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This study benchmarks the newly re-implemented single-reference excited-state methods, IP-EOM-CCSD, EA-EOM-CCSD, and STEOM-CCSD, in ORCA6.0, with a focus on open-shell systems. We compare STEOM against EOM-CCSD, CC3, and CCSDT across a range of systems, including small organic radicals, hydrated transition metal (TM) ions, and TM diatomic systems with both closed and open-shell configurations. For organic radicals, STEOM and EOM-CCSD show comparable performance, aligning closely with CC3 and CCSDT results. In the case of hydrated TM ions, IP-EOM closely matches DLPNO-CCSD results, while deviations from DLPNO-CCSD(T) are consistent. For open-shell TM systems, IP-EOM exhibits a blueshift relative to both the DLPNO-CCSD methods, while EA-EOM-CCSD shows better agreement. When comparing STEOM and CC3 to CCSDT, STEOM shows slightly larger deviations in closed-shell systems but shows excellent agreement in open-shell systems. Computational efficiency is also assessed, revealing a significant speedup in ORCA 6.0 compared to ORCA 5.0, with optimizations improving computation times. This study provides valuable insights into the performance and efficiency of STEOM in various chemical environments, highlighting its strengths and limitations. [ABSTRACT FROM AUTHOR]

Two-dimensional transition metal dichalcogenides and semiconductor metal oxides have shown great potential in photocatalysis. However, their stability and efficiency need to be further improved. In this paper, porous ZnO nanorods with high specific surface area were prepared from metal-organic framework ZIF-8 by a simple hydrothermal method. A MoS2/ZnO composite was constructed by loading MoS2 onto the surface of porous ZnO nanorods. Compared with ZnO materials prepared by other methods, MoS2/ZnO prepared in this paper exhibits superior photocatalytic performance. The enhanced photocatalytic activity of the MoS2/ZnO composite can be attributed to the formation of heterojunctions and strong interaction between them, which greatly facilitate the separation of electrons and holes at the contact interface. In addition, due to the wide absorption region of the visible spectrum, MoS2 can greatly broaden the light absorption range of the material after the formation of the composite material, increase the utilization rate of visible light, and reduce the combination of electrons and holes. This study provides a new way to prepare cheap and efficient photocatalysts. [ABSTRACT FROM AUTHOR]

PurposeInflamed, prone-to-rupture coronary plaques are an important cause of myocardial infarction and their early identification is crucial. Atherosclerotic plaques are characterized by overexpression of the type-2 somatostatin receptor (SST2) in activated macrophages. SST2 ligand imaging (e.g. with [68 Ga]Ga-DOTA-TOC) has shown promise in detecting and quantifying the inflammatory activity within atherosclerotic plaques. However, the sensitivity of standard axial field of view (SAFOV) PET scanners may be suboptimal for imaging coronary arteries. Long-axial field of view (LAFOV) PET/CT scanners may help overcome this limitation. We aim to assess the ability of [68 Ga]Ga-DOTA-TOC LAFOV-PET/CT in detecting calcified, SST2 overexpressing coronary artery plaques.MethodsIn this retrospective study, 108 oncological patients underwent [68 Ga]Ga-DOTA-TOC PET/CT on a LAFOV system. [68 Ga]Ga-DOTA-TOC uptake and calcifications in the coronary arteries were evaluated visually and semi-quantitatively. Data on patients' cardiac risk factors and coronary artery calcium score were also collected. Patients were followed up for 21.5 ± 3.4 months.ResultsA total of 66 patients (61.1%) presented with calcified coronary artery plaques. Of these, 32 patients had increased [68 Ga]Ga-DOTA-TOC uptake in at least one coronary vessel (TBR: 1.65 ± 0.53). Patients with single-vessel calcifications showed statistically significantly lower uptake (SUVmax 1.10 ± 0.28) compared to patients with two- (SUVmax 1.31 ± 0.29, p

Metal–organic frameworks (MOFs), self-assembled by metal ions and organic ligands, have been utilized as active layers in resistive random-access memory (RRAM) devices due to their tunable composition and structure advantages, high porosity, and diverse interactions between guest molecules and host frameworks. As one kind of special MOF, MOF nanosheets not only inherit the benefits of MOFs but also present unique two-dimensional nanoscale thicknesses. Their special properties make them beneficial for fabricating MOF films. Thus, they could be promising materials for RRAM devices. Herein, we synthesized two porphyrin MOF nanosheets and then fabricated MOF films by spin-coating. After that, we used the films for resistive switching (RS) layers in memory devices. The as-fabricated RRAM devices exhibit write-once-read-many-times memory characteristics and good nonvolatile stability. Furthermore, due to the unique luminescence of the porphyrin linker, we investigated the light-induced resistive switching characteristics. The result shows that these porphyrin-based MOF nanosheet films exhibited ternary memory properties. This RS modulation is likely related to the photoinduced electrons and holes forming along channels consisting of porphyrin molecules. This MOF-based light-mediated memory device can be a candidate for achieving environment-responsive devices and has applications in information storage devices. [ABSTRACT FROM AUTHOR]

Low dimensional (LD) organic metal halide hybrids (OMHHs) have recently emerged as new generation functional materials with exceptional structural and property tunability. Despite the remarkable advances in the development of LD OMHHs, optical properties have been the major functionality extensively investigated for most of LD OMHHs developed to date, while other properties, such as magnetic and electronic properties, remain significantly under‐explored. Here, we report for the first time the characterization of the magnetic and electronic properties of a 1D OMHH, organic‐copper (II) chloride hybrid (C8H22N2)Cu2Cl6. Owing to the antiferromagnetic coupling between Cu atoms through chloride bridges in 1D [Cu2Cl62−]∞ chains, (C8H22N2)Cu2Cl6 is found to exhibit antiferromagnetic ordering with a Néel temperature of 24 K. The two‐terminal (2T) electrical measurement on a (C8H22N2)Cu2Cl6 single crystal reveals its insulating nature. This work shows the potential of LD OMHHs as a highly tunable quantum material platform for spintronics. [ABSTRACT FROM AUTHOR]

Efforts are underway to develop highly active catalysts to reduce the high overpotential of the oxygen evolution reaction (OER). Metal–organic frameworks or coordination polymers are promising candidates because of their tunable structures and high surface areas. In this study, Nickel and Cobalt trans‐cinnamate (t‐ca) were synthesized via a hydrothermal method. Their structures were analyzed and found to be isostructural. Both complexes exhibited superior electrocatalytic properties in the OER compared to those of IrO2, with overpotentials of 373 and 390 mV and Tafel slopes of 58 and 66 mV/dec. These excellent characteristics were attributed to the electron delocalization of the metal centers via interactions with π‐π delocalized organic ligands. Ni t‐ca, with stronger ligand interactions, displayed an enhanced OER catalytic performance, emphasizing the importance of metal–ligand interactions and suggesting that further exploration of diverse π–π delocalized organic ligands and metal centers may lead to further advancements in electrocatalytic activity. [ABSTRACT FROM AUTHOR]

