Organic Complexes Research Articles

Aggregation-induced emission organic metal halide complex for X-ray scintillation.

The expanding applications of X-ray scintillation across various areas, from healthcare to security detection call for the development of new-generation scintillators that offer enhanced sensitivity, efficiency, and versatility. Here, we report for the first time the use of organic metal halide complexes with aggregation-induced emission (AIE) for X-ray scintillation, which can be facilely synthesized and processed in the solution phase. By reacting an AIE organic molecule, 4-(4-(diphenylamino) phenyl)-1-(propyl)-pyridinium (TPA-PD) with zinc chloride (ZnCl2) in solution at room temperature, an organic metal halide complex, (TPA-PD)2ZnCl2, is produced with a high synthetic yield of 87%. Optical and radioluminescence characterizations find that (TPA-PD)2ZnCl2 exhibits bluish-green photoluminescence and radioluminescence peaked at around 450 nm, with a photoluminescence quantum efficiency (PLQE) of 65%, and an absolute light yield of 13 423 Photon per MeV. Moreover, short photoluminescence and radioluminescence decay lifetimes are recorded at 1.81 ns and 5.24 ns, respectively. For X-ray scintillation, an excellent response dose-response linearity and a low limit of detection of 80.23 nGyair S-1 are obtained for (TPA-PD)2ZnCl2. By taking advantage of the high X-ray absorption of metal halides and fast radioluminescence of AIE molecules, our design of covalently bonded organic metal halide complexes opens up new opportunities for the development of high-performance solution-processable scintillators.

A new hyperspectral index of biological crust in remote sensing

Biological crusts (BC) are an organic complex, composed of bacteria, cyanobacteria, diatoms, green algae, tiny fungi, ground jackets, and moss plants, as well as other related organisms. BC is distributed about 40% in arid areas, which is one of the important surface landscapes in the intertwined area between oasis and desert. The relationship between BC and drought is close, which can be used to monitor desertification and water resources in remote sensing. However, the current monitoring of BC uses a simple BC index composed of multi-spectrum to extract its area distribution in remote sensing, which makes it difficult to accurately detect its area. This study considers the characteristic bands in the hyper-spectrum cure and designs a hyperspectral index of BS, i.e., HBCI. The HBCI is used, and we successfully estimated the area of biological soil crusts (Kappa=0.86) in the PRISMA image. This finding has help for the regional climate change research.

Improved Charge Delivery within Covalently Ligated Cobalt Phthalocyanine Electrocatalyst for CO2 Reduction

Cobalt(II) phthalocyanine (CoPc) complexes are some of the most active catalysts for CO2 electroreduction reaction (CO2ERR). However, these organic complexes are non-conductive, thus the CO2ERR rate is hindered by the...

Advances in mechanism for the microbial transformation of heavy metals: implications for bioremediation strategies.

Heavy metals are extensively discharged through various anthropogenic activities, resulting in an environmental risk on a global scale. In this case, microorganisms can survive in an extreme heavy metal-contaminated environment via detoxification or resistance, playing a pivotal role in the speciation, bioavailability, and mobility of heavy metals. Therefore, studies on the mechanism for the microbial transformation of heavy metals are of great importance and can provide guidance for heavy metal bioremediation. Current research studies on the microbial transformation of heavy metals mainly focus on the single oxidation, reduction and methylation pathways. However, complex microbial transformation processes and corresponding bioremediation strategies have never been clarified, which may involve the inherent physicochemical properties of heavy metals. To uncover the underlying mechanism, we reclassified heavy metals into three categories based on their biological transformation pathways, namely, metals that can be chelated, reduced or oxidized, and methylated. Firstly, we comprehensively characterized the difference in transmembrane pathways between heavy metal cations and anions. Further, biotransformation based on chelation by low-molecular-weight organic complexes is thoroughly discussed. Moreover, the progress and knowledge gaps in the microbial redox and (de)methylation mechanisms are discussed to establish a connection linking theoretical advancements with solutions to the heavy metal contamination problem. Finally, several efficient bioremediation strategies for heavy metals and the limitations of bioremediation are proposed. This review presents a solid contribution to the design of efficient microbial remediation strategies applied in the real environment.

