Exchange Reaction Research Articles

Removal of tritiated water molecules by isotope exchange reaction between H2O vapor and tritium water

Developing a cost-effective method for separating and concentrating tritium water (HTO) from light water (H2O) without consuming additional energy is crucial for achieving reliable and safe nuclear fission and fusion energy technologies. However, this presents a significant challenge because of the difficulties in obtaining basic information, such as the chemical and physical properties of HTO molecules. Here, we investigate the isotope exchange reaction (IER) between HTO molecules in H2O solution and H2O vapor in the atmosphere. The reduction and purification rates of HTO-containing water were measured by varying the system conditions, such as temperature (20−50 °C) and humidity (50 %–90 %), under an equilibrium state between the liquid phase (water) and vapor phase (air). Our findings indicate that the concentration of HTO in the solution can be significantly reduced by increasing H2O vapor in the atmosphere. This result can be quantitatively explained by considering the entropy of mixing between the solution and vapor phases. The results obtained here provide both basic understanding on the exchange process between liquid- and vapor-water molecules and a passive technology for treating HTO-containing water.

Recent Advances in Halogen-Metal Exchange Reactions.

ConspectusThe halogen-metal exchange reaction is a very powerful method for preparing functionalized organometallic reagents in the fields of organic and organometallic chemistry. Since its inception, significant interest has been directed toward the on-demand development of new halogen-metal exchange reactions, primarily through the upgrading of exchange reagents. The enduring quest for optimal reactivity, superior functional group compatibility, and innovative synthetic applications of exchange reagents remains a fundamental objective. In the past several years, the emergence of some significant discoveries in halogen-metal exchange reactions has proclaimed a renaissance to this field. This Account outlines the latest advances within the domain contributed by the Knochel group, including the main points as follows.The stereoretentive I/Li exchange on stereodefined secondary alkyl iodides was developed for the synthesis of nonstabilized chiral secondary alkyllithium reagents. This provided a straightforward method to access chiral organolithium reagents, which can be trapped by various electrophiles or transmetalated with other metals such as copper, zinc, and magnesium, thus enabling the stereoselective synthesis of a series of functionalized compounds and natural products.Faster halogen-magnesium and halogen-zinc exchanges in toluene were realized using a novel kind of exchange reagent complexed with lithium alkoxide. These highly efficient exchange reactions are much faster than traditional ones and performed in an industrially friendly solvent. These advantages are of great value in practical synthesis, paving the way for new developments in this evolving area.Halogen-lanthanide exchanges and their novel applications in organic synthesis were established. These new exchanges introduced the lanthanide metals into halogen-metal exchange reactions for the first time, thereby opening new avenues in synthetic chemistry. Building on these achievements, a comparative analysis of the exchange reaction rates by kinetic study has quantified the relationship between the electronegativity of metals and the rates of halogen-metal exchanges.Br/Na exchange in continuous flow was achieved using a hexane-soluble exchange reagent, 2-ethylhexylsodium. This approach effectively circumvented the poor solubility of the organosodium reagent, which has proven to be of significant practical value and greatly enhanced the synthetic utility of the organosodium reagent in organic synthesis.These remarkable breakthroughs as mentioned above are fueled mainly by upgrading the exchange reagents, resulting in the development of new halogen-metal exchange reactions and innovative applications in organic synthesis. Given the importance of halogen-metal exchanges in synthetic chemistry, the pursuit of other types of exchange reactions, particularly those involving new metals, will be in continuous demand. This Account provides a timely summary of recent progress and will undoubtedly inspire further advances to drive this research field forward.

Direct Multi-Deuterium Labelling of Pirtobrutinib.