Urban stormwater commonly contains many pollutants. This has threatened the ecological health of receiving waters as well as stormwater reuse safety. In this context, an effective treatment of urban stormwater is essential. This study undertook a feasibility investigation on using membranes to remove heavy metals from urban stormwater. Two of the most commonly used membranes in the field of water treatment, namely flat ceramic membrane and organic flat membrane, were selected. The research outcomes showed both membranes had the potential to treat urban stormwater. In the case of real stormwater in low influent velocity, the removal percentages were 77.48% (Zn), 64.33% (Cu), 98.04% (Pb), 74.45% (Ni), 56.96% (Cr), and 49.81% (Cd) for flat ceramic membranes and 81.76% (Zn), 77.69% (Cu), 98.13% (Pb), 81.49% (Ni), 59.62% (Cr), and 68.55% (Cd) for organic flat membranes. In high influent velocity, they were 78.66%, 67.74%, 97.02%, 60.84%, 49.05%, and 78.06% for flat ceramic membranes and 74.35%, 66.70%, 96.94%, 61.19%, 48.79%, and 88.00% for organic flat membranes. However, the influence of membrane types on treatment performance was secondary to rainfall characteristics and pollutant forms. It was noted that the heavy metal removal percentages had lower variability for events with high rainfall intensity while both membranes indicated a significant preference on treating particulate pollutants by interception mechanisms. The results also highlighted that using membrane technology to treat stormwater might have a relatively low cost due to low membrane fouling. This reduced the cost of replacement and maintenance. These research outcomes provided an effective stormwater treatment approach and can provide improved stormwater quality, ensuring its reuse safety. [ABSTRACT FROM AUTHOR]

As a basic component of the versatile semiconductor devices, metal oxides play a critical role in modern electronic information industry. However, ultra-high precision nanopatterning of metal oxides often involves multi-step lithography and transfer process, which is time-consuming and costly. Here, we report a strategy, using metal-organic compounds as solid precursor photoresist for multi-photon lithography and post-sintering, to realize ultra-high precision additive manufacturing of metal oxides. As a result, we gain metal oxides including ZnO, CuO and ZrO2 with a critical dimension of 35 nm, which sets a benchmark for additive manufacturing of metal oxides. Besides, atomic doping can be easily accomplished by including the target element in precursor photoresist, and heterogeneous structures can also be created by multiple multi-photon lithography, allowing this strategy to accommodate the requirements of various semiconductor devices. For instance, we fabricate an ZnO photodetector by the proposed strategy. By using metal-organic compounds as solid precursor photoresist for multi-photon lithography and post-sintering, Cao et al. report ultra-high precision nano additive manufacturing of 2D and 3D metal oxide semiconductors with dimension down to 35 nm. [ABSTRACT FROM AUTHOR]

Rational: To validate a population-based input function (PBIF) model that alleviates the need for scanning since injection time in dynamic whole-body (WBdyn) PET. Methods: Thirty-seven patients with suspected/known well-differentiated neuroendocrine tumors were included (GAPETNET trial NTC03576040). All WBdyn 68Ga-DOTATOC-PET/CT acquisitions were performed on a digital PET system (one heart-centered 6 min-step followed by nine WB-passes). The PBIF model was built from 20 image-derived input functions (IDIFs) obtained from a respective number of patients' WBdyn exams using an automated left-ventricle segmentation tool. All IDIF peaks were aligned to the median time-to-peak, normalized to patient weight and administrated activity, and then fitted to an exponential model function. PBIF was then applied to 17 independent patient studies by scaling it to match the respective IDIF section at 20-55 min post-injection time windows corresponding to WB-passes 3-7. The ratio of area under the curves (AUCs) of IDIFs and PBIF3-7 were compared using a Bland--Altman analysis (mean bias ± SD). The Patlakestimated mean Ki for physiological uptake (Ki-liver and Ki-spleen) and tumor lesions (Ki-tumor) using either IDIF or PBIF were also compared. Results: The mean AUC ratio (PBIF/IDIF) was 0.98 ± 0.06. The mean Ki bias between PBIF3-7 and IDIF was -2.6 ± 6.2% (confidence interval, CI: -5.8; 0.6). For Ki-spleen and Ki-tumor, low relative bias with low SD were found [4.65 ± 7.59% (CI: 0.26; 9.03) and 3.70 ± 8.29% (CI: -1.09; 8.49) respectively]. For Ki-liver analysis, relative bias and SD were slightly higher [7.43 ± 13.13% (CI: -0.15; 15.01)]. Conclusion: Our study showed that the PBIF approach allows for reduction in WBdyn DOTATOC-PET/CT acquisition times with a minimum gain of 20 min. [ABSTRACT FROM AUTHOR]

Organometallic complexes, which include ligands such as carbon monoxide (CO), carbenes, alkyls, phenyls, p-bound alkynes, alkenes, cyclopentadienyls, and arenes, have been extensively utilized in fields like materials chemistry and catalysis. These complexes also offer opportunities for the development of new medications with unique modes of action. Specifically, we are interested in anticancer drugs that can enhance the effectiveness of platinum treatments, broaden their range of action, reduce adverse effects, and prevent resistance. The distinct physiochemical properties of organometallic complexes have made them valuable in homogeneous catalysis, including the production of lead compounds and therapeutic possibilities. Over the past 20 years, a small group of researchers worldwide has explored the medical applications of these compounds’ unique characteristics, such as their structural diversity, potential for ligand exchange, and redox and catalytic properties. The results have been remarkable, and it is anticipated that numerous other organometallic compounds will undergo clinical trials in the coming years in addition to those already underway. In this brief study, we outline the advantages that organometallic metal complexes have over coordination compounds and pure organic molecules. [ABSTRACT FROM AUTHOR]

We report the synthesis, structure, and characterization of two novel neptunyl complexes (NpO2L1 and NpO2L2) constructed from phenylene‐substituted benzyl ester bis(pyrrole)phenylenediamine (named "pyrrophen") ligands. In both cases, the neptunium center exists in the +6 oxidation state,. As our specific interest is in exploring the chemistry of neptunium compounds containing the linear neptunyl ion (NpO22+) through equatorially coordinating the metal by multidentate organic ligands, we have identified the differences that are likely to cause discrepancy between the two complexes by examining the ions and their coordinative environments through single‐crystal X‐ray crystallography, diffuse reflectance, and Raman spectroscopy. This is the first time pyrrophen has been utilized in Np chemistry and demonstrates a new platform to study 5 f electron participation and coordination. [ABSTRACT FROM AUTHOR]