Intramolecular exciplex featuring a bis-sp3 C-locked acceptor-donor-acceptor sandwich.

Intramolecular exciplex systems featuring thermally activated delayed fluorescence (TADF) have garnered significant attention in the realm of organic light-emitting diodes (OLEDs). Nonetheless, the occurrence of organic sandwich intramolecular exciplexes remains rare due to structural limitations and synthetic challenges. Herein, we present a novel rigid acceptor-donor-acceptor (A-D-A) sandwich complex, dSFQP, characterized by two sp3 C-locking moieties. This compound exhibits TADF characteristics facilitated by a multiple through-space charge-transfer process. X-ray crystallographic analysis confirms the distinctive sandwich configuration. The parallel spatial arrangement and minimized A-D-A configuration enhance electronic interactions, resulting in a high photoluminescence quantum yield, rapid reverse intersystem crossing rate, and sluggish nonradiative decay rate. OLEDs employing dSFQP as the dopant achieve a maximum external quantum efficiency (EQE) of 28.5% with a low efficiency roll-off of merely 2.8% at 1000 cd m-2. Even at a high brightness of 10 000 cd m-2, the EQE remains notably high at 17.5%. Our current results provide an effective way to further innovate the design of new organic charge-transfer complexes.

High-efficiency nickel recovery from spent electroless nickel plating solution: effective degradation of high-concentration nickel complexes to form a nickel ferrite nanomaterial via Fe3O4 catalytic oxidation

High-concentration organic nickel complexes were efficiently degraded and converted into NiFe2O4 nanomaterials via Fe3O4 catalytic oxidation under alkaline conditions, with high removal efficiency of nickel (99.99%) and TOC (81.94%), respectively.

Aggregation-induced emission luminogens for latent fingerprint detection.

For over a century, fingerprints have served as a pivotal tool for identification of individuals owing to their enduring characteristics and easily apparent features, particularly in the realm of criminal investigations. Latent fingerprints (LFPs) are "invisible fingerprints" that are most commonly available at crime scenes and require a rapid, selective, sensitive, and convenient method for detection. However, existing fingerprint development techniques harbour limitations, prompting the exploration of novel approaches that prioritize investigator safety and environmental sustainability. Leveraging the unique photophysical properties of aggregation-induced emission luminogens (AIEgens) has emerged as a promising strategy for on-site analysis of LFP visualization. In this highlight, we have presented a comparative analysis of various AIEgens (organic compounds, metal complexes, nanoparticles, and polymers) for the development and detection of LFPs. Through this examination, insights into the efficiency and potential applications of AIE-based fingerprint development techniques are provided. In addition, several strategies have been proposed for circumventing the limitations of existing AIEgens. We hope that this highlight article will encourage more researchers to investigate AIEgens in LFP detection, contributing to forensic science.

Synthesis, characterization, and bioactivity evaluation of several divalent transition metal ion-bioflavonoid complexes

Interest in organic polyphenol compounds increases if these natural compounds are coordinated with transition metal ions. In this study, four metal complexes were synthesized with flavonoid extracts, and reliable techniques were used for characterization. These complexes showcase unique coloring, low pH, and conductivity levels, with X-ray diffraction revealing varying crystallinity among flavonoid extracts and certain complexes. Fourier transform infrared spectrophotometer exhibits a specific stretching vibration (442–486 cm−1 ν M−O), indicating flavonoid metal complex formation formation. UV–visible spectrum of flavonoid extracts displays absorption bands at 280 and 340 nm, shifting upon metal ion binding to unveil new absorption bands for each complex, producing three peaks between 260–660 nm. The 1HNMR results showed that the proton signals in all complexes shifted to a high field relative to their ligand, possibly due to increased coupling caused by the coordination effect and thus increased planarity of the flavonoid molecules. These organic metal complexes display heightened antioxidant, antimicrobial, and anticancer properties compared to extracts, with enhanced cytotoxicity against THP-1 and Calu-3 cell lines, notably Cu(II) displaying superior cytotoxic effects with IC50 values of 18 and 56 μg/mL for THP-1 and Calu-3 cells respectively.