Herein, we demonstrate an efficient method for multi-deuterium labelling of pirtobrutinib-a Bruton's tyrosine kinase inhibitor recently approved by the FDA-using a straightforward hydrogen isotope exchange (HIE) reaction. A remarkably high level of deuterium incorporation was achieved using an excess of a Kerr-type iridium catalyst. The key factor in the significant deuterium labelling was the decision to employ a deuterium uniformly labelled solvent, chlorobenzene-d5, at an elevated temperature. Virtually, no d0-d3 species were detected, with only traces of d4-d5 isotopomers (< 5%) observable in the mass spectrum of pirtobrutinib-d8, fulfilling requirements for stable isotope-labelled internal standard. The labelled compound-mainly consisting of isotopomers d6-d9 at 82.4% of the total abundance-was isolated in a high yield (73%) and purity (99%). Noteworthy, fluorine group acting as a directing group was observed for the first time. Significant incorporation of deuterium in ortho-positions, exceeding 87%, was observed. Interestingly, chlorinated solvent used in the HIE reactions was non-specifically deuterated yielding up to 0.42 deuterium per chlorobenzene molecule even at an exceptionally low iridium catalyst loading of 4.17 × 10-2 mol%.

Carbon Isotope Fractionation of Complex Organic Molecules in Star-forming Cores

Recent high-resolution and sensitivity Atacama Large Millimeter/submillimeter Array observations have unveiled the carbon isotope ratios (12C/13C) of complex organic molecules (COMs) in a low-mass protostellar source. To understand the 12C/13C ratios of COMs, we investigated the carbon isotope fractionation of COMs from prestellar cores to protostellar cores with a gas-grain chemical network model. We confirmed that the 12C/13C ratios of small molecules are bimodal in the prestellar phase: CO and species formed from CO (e.g., CH3OH) are slightly enriched in 13C compared to the local interstellar medium (by ∼10%), while those from C and C+ are depleted in 13C owing to isotope exchange reactions. COMs are mainly formed on the grain surface and in the hot gas (> 100 K) in the protostellar phase. The 12C/13C ratios of COMs depend on which molecules the COMs are formed from. In our base model, some COMs in the hot gas are depleted in 13C compared to the observations. Thus, we additionally incorporate reactions between gaseous atomic C and H2O ice or CO ice on the grain surface to form H2CO ice or C2O ice, as suggested by recent laboratory studies. The direct C-atom addition reactions open pathways to form 13C-enriched COMs from atomic C and CO ice. We find that these direct C-atom addition reactions mitigate 13C-depletion of COMs, and the model with the direct C-atom addition reactions better reproduces the observations than our base model. We also discuss the impact of the cosmic-ray ionization rate on the 12C/13C ratio of COMs.

Modeling the Co-permeation of hydrogen isotopes through metals in all rate-limited regimes

Tritium safety plays a crucial role in D-T fusion engineering. During normal operations, tritium(T) is typically dissolved with protium(H) or deuterium(D) in structural materials. However, there are still controversial issues related to the synergistic isotopic effects when considering T permeation through metals with H/D. In this work, a numerical model is built to describe the co-permeation behavior of multi-component hydrogen isotopes through metals in all rate-limited regimes. This model involves isotope exchange reactions in the gas phase, molecular dissolution, and atomic recombination at the gas-solid interface, as well as the diffusion process in the bulk. By simulating the mixed hydrogen gas permeation through various metals, different results are observed. In surface limited regime, the effective permeation flux of D is slightly enhanced by the presence of H due to isotopic effect. In diffusion-limited regime, the recombination of heteronuclear hydrogen molecules (HD) will deviate the equilibrium concentration of D on the upstream side from Sievert's Law, thereafter suppressing the D permeation flux on the downstream side.

Facile Access to Organostibines via Selective Organic Superbase Catalyzed Antimony‐Carbon Protonolysis