The document is a contents list for the journal "Dalton Transactions: An International Journal of Inorganic Chemistry." It includes a range of articles on various topics related to inorganic chemistry, such as electrocatalysts for water splitting, phosphors for backlight display applications, and metal-organic compounds in sensing and catalysis. The journal is published by The Royal Society of Chemistry, a leading chemistry community. The document provides a list of articles and their authors, along with images and permissions. [Extracted from the article]

Host‐guest chemistry of chiral metal‐organic frameworks (MOFs) has endowed them with circularly polarized luminescence (CPL), it is still limited for MOFs to systematically tune full‐color CPL emissions and sizes. This work directionally assembles the chiral ligands, metal sites and organic dyes to prepare a series of crystalline enantiomeric D/L‐Cd/Zn‐n MOFs (n=1~5, representing the adding amount of dyes), where D/L‐Cd/Zn with the formula of Cd2(D/L–Cam)2(TPyPE) and Zn2(D/L–Cam)2(TPyPE) (D/L‐Cam=D/L‐camphoric acid, TPyPE=4,4’,4’’,4’’’‐(1,2‐henediidenetetra‐4,1‐phenylene)tetrakis[pyridine]) were used as the chiral platforms. The framework‐dye‐enabled emission and through‐space chirality transfer facilitate D/L‐Cd/Zn‐n bright full‐color CPL activity. The ideal yellow CPL of D‐Cd‐5 and D‐Zn‐4, with |glum| as 4.9 × 10−3 and 1.3×10−3 and relatively high photoluminescence quantum yield of 40.79 % and 45.40 %, are further assembled into a white CPL light‐emitting diode. The crystal sizes of D/L‐Cd/Zn‐n were found to be strongly correlated to the types and additional amounts of organic dyes, that the positive organic dyes allow for the preparation of > 7 mm bulks and negative dyes account for sub‐20 μm particles. This work opens a new avenue to fabricate full‐color emissive CPL composites and provides a potentially universal method for controlling the size of optical platforms. [ABSTRACT FROM AUTHOR]

As both a critical chemical feedstock and an environmental pollutant, the production and utilization of ammonia (NH3) are accompanied by the progress of social civilization. In recent years, research on metal/covalent organic framework materials as NH3 adsorbents has attracted increasing attention due to their high porosity, versatile architecture and tunable functionality. This review was organized to highlight the recent advancement of MOF/COF materials for NH3 sorption, which successively presented the key properties of solid adsorbents and summarized the strategies along with their mechanisms for enhancing NH3 adsorption. In addition, perspectives and outlook regarding the future development of MOF/COF‐based NH3 adsorbents were outlined to meet the requirements of practical applications under various condition. [ABSTRACT FROM AUTHOR]

Dopamine (DA) is a widely present, calcium cholinergic neurotransmitter in the body, playing important roles in the central nervous system and cardiovascular system. Developing fast and sensitive DA detection methods is of great significance. Fluorescence-based methods have attracted much attention due to their advantages of easy operation, a fast response speed, and high sensitivity. This study prepared hydrophilic and high-performance CdS/ZnS quantum dots (QDs) for DA detection. The waterborne CdS/ZnS QDs were synthesized in one step using the amphiphilic polymer PEI-g-C14, obtained by grafting tetradecane (C14) to polyethyleneimine (PEI), as a template. The polyacrylonitrile nanofiber membrane (PAN-NFM) was prepared by electrospinning (e-spinning), and a metal organic frame (ZIF-8) was deposited in situ on the surface of the PAN-NFM. The CdS/ZnS QDs were loaded onto this substrate (ZIF-8@PAN-NFM). The results showed that after the deposition of ZIF-8, the water contact angle of the hydrophobic PAN-NFM decreased to within 40°. The nanofiber membrane loaded with QDs also exhibited significant changes in fluorescence in the presence of DA at different concentrations, which could be applied as a fast detection method of DA with high sensitivity. Meanwhile, the fluorescence on this PAN-NFM could be visually observed as it transitioned from a blue-green color to colorless, making it suitable for the real-time detection of DA. [ABSTRACT FROM AUTHOR]

A sensitive analytical procedure for simultaneous extraction and determination of bisphenol A and alkyl phenols, namely, 4‐sec‐butylphenol, 4‐tert‐butylphenol, and 4‐tert‐amylphenol from aqueous samples with metal–organic framework (MOF)‐based dispersive micro‐solid‐phase extraction (D‐µSPE) and high‐performance liquid chromatography (HPLC) technique is developed. Sample contaminants were preconcentrated with amino‐functionalized aluminum MOF and later eluted with acetonitrile. The reconstituted sample was subjected to HPLC analysis. Various procedural parameters related to D‐µSPE were optimized. Under optimized preconcentration and chromatographic conditions, calibration curves with excellent linearity (R2 > 0.9986) in the working range of 0.25–100 ng mL−1 were prepared. Limit of detection (S/N = 3) for every analyte within the range of 0.020–0.022 ng mL−1 was obtained. Analyte's recovery 91.16%–97.01% (RSD = 1.02–3.01) for intraday and 89.86%–95.83% (RSD = 1.15–3.13) for inter‐day analysis was obtained from real water samples. [ABSTRACT FROM AUTHOR]

Superoxide is a reactive oxygen species that is influential in the redox chemistry of a wide range of biological processes and environmental cycles. Using a novel in situ sensor we report the first water column profiles of superoxide in the Baltic Sea, at concentrations higher than previously observed in other oceans. Our data revealed consistent peaks of superoxide (2.0–15.1 nM) in dark waters just below the mixed layer. The oxic waters, low metal concentrations, and lack of sunlight imply that the peak is likely of biological origin. Several profiles displayed a concomitant dip in dissolved oxygen mirroring this superoxide peak, strongly suggesting a link between the two features. The magnitude and distribution of superoxide observed warrants re‐evaluation of the most relevant sources and controls of superoxide in seawater. Locally, these high concentrations of superoxide may create environments conducive to reactions with trace metals and organic matter and present an overlooked sink of oxygen in the Baltic Sea. Plain Language Summary: The combination of unusual inflow activity and topographic conditions with strong anthropogenic influence in the Baltic Sea, offer a unique environment to study redox chemistry. To gain further insight into the biogeochemical cycles in this area we made the first measurements of superoxide, a reactive oxygen species that plays significant roles in organismal health, as well as the chemistry of metals and carbon in seawater. We made direct measurements of superoxide in seawater, leading to continuous profiles between 2 and 80 m at 7 different locations in the Baltic Sea. Our results revealed the presence of widespread superoxide maxima that consistently appeared in dark waters at depths between 23 and 35 m. In some instances, the superoxide peaks are mirrored by dips in oxygen concentrations. This work demonstrates that light‐independent processes were the dominant source of superoxide in the Baltic Sea in September, and point to an association between heterotrophic activity, oxygen loss, and superoxide production. The high levels of superoxide observed in this study suggest that a reevaluation of the abundances of this compound in seawater is necessary, and underline the advantages of in situ techniques for capturing total superoxide concentrations. Key Points: Superoxide maxima consistently appear in dark waters below the mixed layerCorresponding dips in oxygen at depths of superoxide maxima suggest link between heterotrophic respiration and superoxide production [ABSTRACT FROM AUTHOR]