Crystal structure and electronic structure calculations of a novel organic triphosphate complex: excellent electrochemical properties with ultra-efficient lithium storage capacity

A new organic–inorganic hybrid molecule, cyclohexyl ammonium dihydride triphosphate, was synthesized at room temperature with slow evaporation, yielding a new triphosphate complex HO10P3·(C6H14N)4·2(H2O) using the chemical ion exchange process.

Investigation of the electronic and optical properties of Al13–dianhydride complexes by (time-dependent) density functional theory

The second-order nonlinear optical properties of inorganic–organic complexes constructed from Al13 and dianhydrides were investigated using (time-dependent) density functional theory.

Two new 6-nitrobenzimidazole ligand-modified polymolybdate-based metal–organic complexes with excellent capacitive and electrocatalytic performances

6-Nitrobenzimidazole ligand was first introduced into polyoxometalate-based metal–organic architecture, and two unique butterfly-like complexes were obtained. Their applications in electrochemical energy storage and electrocatalysis were studied.

New Insights into the Organic Complexation of Bioactive Trace Metals in the Global Ocean from the GEOTRACES Era

The GEOTRACES program has greatly expanded measurements of dissolved trace metal concentrations across ocean basins, but to understand the behavior and cycling of metals and their impacts on primary productivity, we must understand the chemical forms in which they are present in the environment. Organic ligands play a central role in the speciation and cycling of trace metals in the marine environment, controlling their chemical reactivity and bioavailability. Here, we present an overview of the contributions the GEOTRACES program has made to understanding ocean metal speciation through advancing our knowledge of the distribution, sources, and sinks of metal-binding organic ligands across the global ocean, particularly for iron. Detailed assessments and intercalibration of the speciation methods most commonly applied have allowed integration of metal-binding ligand measurements across datasets. Work to characterize specific ligand groups within the wider pool of dissolved organic matter, along with their sources and sinks, is starting to unravel the role of metal-binding organic ligands in global biogeochemical cycles. Recent advances in complementary analytical techniques using liquid chromatography and mass spectrometry present a molecular picture of metal speciation and bioavailability—and also pose new questions. Moving forward, we need to address knowledge gaps in our understanding of how metal speciation and complexation relates to bioavailability in order to recognize the impacts of ocean metal distributions and cycling on marine productivity and the global carbon cycle.

Synchronous primary multiple cancer: distal cholangiocarcinoma of the intrapancreatic common bile duct and intraductal papillary mucinous tumor associated with ductal adenocarcinoma of the pancreatic tail

We present a combination of distal cholangiocarcinoma of the intrapancreatic common bile duct and intraductal papillary mucinous tumor associated with ductal adenocarcinoma of the pancreatic tail. This clinical case is unique. When analyzing the literature, we found no any case of similar primary multiple malignant tumor. Importantly, final diagnosis of simultaneous malignant pancreatobiliary neoplasia is possible only via intraoperative biopsy after adequate morphological dissection and research of resected organ complex including molecular genetic analysis due to identical histological and immunohistochemical picture of ductal neoplasia.

Recent Advances in the Cascade Cyclization Reactions of 1,7‐Enynes

AbstractElaborated molecular architectures, especially carbocyclic, heterocyclic, endocyclic, and polycyclic molecular structures, serve as an important class of organic complexes because they are frequently occurring core structural units in a variety of biologically and pharmacologically relevant natural products, drug molecules, agrochemicals, and functional materials. A main challenge of current synthetic approaches is the development of strategically efficient and selective formation of these compounds from easy‐to‐handle starting materials. The cascade cyclizations of 1,7‐enynes have afforded an indispensable method for accessing molecular complexity and diversity, thus highlighting their potential significance in both academic and industrial communities. In the last decades, tremendous efforts have been devoted to discovering convenient routes to access sophisticated annulation derivatives, and a wide range of powerful and straightforward synthetic strategies have been reported. In this review, the latest achievements in the cascade cyclization reactions of 1,7‐enynes are summarized, which could be separated into three categories: (1) Visible‐light‐induced reactions of 1,7‐enynes; (2) Metal‐free catalyzed reactions of 1,7‐enynes; (3) Transition‐metal‐catalyzed reactions of 1,7‐enynes.