AbstractThe selective formation of antimony‐carbon bonds via organic superbase catalysis under metal‐ and salt‐free conditions is reported. This novel approach utilizes electron‐deficient stibine, Sb(C6F5)3, to give upon base‐catalyzed reactions with weakly acidic aromatic and heteroaromatic hydrocarbons access to a range of new aromatic and heteroaromatic stibines, respectively, with loss of C6HF5. Also, the significantly less electron‐deficient stibines, Ph2SbC6F5 and PhSb(C6F5)2 smoothly underwent base‐catalyzed exchange reactions with a range of terminal alkynes to generate the stibines of formulae PhSb(C≡CPh)2, and Ph2SbC≡CR [R=C6H5, C6H4‐NO2, COOEt, CH2Cl, CH2NEt2, CH2OSiMe3, Sb(C6H5)2], respectively. These formal substitution reactions proceed with high selectivity as only the C6F5 groups serve as a leaving group to be liberated as C6HF5 upon formal proton transfer from the alkyne. Kinetic studies of the base‐catalyzed reaction of Ph2SbC6F5 with phenyl acetylene to form Ph2SbC≡CPh and C6HF5 suggested the empirical rate law to exhibit a first‐order dependence with respect to the base catalyst, alkyne and stibine. DFT calculations support a pathway proceeding via a concerted σ‐bond metathesis transition state, where the base catalyst activates the Sb‐C6F5 bond sequence through secondary bond interactions.

Facile Access to Organostibines via Selective Organic Superbase Catalyzed Antimony-Carbon Protonolysis.

The selective formation of antimony-carbon bonds via organic superbase catalysis under metal- and salt-free conditions is reported. This novel approach utilizes electron-deficient stibine, Sb(C6F5)3, to give upon base-catalyzed reactions with weakly acidic aromatic and heteroaromatic hydrocarbons access to a range of new aromatic and heteroaromatic stibines, respectively, with loss of C6HF5. Also, the significantly less electron-deficient stibines, Ph2SbC6F5 and PhSb(C6F5)2 smoothly underwent base-catalyzed exchange reactions with a range of terminal alkynes to generate the stibines of formulae PhSb(C≡CPh)2, and Ph2SbC≡CR [R=C6H5, C6H4-NO2, COOEt, CH2Cl, CH2NEt2, CH2OSiMe3, Sb(C6H5)2], respectively. These formal substitution reactions proceed with high selectivity as only the C6F5 groups serve as a leaving group to be liberated as C6HF5 upon formal proton transfer from the alkyne. Kinetic studies of the base-catalyzed reaction of Ph2SbC6F5 with phenyl acetylene to form Ph2SbC≡CPh and C6HF5 suggested the empirical rate law to exhibit a first-order dependence with respect to the base catalyst, alkyne and stibine. DFT calculations support a pathway proceeding via a concerted σ-bond metathesis transition state, where the base catalyst activates the Sb-C6F5 bond sequence through secondary bond interactions.

Quantum dynamical study on 15N ＋ 14N14N isotope exchange reactions at high energies

In this study, we conduct quantum dynamical calculations at relatively high energies on the exchange reaction 15N ＋ 14N14N →15N14N ＋ 14N on its ground electronic N3 (4A′′) potential energy surface (PES) utilizing the time-dependent wave packet (TDWP) propagation method. Our primary focus is on analyzing the reaction mechanism for 15N ＋ ortho-14N14N (j = 0) and para-14N14N (j = 1) cases. We also explore the influence of varying J (up to 120) of the three-body system and the initial vibrational level (ν = 1, 5, 10) of the diatom on the reaction probability (RP) for ortho and para configurations.

Dual-driven AND molecular logic gates for label-free and sensitive ratiometric fluorescence sensing and inhibitors screening

Due to the complexity of regulatory networks of disease-related biomarkers, developing simple, sensitive, and accurate methods has remained challenging for precise diagnosis. Herein, an “AND” logic gates DNA molecular machine (LGDM) was constructed, which was powered by the catalytic hairpin assembly (CHA). It was coupled with dual-emission CdTe quantum dots (QDs)-based cation exchange reaction (CER) for label-free, sensitive, and ratiometric fluorescence detection of APE1 and miRNA biomarkers. Benefiting from synergistic signal amplification strategies and a ratiometric fluorometric output mode, this LGDM enables accurate logic computing with robust and significant output signals from weak inputs. It offers improved sensitivity and selectivity even in cell extracts. Using dual-emission spectra CdTe QDs, with a ratiometric signal output mode, ensured good stability and effectively prevented false-positive signals from intrinsic biological interferences compared to the approach relying on a single signal output mode, which enabled the LGDM to achieve rapid, efficient, and accurate natural drug screening against APE1 inhibitors in vitro and cells. The developed method provides impetus to streamline research related to miRNA and APE1, offering significant promise for widespread application in drug development and clinical analysis.