Due to their unique physical and chemical properties, metal-organic cage structures have great potential for applications in various fields. However, current studies have mainly focused on highly symmetric structures assembled from single metal ions and organic ligands, limiting their diversity and complexity, and there are still relatively few studies on the dynamic formation process of metal-organic cages. Herein, we constructed a series of metal-organic cages with different sizes assembled from the highly-stable coordination of 2,2':6',2"-terpyridine-based tetratopic ligands and various metals ions such as Zn, Cu, Co and Fe. Furthermore, the intermolecular exchange process between the metal-organic cages was explored through the dynamic exchange of ligands, and the formation of a series of hybrid supramolecular nanocages together with their final tendency to form a predominant structure of M24L14L28 was observed. In addition, the binding of metal-organic cages with 5,10,15,20-tetrakis(3,4,5-trimethoxyphenyl) porphyrin-Zn was also investigated. This study not only expands the complexity and diversity of metal-organic cages, but also provides a new perspective for studying the dynamic behaviour of metal-organic cages. [ABSTRACT FROM AUTHOR]

Potassium ion batteries gradually have aroused worldwide interest due to the limited lithium resource. However, the research on the solid‐state potassium‐ion batteries is at its very early stage. The lack of electrolytes with high ionic conductivity and interfacial stability is the major obstacle. In this work, a new phase of potassium carbazolide (KC12H8N, β‐KCZ) is synthesized and expected to be less rigid in the stacking layers than the reported α‐KCZ, indicating weaker cation−π interactions. Upon complexing KCZ with THF, a new type of potassium solid‐state electrolyte is successfully developed (KxCZ‐yTHF), particularly, an optimal composition K0.9CZ‐0.7THF reveals an ionic conductivity as high as 4.2 × 10−4 S cm−1 at 100 °C, which is among the top K+ conductors at this temperature. Furthermore, KxCZ‐yTHF also demonstrates a remarkable electrochemical stability window of 3.1 V, as well as outstanding interfacial stability and compatibility against K2S electrode during a 400‐h electrochemical cycling test. Other advantages of this electrolyte include cold pressing for molding, ease for scaling up, and high safety upon exposure to air. To the best of the knowledge, this is the first report that a potassium organic compound is employed as potassium solid‐state electrolyte. [ABSTRACT FROM AUTHOR]

Photocatalytic nitrate reduction reaction (NitRR) is a promising route for environment remediation and sustainable ammonia synthesis. To design efficient photocatalysts, the recently emerged nanoarchitectonics approach holds great promise. Here, we report a nanohouse‐like S‐scheme heterjunction photocatalyst with high photocatalytic NitRR performance. The nano‐house has a floor of plate‐like metal organic framework‐based photocatalyst (NH2‐MIL‐125), on which another photocatalyst Co(OH)2 nanosheet is grown while ZIF‐8 hollow cages are also constructed as the surrounding wall/roof. Experimental and simulation results indicate that the positively charged, highly porous and hydrophobic ZIF‐8 wall can modulate the environment in the nanohouse by (i) NO3− enrichment/NH4+ discharge and (ii) suppression of the competitive hydrogen evolution reaction. In combination with the enhanced electron‐hole separation and strong redox capability in the NH2‐MIL‐125@Co(OH)2 S‐scheme heterjunction confined in the nano‐house, the designed photocatalyst delivers an ammonia yield of 2454.9 μmol g−1 h−1 and an apparent quantum yield of 8.02 % at 400 nm in pure water. Our work provides new insights into the design principles of advanced photocatalytic NitRR photocatalyst. [ABSTRACT FROM AUTHOR]

Herein, a disubstitution strategy of metal ions and organic ligands is employed to synthesize metal–organic framework (MOF) nanosheets with a three-dimensional (3D) porous structure and a highly active metal–sulfur (M–S, M = Co and Ni) region. The obtained MOFs//Zn batteries exhibit excellent electrochemical properties and the electrochemical reaction mechanism was elucidated through a series of ex situ characterizations. [ABSTRACT FROM AUTHOR]

The crystal structure of hexaglycinium tetra-μ-iodido-octaiodidotriplumbate, (C2H6NO2)6[Pb3I12] or (GlyH)6[Pb3I12], is reported. The compound crystallizes in the triclinic space group P1. The [Pb3I12]6− anion is discrete and located around a special position: the central Pb ion located on the inversion center is holodirected, while the other two are hemidirected. The supramolecular nature is mainly based on C—H⋯I, N—H⋯I, O—H⋯I and N—H⋯O hydrogen bonds. Dimeric cations of type (A+⋯A+) for the amino acid glycine are observed for the first time. [ABSTRACT FROM AUTHOR]

Electrocatalytic carbon dioxide (CO2) reduction to valuable chemical compounds is a sustainable technology with enormous potential to facilitate carbon neutrality by transforming intermittent energy sources into stable fuels. Among various electrocatalysts, metal--organic frameworks (MOFs) have garnered increasing attention for the electrochemical CO2 reduction reaction (CO2RR) owing to their structural diversity, large surface area, high porosity and tunable chemical properties. Ligands play a vital role in MOFs, which can regulate the electronic structure and chemical environment of metal centers of MOFs, thereby influencing the activity and selectivity of products. This feature article discusses the strategies for the rational design of ligands and their impact on the CO2RR performance of MOFs to establish a structure--performance relationship. Finally, critical challenges and potential opportunities for MOFs with different ligand types in the CO2RR are mentioned with the aim to inspire the targeted design of advanced MOF catalysts in the future to achieve efficient electrocatalytic CO2 conversion. [ABSTRACT FROM AUTHOR]