(Invited) Ion Transport in Solid-State Electrolytes Based on TTF - TCNQ Charge-Transfer Complexes

Current research on solid-state organic electrolytes mainly focuses on polymer electrolytes where ion transport is facilitated by chain segmental motion. The ionic conductivity of these polymer electrolytes at room temperature in too low for many practical applications. A limited number of prior reports suggest that solid-state electrolytes including organic crystalline charge-transfer complexes can have surprisingly high ionic conductivity. We report1 that processing and environmental conditions drastically impact electron and ion charge transport properties of charge-transfer complex electrolytes based on tetrathiafulvalene-tetracyanoquinodimethane (TTF-TCNQ) mixed with lithium bis(trifluoromethylsulfonylimide) (LiTFSI). Thermal annealing and water vapor treatment decrease electronic conductivity and increase ionic conductivity. The electrolyte with 1-1-2-0.45 molar ratio of TTF-TCNQ-LiTFSI-H2O has an ionic conductivity of 2 × 10-3 S/cm at 25 °C with electronic conductivity of order 10-7 S/cm. Thermal annealing helps reduce connectivity of the charge-transfer complexes and expose more surfaces to interact with LiTFSI, thereby decreasing electronic conductivity. Exposure of the sample to water vapor then causes a substantial increase in ionic conductivity, even when the material remains in the solid state. In this presentation, we will also report on additional experimental studies of solid-state electrolytes incorporating TTF-TCNQ.Reference 1. L. Yang and J. L. Schaefer, “Water-Assisted Ion Conduction in Solid-State Charge-Transfer Complex Electrolytes for Lithium Batteries,” ChemRxiv, 2023. https://doi.org/10.26434/chemrxiv-2023-9k024

Engineering hierarchically porous carbon nanorods electrode materials for high performance zinc ion hybrid supercapacitors

Well-defined carbon materials with tailored unique pore structure are crucial to develop advanced zinc ion hybrid supercapacitors (ZIHCs), but effective synthesis is still a challenge. Herein, hierarchically porous carbon nanorods (HPCNs) are successfully synthesized by Pluronic P123 (PEO20PPO70PEO20) mediated dynamic dual template method that tetraethylsiloxane (TEOS) and sucrose are adopted as silicon (Si) and carbon (C) precursors, respectively. During synthesis, the rod-like organic mesomorphous complexes are generated by self-assembly of cetyltrimethyl ammonium/poly-(acrylic acid) (CTAB/PAA) under the assistance of Pluronic P123 as dynamic soft templates and in-situ formed silica particles as hard templates. The synthesized HPCNs have uniform rod-like morphology, high surface area and notable specific capacity. Furthermore, the HPCNs are activated to afford AHPCNs with enriched micropores and increased surface area of 905 m2 g−1. Consequently, ZIHCs with the AHPCNs as cathode display attractive electrochemical performances including large capacity (157.1 mAh g−1 at 0.1 A g−1), exceptional rate performance (110.3 mAh g−1 at 20 A g−1), high energy density (125.7 Wh kg−1) and power density (16 kW kg−1). Moreover, ZIHCs demonstrated brilliant capacity retention of 100% even after 10,000 cycles at 5 A g−1. Our work presents an effective approach for controllable engineering of hierarchically porous carbon nanorod materials. Meanwhile, it also offers theoretical and technical support to develop advanced zinc ion capacitor energy storage devices.