Tuning Reprocessing Temperature of Aliphatic Polyurethane Networks by Alkoxyamine Selection.

Recent studies have shown that the largest employed thermoset family, polyurethanes (PUs), has great potential to be reprocessed due to the dynamic behavior of carbamate linkage. However, it requires high temperatures, especially in the case of aliphatic PUs, which causes side reactions besides the desired exchange reaction. To facilitate the reprocessing of aliphatic PUs, in this work, we have explored the dynamic potential of alkoxyamine bonds in PU networks to facilitate the reprocessing under mild conditions considering their fast recombination ability. Taking advantage of the structural effect of the nitroxide and alkyl radicals on the dissociation energy, two different alkoxyamine-based diols have been designed and synthesized to generate PU networks. Our study shows that replacing 50 mol % of a nondynamic diol chain extender with these dynamic blocks boosts the relaxation times of the networks, enabling reprocessing at temperatures as low as 80 °C.

Nordihydroguaiaretic Acid-Cross-Linked Phenylboronic Acid-Functionalized Polyplex Micelles for Anti-angiogenic Gene Therapy of Orthotopic and Metastatic Tumors.

Polyplexes are required to be equipped with multiple functionalities to accomplish adequate structure stability and gene transfection efficacy for gene therapy. Herein, a 4-carboxy-3-fluorophenylboronic acid (FPBA)-functionalized block copolymer of PEG-b-PAsp(DET/FBA) and PAsp(DET/FBA) (abbreviated as PB and HB) was synthesized and applied for engineering functional polyplex micelles (PMs) through ionic complexation with pDNA followed by strategic cross-linking with nordihydroguaiaretic acid (NDGA) in respect to the potential linkage of polyphenol and FPBA moieties. In relation to polyplex micelles void of cross-linking, the engineered multifunctional polyplex micelles (PBHBN-PMs) were determined to possess improved structural tolerability against the exchange reaction with charged species. Besides, the FPBA/NDGA cross-linking appeared to be selectively cleaved in the acidic endosomal compartments but not the neutral milieu. Furthermore, the PBHB-PMs with the optimal FPBA/NDGA cross-linking degree were identified to possess appreciable cellular uptake and endosomal escape activities, eliciting a significantly high level of gene expression relative to P-PMs and PB-PMs. Eventually, in vivo antitumor therapy by our proposed multifunctional PMs appeared to be capable of facilitating expression of the antiangiogenic genomic payloads (sFlt-1 pDNA) via systemic administration. The enriched antiangiogenic sFlt-1 in the tumors could silence the activities of angiogenic cytokines for the inhibited neo-vasculature and the suppressed growth of orthotopic 4T1 tumors. Of note, the persistent expression of the antiangiogenic sFlt-1 is also presumed to migrate into the blood circulation, thereby accounting for an overall antiangiogenic environment in preventing the potential pulmonary metastasis. Hence, our elaborated multifaceted PMs inspired fascinating potential as an intriguing gene delivery system for the treatment of clinical solid tumors and metastasis.

Carbon Isotope Chemistry in Protoplanetary Disks: Effects of C/O Ratios

Carbon isotope fractionation of CO has been reported in the disk around TW Hya, where elemental carbon is more abundant than elemental oxygen ([C/O]elem > 1). We investigated the effects of the [C/O]elem ratio on carbon fractionation using astrochemical models that incorporate isotope-selective photodissociation and isotope exchange reactions. The 12CO/13CO ratio could be lower than the elemental carbon isotope ratio due to isotope exchange reactions when the [C/O]elem ratio exceeds unity. The observed 12CO/13CO and H12CN/H13CN ratios around TW Hya could be reproduced when the [C/O]elem ratio is 2–5. In the vicinity of the lower boundary of the warm molecular layer, the formation of ices leads to the gas-phase [C/O]elem ratio approaching unity, irrespective of the total (gas + ice) [C/O]elem ratio. This phenomenon reduces the variation in the 12CO/13CO ratio across different [C/O]elem ratios.