Sensing technology is gaining attention and continuously advancing, making it a recommended element of individualized healthcare management. This is due to the powers exhibited by organometallic compounds, which are further enhanced by the field of bioengineering. Organometallic compounds have a wide range of biological activity and find uses in industrial and material science fields. Their unique ability to specifically target and overcome constraints faced by traditional counterparts makes them potential contenders for sensor technology. These compounds are highly sensitive to changes in their environment, allowing them to be utilized as sensors for detecting various chemicals or conditions. Additionally, the versatility of organometallic compounds enables their integration into different sensor platforms, making them suitable for environmental monitoring, medical diagnostics, and industrial quality control. This article provides a comprehensive summary of recent advancements in the design and synthesis of organometallic compounds, with a specific emphasis on their potential use as sensors. It also discusses the changes made to the structure, the processes used for functionalization, the incorporation of microfluidics, and the resulting impact on the materials’ sensing capabilities. These biologically derived methods align with sustainability goals and enhance the affordability, applicability, and effectiveness of sensing. [ABSTRACT FROM AUTHOR]

Carbon dioxide (CO2) is the primary greenhouse gas responsible for global warming, posing a significant challenge to the global environment. To reduce CO2 emission and support the sustainable development, efficient conversion of CO2 into chemical feedstocks has gained a lot of attention. One promising strategy inspired by natural photosynthesis is solar‐driven CO2 reduction, which uses appropriate photocatalytic systems to generate CO, HCOOH, CH4, CH3OH, etc. However, developing low‐cost, environmentally friendly, and non‐toxic materials for the catalytic conversion of CO2 remains a significant challenge. Light‐absorbing photosensitizers play an important role in photocatalytic systems. Recently, non‐precious metal photosensitizers such as organic compounds and earth‐abundant metal complexes have been intensively studied for developing low‐cost photocatalytic systems. This review focuses on recent reports on organic and non‐precious metal photosensitizers for photocatalytic CO2 reduction. [ABSTRACT FROM AUTHOR]

Metal single‐atom catalysts (SACs) play an essential role in small molecule related energy conversion. Metal‐organic frameworks (MOFs), which contain the highly ordered arrays of organic linkers and metal nodes, as well as the clearly defined pore structures, are considered as an ideal platform to fabricate atomically dispersed metal sites. In this review, we summarize the approaches for fabricating MOF‐based SACs by utilizing their structure characteristics. A brief discussion is also given about the feasible techniques to characterize SACs. A series of representative examples of MOF‐based SACs and their energy‐related applications, mainly in photocatalysis and electrocatalysis, are discussed. The challenges and future development opportunities of MOF‐based SACs are highlighted. [ABSTRACT FROM AUTHOR]

Poly‐[n]‐catenanes (PCs) self‐assembled of three‐dimensional (3D) metal organic cages (MOCs) (hereafter referred to as PCs‐MOCs) are a relatively new class of mechanically interlocked molecules (MIMs) that combine the properties of MOCs and polymers. The synthesis of PCs‐MOCs is challenging because of the difficulties associated with interlocking MOCs, the occurrence of multiple weak supramolecular electrostatic interactions between cages, and the importance of solvent templating effects. The high density of mechanical bonds interlocking the MOCs endows the MOCs with mechanical and physical properties such as enhanced stability, responsive dynamic behavior and low solubility, which can unlock new functional properties. In this Minireview, we highlight the benefit of interlocking MOCs in the formation of PCs‐MOCs structures as well as the synthetic approaches exploited in their preparation, from thermodynamic to kinetic methods, both in the solution and solid‐states. Examples of PCs‐MOCs self‐assembled from various types of nanosized cages (i.e., tetrahedral, trigonal prismatic, octahedral and icosahedral) are described in this article, providing an overview of the research carried out in this area. The focus is on the structure–property relationship with examples of functional applications such as electron conductivity, X‐ray attenuation, gas adsorption and molecular sensing. We believe that the structural and functional aspects of the reviewed PCs‐MOCs will attract chemists in this research field with great potential as new functional materials in nanotechnological disciplines such as gas adsorption, sensing and photophysical properties such as X‐ray attenuation or electron conductivity. [ABSTRACT FROM AUTHOR]

Metal-based drugs are finding new medical applications, particularly in antibacterial therapies. Compounds such as Prontosil and ciprofloxacin, as well as its derivatives such as beta-lactam drugs, aminoglycosides, vancomycin, fosfomycin, as well as tetracyclines, play critical roles in the prevention of bacterial and fungal infections. The increasing prevalence of microbial resistance is prompting the use of metal complexes to tackle fungal and bacterial strains. Mercury-based complexes, which are known for their unusual characteristics and reactivity, have received a lot of interest in the field of medicine recently. Additionally, Schiff base complexes are widely used as antifungal, antibacterial, and anticancer drugs, as well as in dye manufacturing. This article discusses current advances in the use of mercury compounds for combating fungus and bacteria, offering information on their efficacy and future applications. [ABSTRACT FROM AUTHOR]

Exposure assessments to metalworking fluids (MWF) is difficult considering the complex nature of MWF. This study describes a comprehensive exposure assessment to straight and water-based MWFs among workers from 20 workshops. Metal and organic carbon (OC) content in new and used MWF were determined. Full-shift air samples of inhalable particulate and gaseous fraction were collected and analysed gravimetrically and for metals, OC, and aldehydes. Exposure determinants were ascertained through observations and interviews with workers. Determinants associated with personal inhalable particulate and gaseous fractions were systematically identified using mixed models. Similar inhalable particle exposure was observed for straight and water-based MWFs (64–386 µg/m3). The gaseous fraction was the most important contributor to the total mass fraction for both straight (322–2362 µg/m3) and water-based MWFs (101–699 µg/m3). The aerosolized particles exhibited low metal content irrespective of the MWF type; however, notable concentrations were observed in the sumps potentially reaching hazardous concentrations. Job activity clusters were important determinants for both exposure to particulate and gaseous fractions from straight MWF. Current machine enclosures remain an efficient determinant to reduce particulate MWF but were inefficient for the gaseous fraction. Properly managed water-based MWF meaning no recycling and no contamination from hydraulic fluids minimizes gaseous exposure. Workshop temperature also influenced the mass fractions. These findings suggest that exposures may be improved with control measures that reduce the gaseous fraction and proper management of MWF. [ABSTRACT FROM AUTHOR]