Revisiting the applicability and constraints of molybdenum- and uranium-based paleo redox proxies: comparing two contrasting sill fjords

Abstract. Sedimentary molybdenum (Mo) and uranium (U) enrichments are often used as redox proxies to reconstruct bottom water redox changes. However, these redox proxies may not be equally reliable across a range of coastal settings due to varying depositional environments. Fjords vary greatly in their depositional conditions, due to their unique bathymetry and hydrography, and are highly vulnerable to anthropogenic and climatic pressures. Currently, it is unknown to what extent Mo and U sequestration is affected by variable depositional conditions in fjords. Here, we use pore water and sequential extraction data to investigate Mo and U enrichment pathways in sediments of two sill fjords on the Swedish west coast with contrasting depositional environments and bottom water redox conditions. Our data suggest that sedimentary authigenic Mo and U pools differ between the two fjords. At the (ir)regularly dysoxic (oxygen = 0.2–2 mL L−1) Gullmar Fjord, authigenic Mo largely binds to manganese (Mn) oxides and to a lesser extent to iron (Fe) oxides; Mo sulfides do not play a major role due to low sulfate reduction rates, which limits the rate of Mo burial. Authigenic U largely resides in carbonates. At the (ir)regularly euxinic (oxygen = 0 mL L−1; total hydrogen sulfide ≥ 0 mL L−1) Koljö Fjord, authigenic Mo is significantly higher due to binding with more refractory organic matter complexes and Mo-Fe-sulfide phases. Uranium is moderately enriched and largely bound to organic matter. We found no direct evidence for temporal changes in bottom water redox conditions reflected in Mo and U enrichments at either Gullmar Fjord or Koljö Fjord. While sulfidic bottom waters favor Mo sequestration at Koljö Fjord, enrichment maxima reflect a combination of depositional conditions rather than short-term low-oxygen events. Our data demonstrate that secondary pre- and post-depositional factors control Mo and U sequestration in fjords to such an extent that bottom water redox conditions are either not being systematically recorded or overprinted. This explains the large variability in trace metal enrichments observed in fjords and has implications for applying Mo and U as proxies for environmental redox reconstructions in such systems.

Immunohistochemical detection of PIEZO1 and PIEZO2 in human digital Meissner´s corpuscles

BackgroundThe cutaneous end organ complexes or cutaneous sensory corpuscles are specialized sensory organs associated to low-threshold mechanoreceptors. Mechano-gated proteins forming a part of ion channels have been detected in both the axon and terminal glial cells of Meissner corpuscles, a specific cutaneous end organ complex in the human glabrous skin. The main candidates to mechanotransduction in Meissner corpuscles are members of the Piezo family of cationic ion channels. PIEZO2 has been detected in the axon of these sensory structures whereas no data exists about the occurrence and cell localization of PIEZO1. MethodsSkin samples (n = 18) from the palmar aspect of the distal phalanx of the first and second fingers were analysed (8 female and 10 males; age range 26 to 61 26–61 years). Double immunofluorescence for PIEZO1 and PIEZO2 together with axonal or terminal glial cell markers was captured by laser confocal microscopy, and the percentage of PIEZOs positive Meissner corpuscles was evaluated. ResultsMCs from human fingers showed variable morphology and degree of lobulation. Regarding the basic immunohistochemical profile, in all cases the axons were immunoreactive for neurofilament proteins, neuron specific enolase and synaptophysin, while the lamellar cells displayed strong S100P immunoreactivity. PIEZO1 was detected co-localizing with axonal markers, but never with terminal glial cell markers, in the 56% of Meissner corpuscles; weak but specific immunofluorescence was additionally detected in the epidermis, especially in basal keratinocytes. Similarly, PIEZO2 immunoreactivity was found restricted to the axon in the 85% of Meissner corpuscles. PIEZO2 positive Merkel cells were also regularly found. ConclusionsPIEZO1 and PIEZO2 are expressed exclusively in the axon of a subpopulation of human digital Meissner corpuscles, thus suggesting that not only PIEZO2, but also PIEZO1 may be involved in the mechanotransduction from low-threshold mechanoreceptors.