Chemical implication of the partition coefficient of 137Cs between the suspended and dissolved phases in natural water

After the Fukushima Daiichi nuclear power plant accident, the terrestrial environment became severely contaminated with radiocesium. Consequently, the river and lake water in the Fukushima area exhibited high radiocesium levels, which declined subsequently. The partition coefficient of 137Cs between the suspended sediment (SS) and dissolved phases, Kd, was introduced to better understand the dynamic behavior of 137Cs in different systems. However, the Kd values in river water, ranging from 2 × 104 to 7 × 106 L kg−1, showed large spatiotemporal variability. Therefore, the factors controlling the 137Cs partition coefficient in natural water systems should be identified. Herein, we introduce a chemical model to explain the variability in 137Cs Kd in natural water systems. The chemical model includes the complexation of Cs+ with mineral and organic binding sites in SS, metal exchange reactions, and the presence of colloidal species. The application of the chemical model to natural water systems revealed that Cs+ is strongly associated with binding sites in SS, and a major chemical interaction between 137Cs and the binding sites in SS is the isotope exchange reaction between stable Cs and 137Cs, rather than metal exchange reactions with other metal ions such as potassium ions. To explain the effect of the SS concentration on Kd, the presence of colloidal 137Cs passing through a filter is significant as the dominant dissolved species of 137Cs in river water. These results suggest that a better understanding of stable Cs dissolved in natural water is important for discerning the geochemical and ecological behaviors of 137Cs in natural water.

Sulfidation of Zinc oxide by interaction with Antimony sulfide

The mechanism of interaction between ZnO and Sb2S3 in the temperature range of 500-700°С was studied. The methods of differential thermal analysis, X-ray diffraction, diffuse reflectance spectroscopy and IR transmission spectroscopy, as well as thermodynamic calculations established the exchangeable acid-base reaction mechanism with the removal of the most volatile of the products – Sb2O3. The final and only product of interaction in the system is ZnS of cubic modification (sphalerite) without phase impurities. Condensate mainly contains Antimony oxides of various compositions. In the same way, it is possible to remove oxygen-containing impurities (mainly ZnO) from zinc sulfide obtained by the method of self-propagating high-temperature synthesis.

Selective separation of rhenium from oxygen-pressure leach solution of molybdenite concentrate using modified D201 resin: Experiments and theoretical calculations

Recovering rhenium from highly acidic rhenium-containing leach solutions is challenging for most resins, particularly in multiplexed systems. Herein, we introduce a scheme for selectively obtaining rhenium from a multielement solution containing high concentrations of sulfuric acid using modified D201 resin. Considering the dosage of resin and parameters such as pH and adsorption temperature, the adsorption efficiencies under optimal conditions for rhenium, molybdenum, iron, and cerium were 97.46 %, 0.38 %, 0.94 %, and 1.10 %, respectively. The selective recovery mechanism of rhenium was investigated by fitting the experimental data to kinetic and adsorption isotherm models. The pseudo-second-order and Langmuir models better fit results corresponding to the experimental data, which indicates monolayer chemisorption of ReO4− formed on the resin surface. Meanwhile, various characterizations such as SEM-EDS, FTIR, XPS, etc., indicate that ReO4− initially combines with the protonated −CHN+H2CH2Cl on the modified resin surface and then undergoes ion exchange reaction with doped Cl−. Furthermore, because of the diverse forms and similar properties of molybdenum and rhenium ions in acidic solutions, a theoretical model based on density functional theory was used to simulate the selective adsorption process in leach solution with a pH of 1.7. The simulation results demonstrate a highest occupied molecular orbital–lowest unoccupied molecular orbital energy gap, observed in the following order: ΔEMoO22+ = ΔEReO4− < ΔEMoO42− < ΔEMo7O246−, which implies that MoO22+ and ReO4− were most likely to transition from their ground states to excited states and react with the electron donor and acceptor groups, respectively. Compared with MoO42−, ReO4− is more likely to react with the electron acceptor group and provides the corresponding methods and a theoretical reference for selective separation of rhenium in multielement solutions.