The realm of application of organometallic catalysis to organic synthesis has witnessed a transformative shift in recent years, owing much to the evolution of ate complexes from mere reagents to versatile catalysts. Ate complexes, formed through the coordination of a neutral Lewis acid with an organic anionic base, have emerged as pivotal intermediates that not only facilitate organic transformations but also serve as efficient catalysts in a wide range of chemical reactions. This review presents the fascinating journey of ate complexes, highlighting their development from stoichiometric reagents to active catalysts. Historically, ate complexes were primarily regarded as stoichiometric species essential for various metal-catalyzed transformations. However, constant research has unveiled their potential as catalysts in their own right, reshaping the landscape of modern organic synthesis. In this minireview, we discuss the pivotal role of ate complexes in the evolution of organic synthesis, from their early days as reactive intermediates to their current stature as catalytic pioneers offering a glimpse into the exciting future of this dynamic field. [ABSTRACT FROM AUTHOR]

Electrochemiluminescence (ECL) has gained renewed interest due to the strong parallel development of luminophores in the field of organic light emitting diodes (OLEDs) with which this technique shares several aspects. In this perspective review we discuss the most relevant advances of the past 15 years in the study of organic and organometallic compounds as ECL emitters, by dividing them in three different classes: i) fluorescent emitters, ii) phosphorescent emitters and iii) Thermally Activated Delayed Fluorescence (TADF) emitters; then, water‐soluble organic luminophores will be also discussed. We focus on how their design, their photo‐ and electrochemical properties and, in particular, the nature of the emitter, affect their efficiency in ECL. Regardless of the type of luminophore or the photoluminescence quantum yield (PLQY), the literature converges on the fact that the most determining aspect is the stability of the oxidized/reduced form of the emitter. Even if phosphorescent emitters can show outstanding efficiency, this often requires the absence of oxygen. In the case of TADFs, there is also a strong dependence of photoluminescence both in terms of PLQY and emission energy on the polarity of the media, so compounds, that appear promising in organic solvents, may be very inefficient in aqueous media. [ABSTRACT FROM AUTHOR]

This article commemorates the 50th anniversary of the passing of Karl Ziegler, a Nobel Prize-winning German chemist, by exploring his scientific journey and remarkable contributions. Ziegler's unwavering passion for science, unique thinking, and exceptional experimental skills formed the bedrock of his scientific endeavors. His research primarily focused on free radical compounds, polycyclic compounds, and organometallic compounds. The Ziegler-Natta catalyst, which he co-invented and named alongside Giulio Natta, had far-reaching implications for the global polyolefin industry, giving rise to a market worth billions of dollars. [ABSTRACT FROM AUTHOR]

BACKGROUND: Environmental and ecological hazards caused by the accumulation of polyethylene terephthalate (PET) are becoming a global concern. The use of enzymes to address the plastic crisis has achieved many successes, but the difficulty in degrading high‐crystallinity PET has limited its application. Numerous studies have investigated the degradation of PET with arbitrary crystallinity to bis‐2‐(2‐hydroxyethyl) terephthalate (BHET) using chemical pre‐treatment methods such as glycolysis, but few have tested its biocompatibility with enzymatic alliances. RESULTS: Herein, we report the enzymatic characterization and subsequent engineering of the state‐of‐the‐art IsPETasePA and MHETase (where MHET is mono(2‐hydroxyethyl) terephthalate), a dual‐enzyme system which can be used for the degradation from BHET to a single‐product terephthalate (TPA). Modulators, including surfactants, organic solvents and metal ions, enhanced the enzyme activity of IsPETasePA and MHETase by up to 1.1‐fold and 2.3‐fold, respectively. 100% TPA yield (BHET of 25 g L−1) was achieved within 5 h. We also analyzed the mechanism of optimal ion modulator modification by dynamics simulation, and it synergistically achieved enhancement of MHET degradation ability by improving stability and binding energy. CONCLUSION: The introduction of modulators improves the efficiency of the dual‐enzyme system in degrading BHET. This work provides a valuable strategy for the complete degradation of BHET to TPA, laying the groundwork for the realization of PET recycling. © 2024 Society of Chemical Industry (SCI). [ABSTRACT FROM AUTHOR]

Copper-based conductive ink has received attention to fabricate thin, flexible, and lightweight devices through printing techniques. In particular, the copper formate based conductive inks, called metal organic decomposition (MOD) inks, which are fabricated by using amine ligand coordinated copper formate have been well studied because of higher oxidative resistant against air than that of metallic copper before thermal annealing. The copper formate moiety of amine ligand coordinated copper formate complexes varies by changing the coordinated amine species, however, for the thermal decomposition temperature of such ink is not well understand. Here, we analyzed the influence of the amine ligand on the thermal decomposition temperature drop of copper formate moiety. Amine-copper formate complexes bearing several amine ligands containing primary amine, pyridine, and imidazole groups were fabricated. The relationship between the evaluated decomposition temperature and the differences between the wavenumbers of symmetric and antisymmetric vibration mode peaks in Fourier transform infrared (FTIR) spectra was found to be nearly linear. This finding demonstrates that the thermal decomposition temperature is governed by the structural modification of formate ions by the coordination of amine groups. Based on this finding, the order of thermal decomposition temperature of the copper moiety is predictable by using FTIR measurement. [ABSTRACT FROM AUTHOR]

Zinc salicylate dihydrate (Zn(HSal)2·2H2O) is an organic-inorganic hybrid compound known for its wide range of applications. In this article, a detailed semiempirical study of zinc salicylate is presented, focusing on its structural, electronic, and thermodynamic properties. The PM3 method, known for its computational efficiency and reasonable accuracy, was used to model the molecular structure and compare with the experimentally obtained properties of Zn(HSal)2 · 2H2O. Based on the obtained calculation results and available experimental data published in the literature, it was found that semi-empirical calculations involving the solvent effect (H2O) agree well with data from X-ray diffraction analysis, while calculations for the gas phase do not agree with experimental data with the required accuracy. Quantum chemical descriptors such as HOMO-LUMO energies, energy gap (ΔEgap), electronegativity (χ), global hardness (η), softness (σ), dipole moment (μ), electrophilic (ω) and nucleophilic (ε) indices were also calculated. The results show that the PM3 method effectively captures the essential features of zinc salicylate, including its geometry and electronic distribution. The obtained results also provide valuable insights into the semiempirical modeling of organometallic compounds and highlight the usefulness of the PM3 method in predicting the behavior of complex molecular systems. [ABSTRACT FROM AUTHOR]