Understanding atrazine elimination via treatment of the enzyme-based Fenton reaction: Kinetics, mechanism, reaction pathway, and metabolites toxicity

The degradation kinetics and mechanism of atrazine (ATZ) via an enzyme-based Fenton reaction were investigated at various substrate concentrations and pH values. Toxicological assessment was conducted on ATZ and its degradation products, and the associated reaction pathway was examined. The in situ production of hydrogen peroxide (H2O2) was monitored within the range of 3–15 mM, depending on the increase in glucose concentration, while decreasing the pH to 3.2–5.1 (initial pH of 5.8) or 6.5–7.4 (initial pH of 7.7). The degradation efficiency of ATZ was approximately 2–3 times higher at an initial pH of 5.8 with lower glucose concentrations than at an initial pH of 7.7 with higher substrate concentrations during the enzyme-based Fenton reaction. The apparent pseudo-first-order rate constant for H2O2 decomposition under various conditions in the presence of ferric citrate was 1.9–6.3 × 10−5 s−1. The •OH concentration ([•OH]ss) during the enzyme-based Fenton reaction was 0.5–4.1 × 10−14 M, and the second-order rate constant for ATZ degradation was 1.5–3.3 × 109 M−1 s−1. ATZ intrinsically hinders the growth and development of Arabidopsis thaliana, and its inhibitory effect is marginal, depending on the reaction time of the enzyme-based Fenton process. The ATZ transformation during this process occurs through dealkylation, hydroxylation, and dechlorination via •OH-mediated reactions. The degradation kinetics, mechanism, and toxicological assessment in the present study could contribute to the development and application of enzyme-based Fenton reactions for in situ pollutant abatement. Moreover, the enzyme-based Fenton reaction could be an environmentally benign and applicable approach for eliminating persistent organic matter, such as herbicides, using diverse H2O2-producing microbes and ubiquitous ferric iron with organic complexes.

Ligand exchange provides new insight into the role of humic substances in the marine iron cycle

Organic complexation of iron plays a crucial role in preventing its precipitation, facilitating its transport, and modulating its reactivity and bioavailability in natural waters. Although humic substances (HS) complexes serve as the primary source of terrestrial iron reaching ocean waters, the transition from Fe-HS species to other forms of organic complexation with ocean autochthonous ligands has not yet been properly described. Taking advantage of the electrolability of Fe-HS complexes, we monitored the ligand exchange of iron-saturated Suwannee River fulvic and humic acids (SRFA and SRHA) after the addition of desferrioxamine B (DFOB) and other ligands for comparison. We observed that Fe-HS concentrations gradually decreased until reaching an apparent steady state, typical of a reversible reaction within 1 to 15 h. The dissociation kinetics and species partitioning of Fe-SRHS complexes at the equilibrium showed some features contrary to the current paradigm of HS iron complexation. The affinity of SRFA to bind iron is close to that of DFOB and for SRHA is even higher. The heterogeneity of the HS iron binding groups was confirmed, although experiments in NaCl solutions revealed that in seawater it is substantially caused by the interaction of major divalent ions. The different dissociation kinetics of Fe-SRHS complexes obtained with different competing ligands and the absence of Fe-DFOB dissociation in the presence of iron-free SRFA indicate an intimate associative mechanism of ligand exchange, with the presence of a ternary complex (SRHS-Fe-DFOB) that does not form if the departing complex is Fe-DFOB. We hypothesize that at the concentrations of HS and siderophores found in the open ocean, iron ligand exchange is limited and organic iron speciation will be close to being regulated on a “first come, first served” basis. Experiments conducted under saturation of all iron complexes support the formation of a permanent concentration of a ternary complex. Our findings show the real complexity of cation-ligand interactions in seawater, with implications for the interpretation of recent chromatographic and electrochemical measurements and for the understanding of iron partitioning in the presence of ubiquitous HS.