Self-shedding MOF-nanocarriers modulated CdS/MoSe2 heterojunction activity through in-situ ion exchange: An enhanced split-type photoelectrochemical sensor for deoxynivalenol

Deoxynivalenol (DON), a mycotoxin produced by Fusarium, poses a significant risk to human health and the environment. Therefore, the development of a highly sensitive and accurate detection method is essential to monitor the pollution situation. In response to this imperative, we have devised an advanced split-type photoelectrochemical (PEC) sensor for DON analysis, which leverages self-shedding MOF-nanocarriers to modulate the photoelectric response ability of PEC substrate. The PEC sensing interface was constructed using CdS/MoSe2 heterostructures, while the self-shedding copper peroxide nanodots@ZIF-8 (CPNs@ZIF-8) served as the Cu2+ source for the in-situ ion exchange reaction, which generated a target-related signal reduction. The constructed PEC sensor exhibited a broad linear range of 0.1 pg mL−1 to 500 ng mL−1 with a low detection limit of 0.038 pg mL−1, demonstrating high stability, selectivity, and proactivity. This work not only introduces innovative ideas for the design of photosensitive materials, but also presents novel sensing strategies for detecting various environmental pollutants.

Biomimetic gold nanocages incorporating copper-human serum albumin for tumor immunotherapy via cuproptosis-lactate regulation

Cancer immunotherapy remains a significant challenge due to insufficient proliferation of immune cells and the sturdy immunosuppressive tumor microenvironment. Herein, we proposed the hypothesis of cuproptosis-lactate regulation to provoke cuproptosis and enhance anti-tumor immunity. For this purpose, copper-human serum albumin nanocomplex loaded gold nanocages with bacterial membrane coating (BAu-CuNCs) were developed. The targeted delivery and disassembly of BAu-CuNCs in tumor cells initiated a cascade of reactions. Under near infrared (NIR) laser irradiation, the release of copper-human serum albumin (Cu-HSA) was enhanced that reacted with intratumoral glutathione (GSH) via a disulfide exchange reaction to liberate Cu2+ ions and exert cuproptosis. Subsequently, the cuproptosis effect triggered immunogenic cell death (ICD) in tumor by the release of damage associated molecular patterns (DAMPs) to realize anti-tumor immunity via robust production of cytotoxic T cells (CD8+) and helper T cells (CD4+). Meanwhile, under NIR irradiation, gold nanocages (AuNCs) promoted excessive reactive oxygen species (ROS) generation that played a primary role in inhibiting glycolysis, reducing the lactate and ATP level. The combine action of lower lactate level, ATP reduction and GSH depletion further sensitized the tumor cells to cuproptosis. Also, the lower lactate production led to the significant blockage of immunosuppressive T regulatory cells (Tregs) and boosted the anti-tumor immunity. Additionally, the effective inhibition of breast cancer metastasis to the lungs enhanced the anti-tumor therapeutic impact of BAu-CuNCs + NIR treatment. Hence, BAu-CuNCs + NIR concurrently induced cuproptosis, ICD and hindered lactate production, leading to the inhibition of tumor growth, remodeling of the immunosuppressive tumor microenvironment and suppression of lung metastasis. Therefore, leveraging cuproptosis-lactate regulation, this approach presents a novel strategy for enhanced tumor immunotherapy.

Deuterated Alkyl Sulfonium Salt Reagents; Importance of H/D Exchange Methods in Drug Discovery.