Organometallic compounds are gaining prominence today as they are found to be potent anticancer agents due to their diverse chemical nature along with the metal with which they are chelated. In these organometallic compounds, many different hetero-organic compounds like Schiff bases, Indoles, Quinolines, Pyrroles are chelated with different metals. As these heterocyclic compounds are proven cytotoxic agents at a higher dose, their potency get enhanced by many fold by metal complexation. Schiff base derivatives are reportedly more powerful agents against tumours of different types, they are gaining prominence as antitumour agents. In this present study, different derivatives of Schiff bases are synthesized and chelated with Aluminium (Al) and characterised with IR, NMR, LCMS and also subjected to metal analysis by ICPMS. Later, these compounds were screened by in vitro analysis of their cytotoxic potentials against cancer cell lines by MCF method and are found to be potent cytotoxic agents. Among all, MC-2 and MC-3 are nearer to the cytotoxic range given by NIH. Hence, we anticipate that although all the synthesized organometal complexes are potential cytotoxic agents, however MC 1 and MC 5 are significantly good cytotoxic agents. However, further study is needed to justify this claim. [ABSTRACT FROM AUTHOR]

• The recent progress of different reactions in electrocatalysis is reviewed. • The development of metal-organic skeleton compounds (MOFs) in electrocatalysis was reviewed. • The research focus and prospect of electrocatalysis are prospected. Metal-organic frameworks (MOFs) have favorable characteristics such as large specific surface area, high porosity, structural diversity, and pore surface modification, giving them great potential for development and attractive prospects in the research area of modern materials electrocatalysis. However, unsatisfactory catalytic activity and poor electronic conductivity are the main challenges facing MOFs. This review focuses on MOF-based materials used in electrocatalysis, based on the types of catalytic reactions that have used MOF-based materials in recent years along with their applications, and also looks at some new electrocatalytic materials and their future development prospects. [Display omitted] [ABSTRACT FROM AUTHOR]

Highlights: The structural composition and morphological characteristics of the MOFs are described. The synthesis methods of MOF materials are described, and the effects of postmodification methods on MOF materials are described; The antimicrobial mechanism and classification of MOF materials and the antimicrobial characteristics of Ag-, Cu-, and Zn-based MOF materials are described. This paper highlights the challenges in the development of MOF materials and provides an outlook on the future of MOF materials. Metal-organic frameworks (MOFs) are metal-organic skeleton compounds composed of self-assembled metal ions or clusters and organic ligands. MOF materials often have porous structures, high specific surface areas, uniform and adjustable pores, high surface activity and easy modification and have a wide range of prospects for application. MOFs have been widely used. In recent years, with the continuous expansion of MOF materials, they have also achieved remarkable results in the field of antimicrobial agents. In this review, the structural composition and synthetic modification of MOF materials are introduced in detail, and the antimicrobial mechanisms and applications of these materials in the healing of infected wounds are described. Moreover, the opportunities and challenges encountered in the development of MOF materials are presented, and we expect that additional MOF materials with high biosafety and efficient antimicrobial capacity will be developed in the future. [ABSTRACT FROM AUTHOR]

This is the 16th Atomic Spectrometry Update (ASU) to focus on advances in elemental speciation and covers a period of approximately 12 months from January 2023. This ASU review deals with all aspects of the analytical atomic spectrometry speciation methods developed for: the determination of oxidation states; organometallic compounds; coordination compounds; metal and heteroatom-containing biomolecules, including metalloproteins, proteins, peptides and amino acids; and the use of metal-tagging to facilitate detection via atomic spectrometry. As with all ASU reviews the focus of the research reviewed includes those methods that incorporate atomic spectrometry as the measurement technique. However, because speciation analysis is inherently focused on the relationship between the metal(loid) atom and the organic moiety it is bound to, or incorporated within, atomic spectrometry alone cannot be the sole analytical approach of interest. For this reason, molecular detection techniques are also included where they have provided a complementary approach to speciation analysis. The number of publications covered this year has increased since last year but remains relatively low compared to many of the years that this ASU has been published for. However, there is a good breadth of elements covered, over 20 this year, with the most popular elements still being As, Hg and Se whilst Ge and Tc both make their first appearances this year. Another item to note is the decreasing quality of the abstract for many of the papers, with detail on the methodology, key results with data included, conclusions and implications thereof missing. This is likely to lead to fewer researchers reading the article. [ABSTRACT FROM AUTHOR]

In this letter, we demonstrate the successful development of graphene Schottky barrier diodes (Gr SBDs), which act as an efficient semi-transparent contact to n-GaN. We show that Gr SBDs can be used for deep trap investigations in n-GaN by capacitance-based spectroscopic techniques. To demonstrate its functionality, Gr Schottky barrier diodes on an n-GaN sample grown by the metal organic vapor phase technique were fabricated and then used in the measurements of steady-state photo-capacitance (SSPC) and deep level optical spectroscopy (DLOS). It is shown that the SSPC and DLOS spectra obtained for Gr SBDs are in excellent agreement with Ni-based semi-transparent contacts to n-GaN used in this study for comparison. Deep trap levels located at Ec-3.3 eV, Ec-2.6 eV, and Ec-1.84 eV for Ni SBD and Ec-3.3 eV and Ec-2.6 eV for Gr SBD were found, respectively. The presence of a trap level with Ec-1.84 eV observed only in the Ni SBD samples suggests that this trap originates from different sample treatments prior to Schottky contact deposition. Additionally, the optical capture cross-section data (σ0) derived from DLOS were fitted using the Lucovsky model under the assumption of no lattice relaxation for all deep traps observed in this study. Discrepancies in trap concentration derived from SSPC measurements among different diodes for a trap with EC-3.3 eV were attributed to reduced light transmission through the Gr contact in the UV spectral range and the presence of some macroscopic defects related to Gr transfer to the n-GaN film. [ABSTRACT FROM AUTHOR]

Midinfrared photonic devices are used as lasers and photodetectors in optical gas sensors and fiber‐optic communications. Herein, the pair number dependence and strain compensation dependence of the InAsSb/InAsP superlattice structure to increase luminescence intensity and reduce crystal defects is investigated. InAs substrates are used to demonstrate various effects of strain compensation, including its role in increasing luminescence intensity and improving the surface flatness. Furthermore, the photoluminescence spectra of a grown superlattice between the InAs substrate and GaAs substrate with two‐temperature‐step growth are shown. [ABSTRACT FROM AUTHOR]

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The solvent method for CO2 capture has the advantages of mature technology and low cost, and is widely used. As commonly used absorbents, organic amines have the advantages of fast absorption rate and large absorption capacity. However, due to the chemical reaction between organic amines and CO2, the solution becomes corrosive, resulting in corrosion of equipment pipelines. The corrosion mechanism of organic amine solutions was reviewed. Hydrogenated amine ions, bicarbonate ions and water molecules are the main oxidants, which provide conditions for the occurrence of corrosion. The effects of the types and concentrations of organic amine solution, CO2 loadings, temperatures, O2 content and degradation products on the corrosiveness of the solution were discussed. Among them, CO2 loadings and temperatures are the main factors. The methods of using inorganic and organic corrosion inhibitors, adjusting the pH value of the solution and using stainless steel materials were summarized. The organic corrosion inhibitors for amine solutions are more worthy value of attention. The development direction of future corrosion inhibition technology was put forward. It is necessary to develop new corrosion inhibitors and combine them with corrosion resistant materials, which can provide a reference for further research and solving the corrosion problem of organic amine solutions. [ABSTRACT FROM AUTHOR]

