biocompatible Materials , Caproates , Escherichia coli/growth & development , Lactones , Propionates , Skin , Wound Healing/drug effects , Anti-Bacterial Agents/chemistry , Anti-Bacterial Agents/pharmacology , Biocompatible Materials/chemistry , Biocompatible Materials/pharmacology , Caproates/chemistry , Caproates/pharmacology , Cell Line , Coumaric Acids , Humans , Lactones/chemistry , Lactones/pharmacology , Propionates/chemistry , Propionates/pharmacology , Skin/injuries , Skin/metabolism , Skin/microbiology
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