Deuterated drugs (heavy drugs) have recently been spotlighted as a new modality for small-molecule drugs because the pharmacokinetics of pharmaceutical drugs can be enhanced by replacing C-H bonds with more stable C-D bonds at metabolic positions. Therefore, deuteration methods for drug candidates are a hot topic in medicinal chemistry. Among them, the H/D exchange reaction (direct transformation of C-H bonds to C-D bonds) is a useful and straightforward method for creating novel deuterated target molecules, and over 20 reviews on the synthetic methods related to H/D exchange reactions have been published in recent years. Although various deuterated drug candidates undergo clinical trials, approved deuterated drugs possess CD3 groups in the same molecule. However, less diversification, except for the CD3 group, is a problem for future medicinal chemistry. Recently, we developed various deuterated alkyl (dn-alkyl) sulfonium salts based on the H/D exchange reaction of the corresponding hydrogen form using D2O as an inexpensive deuterium source to introduce CD3, CH3CD2, and ArCH2CD2 groups into drug candidates. This concept summarises recent reviews related to H/D exchange reactions and novel reagents that introduce the CD3 group, and our newly developed electrophilic dn-alkyl reagents are discussed.

Tracking Cation Exchange in Individual Nanowires via Transistor Characterization.

Cation exchange is a versatile method for modifying the material composition and properties of nanostructures. However, control of the degree of exchange and material properties is difficult at the single-particle level. Successive cation exchange from CdSe to Ag2Se has been utilized here on the same individual nanowires to monitor the change of electronic properties in field-effect transistor devices. The transistors were fabricated by direct synthesis of CdSe nanowires on prepatterned substrates followed by optical lithography. The devices were then subjected to cation exchange by submerging them in an exchange solution containing silver nitrate. By removal of the devices from solution and probing the electrical transport properties at different times, the change in electronic properties of individual nanowires could be monitored throughout the entire exchange reaction from CdSe to Ag2Se. Transistor characterization revealed that the electrical conductivity can be tuned by up to 8 orders of magnitude and the charge-carrier mobility by 7 orders of magnitude. While analysis of the material composition by energy dispersive X-ray spectroscopy confirmed successful cation exchange from CdSe to Ag2Se, X-ray fluorescence spectroscopy proved that cation exchange also took place below the contacts. The method presented here demonstrates an efficient way to tune the material composition and access the resulting properties nondestructively at the single-particle level. This approach can be readily applied to many other material systems and can be used to study the electrical properties of nanostructures as a function of material composition or to optimize nanostructure-based devices after fabrication.

Optical maneuvering of photofunctioning hybrid perovskite for future photonics potential application

Hybrid perovskites, known for their multidimensional opto-electronic properties and capability to generate multi-color emission bands, are highly sought after for light-emitting devices due to their liquid crystalline behavior in the solution phase. This behavior enables easier ion mobility, facilitating ion exchange processes. Exploiting the liquid crystalline properties of perovskites, we applied a halogen exchange reaction in the solution phase using tightly focused laser trapping techniques. Our study demonstrates the successful development of high-luminescent bulk single crystals of methylammonium lead halide alloy MAPb(Br/I)3, which exhibit multi-color emission capabilities, underscoring their potential for optoelectronic applications. We fabricated bulk single crystals of MAPbBr3, measuring 20 × 20 μm2, displaying bright green luminescence. Using a tightly focused trapping laser beam (1064 nm, 1 Watt) with a high numerical aperture (0.9, 60X objective lens), we irradiated a specific area of the green luminescent MAPbBr3 single crystal immersed in a 200 μM methylammonium iodide (MAI) solution for 30 min at room temperature. This treatment induced a red emission band at 605 nm at the irradiated location, while surrounding areas retained the original green luminescence. In a parallel experiment, increasing the iodide concentration to 300 μM caused the emission color of a similar-sized crystal to change uniformly from green to red. Photoluminescence spectroscopy and EDS confirmed the halide exchange from MAPbBr3 to MAPbBr2.3I0.7. This method, influenced by laser parameters such as power, wavelength, and aperture, provides new opportunities for multi-color emission patterning and offers significant insights for advancing optoelectronics.