Phytoremediation, an eco-friendly and cost-effective technique for remediating heavy metal-contaminated soils, can be significantly enhanced through the application of soil amendments. This study investigates the impact of Foliar spraying of both organic (fulvic acid, auxin, Compost, and coconut coir) and inorganic (sulfur) amendments on the phytoavailability, accumulation, and recovery of heavy metals: Arsenic-As, Mercury-Hg, Cadmium-Cd and Lead-Pb in contaminated soils. Field experiment was conducted using hyperaccumulator plant species; T. capensis and H. psittacorum with varying amendment treatments to assess their effectiveness in improving phytoremediation outcomes. The results demonstrate that specific amendments significantly increase heavy metal uptake and translocation within plants by altering soil pH, cation exchange capacity, and microbial activity, thus enhancing metal solubility and bioavailability. Furthermore, the study evaluates the potential of these amendments to not only facilitate metal recovery but also to restore soil health and fertility. The findings underscore the potential of tailored amendment strategies in optimizing phytoremediation processes, offering a sustainable solution for heavy metal remediation in polluted environments. [ABSTRACT FROM AUTHOR]

This article discusses the synthesis and reactivity of a new sulfonium salt that can transfer a sulfonitrene unit to C=C double bonds. The salt was synthesized on a large scale and is stable in air and water. It was used in two different transformations, expanding indenes to isoquinolines and contracting arylcyclobutenes to cyanocyclopropanes. The reagent is versatile and can tolerate various functional groups, making it a useful tool in skeletal editing. The authors acknowledge funding and provide supporting information for further details. [Extracted from the article]

Biological degradation method, as an environmentally friendly, low-carbon, and clean pollution treatment technology, is widely used for the harmless disposal of oily sludge. The biodegradability of oily sludge with stable emulsification system, high oil, and water content is poor. Therefore, it is necessary to pre-treat the oily sludge to improve its biodegradability, including recover the petroleum resources and remove heavy metals and bio-toxic organic matters. This review systematically summarizes five oily sludge treatment methods and their influences on sludge biodegradability, including pyrolysis, chemical hot washing, solvent extraction, chemical oxidation, and hydrothermal. Pyrolysis at temperatures above 750 °C produces high molecular weight polycyclic aromatic hydrocarbons, chemical hot washing and chemical oxidation would cause secondary pollution, solvent extraction method could not be applied due to the high cost and high toxicity of the extractant, and the oil removal of hydrothermal method is inefficient. Additionally, the principles, advantages, and disadvantages of those treatments and the factors affecting microbial degradation were analyzed, which provide the development direction of pretreatment technology to improve the biodegradability of oily sludge. [ABSTRACT FROM AUTHOR]

The article presents the results of study of ferruginous mineral waters. The waters under consideration are discharged on the territory of Western Transbaikalia and belong to the anoxic sulfide-free and acidic types. The peculiarities of the formation of gas, major and trace elements, and dissolved organic substance composition have been established using modern methods. It has been shown that the chemical composition of the waters is greatly influenced by acid–base conditions. Acidic ferruginous waters contain large amounts of heavy metals; organic matter is mainly represented by low molecular weight organic compounds. The only metals present in significant amounts in ferruginous waters are manganese and zinc. Dissolved organic matter is represented by diverse types of high-molecular weight compounds that are formed as a result of biotic processes. [ABSTRACT FROM AUTHOR]

Tailoring of organometallics structure toward desirable properties continues to be both fascinating and challenging in the field of materials science. Herein, a novel ferrocene derivative with long straight‐chain alkane mono‐substituent is synthesized and used as multifunctional organometallic additive in the base oil. This ferrocene‐based organometallic compound (MFc) is synthesized via the Friedel‐Crafts acylation of ferrocene with myristyl chloride, followed by reduction with sodium borohydride. The chemical structure, crystallizability, surface morphology, and the thermal properties of the as‐synthesized compound are systematically characterized. As the iron‐containing standard substance, the MFc was preferable dissolve in lubricating oil with the iron element content as high as 2*105 ppm. Resultantly, the MFc/oil solutions exhibited excellent stability even after high‐speed centrifugal treatment, long‐term storage up to 3 months, and ultra‐low temperature treatment at −40°C for 24 h. Moreover, the MFc as a functional lubricant additive could reduce the average wear scar diameter, wear volume, and coefficient of friction with 40%, 73%, and 18%, respectively, as compared to the corresponding pure base oil. This synthetic strategy provides a novel perspective for the design of functional organometallics, and the as‐synthesized novel ferrocene derivative may find a wide range of advanced potential applications in analytical chemistry, tribology, and interfacial science. [ABSTRACT FROM AUTHOR]

It was shown by EPR spectroscopy that Ti(IV) was gradually reduced to Ti(III) when a titanium(IV) dichloride complex with a saligenin ligand was used as a model pre-catalyst in the presence of (EtnAlCl3–n + Bu2Mg) as an activator. Pre-activation of this complex (by stirring in an inert atmosphere with a half-load of the Al/Mg activator before being introduced into the reactor) significantly (about twofold) enhanced its catalytic activity, up to 4100 kgPE molTi–1 h–1 atm–1. All the synthesized polyethylene samples were linear ultrahigh-molecular-weight polymers (UHMWPEs) with Mv = 1.0–3.5×106 g/mol. This pre-activation technique was further employed to test a series of Al/Mg activators that differed in the nature of their organometallic compounds and in their Al/Mg molar ratio. The test data suggest that the catalytic system under study had active sites with titanium being present mainly in the oxidation state of +3. Most samples of UHMWPE produced with the pre-activated complex proved suitable for solvent-free processing into high-strength oriented films. [ABSTRACT FROM AUTHOR]

Nucleation of particles into crystalline structures can be observed in a wide range of systems from metallic and metal–organic compounds to colloidal and polymeric patch particles. Here, we perform kinetic Monte Carlo simulations to study the nucleation kinetics of particles with different ligancies z at constant supersaturation s. This approach allows one to determine several physico-chemical quantities as a function of s, including the growth probability P(n), the critical nucleus size n*, and the stationary nucleation rate Js. Our numerical results are rationalized in terms of a self-consistent nucleation theory where both n* and Js present a non-trivial dependence on s, but which can be determined from the values of effective z-dependent parameters. [ABSTRACT FROM AUTHOR]