Michaelis-Menten kinetics during dry etching processes.

The chemical etching of germanium in Br2 environment at elevated temperatures is described by the Michaelis-Menten equation. The validity limit of Michaelis-Menten kinetics is subjected to the detailed analysis. The steady-state etching rate requires synergy of two different process parameters. High purity gas should be directed to the substrate on which intermediate reaction product does not accumulate. Theoretical calculations indicate that maximum etching rate is maintained when 99.89% of the germanium surface is covered by the reaction product, and 99.9999967% of the incident Br2 molecules are reflected from the substrate surface. Under these conditions, single GeBr2 molecule is formed after 30 million collisions of Br2 molecules with the germanium surface.

Functional Green-Emitting Mn2+-doped Zinc Germanate Persistent Luminescent Nanoparticles for Dual-Mode Immunochromatographic Detection.

Immunochromatography is a commonly used immediate detection technique, using signal labels to generate detection signals for rapid medical diagnosis. However, its detection sensitivity is affected by background fluorescence caused by the excitation light source. We have developed an immunochromatographic test strip using Zn2GeO4:Mn2+ (ZGM) persistent luminescent nanoparticles (PLNPs) for immediate fluorescence detection and highly sensitive persistent luminescence (PersL) detection without background fluorescence interference. ZGM emits a strong green light when exposed to ultraviolet (UV) excitation, and its green PersL can persist for over 30 min after the excitation light is turned off. We modified the surface of ZGM with heparin-binding protein (HBP) antibodies to create immunochromatographic test strips for the detection of HBP as the target analyte. Under UV excitation, the chromatography test paper can be visually observed at concentrations as low as 25 ng/mL. After the excitation light source is switched off, PersL can achieve a detection limit of 4.7 ng/mL without background interference. This dual-mode immunochromatographic detection, based on ZGM, shows great potential for in vitro diagnostic applications.

Elemental distributions of solid waste collected from the germanium extraction process.

The solid waste produced from the germanium extraction process has attached much attention to its potential germanium sources. However, the elemental distribution of solid waste is still unclear. Therefore, the solid waste was studied using a sequential extraction procedure and characterizations including XRD, FTIR, XPS, SEM-EDS, and XAFS. It has been found that Ca, S, Fe, and Si could present crystal occurrence forms such as calcium sulfate, iron oxide hydroxide, or quartz. Furthermore, Si and Al can form a certain amount of amorphous substance. Accordingly, the sequential leaching results tell that Ca and S can be mostly leached out in pure water or weak acid solution, and more than 50% of Fe, Al, and Si were leached out in the reducible or oxidizable environment. Additionally, a part of S could be associated with Pb, generating a mostly Pb-bearing sulfate structure. Most of Zn was leached out from the reducible step, and only a very small part of Zn presented in the residual state, indicating that the majority of Zn might exist in an oxidation state and a small amount of Zn is associated in the amorphous phase. In terms of Ge, As, and Cr, almost all of them existed in the residual state. Ge should be in the occurrence of Si/Al amorphous structure. Similarly, Cr should be most likely to associate with silicates. Furthermore, As is mainly associated with iron mineral through the formation of the binuclear bidentate corner-sharing complex.

An extended bore length solid-state digital-BGO PET/CT system: design, preliminary experience, and performance characteristics.

PURPOSE: A solid-state PET/CT system uses bismuth germanium oxide (BGO) scintillating crystals coupled to silicon photomultipliers over an extended 32 cm axial field-of-view (FOV) to provide high spatial resolution and very high sensitivity. Performance characteristics were determined for this digital-BGO system, including NEMA and EARL standards. METHODS: Spatial resolution, scatter fraction (SF), noise equivalent count rate (NECR), sensitivity, count rate accuracy, and image quality (IQ) were evaluated for the digital-BGO system as per NEMA NU 2-2018, at 2 sites of first clinical install. System energy resolution was measured. Bayesian penalized-likelihood reconstruction (BPL) was used for IQ. EARL Standards 2 studies were reconstructed by BPL combined with a contrast-enhancing deep learning algorithm. An Esser PET phantom was evaluated. Three patient examples were obtained with low-dose radiotracer activity: 2 MBq/kg of [18F]FDG ([18F]-2-fluoro-2-deoxy-D-glucose), 2.3 MBq/kg [68Ga]Ga-DOTA-TATE ([dodecane tetra-acetic acid,Tyr3]-octreotate), and 14.5 MBq/kg [82Rb]RbCl ([82Rb]-rubidium-chloride). Total scan times were ≤ 8 min. RESULTS: NEMA sensitivity was 47.6 cps/kBq at the axial center. Spatial resolution at 1 cm from the center axis was ≤4.5 mm (filtered back projection) and ≤3.8 mm (ordered subset expectation maximization). SF was 35.6%, count rate accuracy was 2.16%, and peak NECR was 485.2 kcps at 16.9 kBq/mL. Contrast for IQ was 61.1 to 90.7% (smallest to largest sphere) with background variations from 7.6 to 2.1%, and a "lung" error of 4.7%. The average detector energy resolution was 9.67%. Image quality for patient scans was good. EARL Standards 2 criteria were robustly met and Esser phantom features ≥4.8 mm were resolved at 2 min per bed position. CONCLUSION: A solid-state 32 cm axial FOV digital-BGO PET/CT system provides good spatial and energy resolution, high count rates, and superior NEMA sensitivity in its class, enabling fast clinical acquisitions with low-dose radiotracer activity.

Stabilization of Colloidal Germanium Nanoparticles: From the Study to the Prospects of the Application in Thin-Film Technology.

We present the stabilization of halide-terminated Ge nanoparticles prepared via a disproportionation reaction of metastable Ge(I)X solutions with well-defined size distribution. Further tailoring of the stability of the Ge nanoparticles was achieved using variations in the substituent. Ge nanoparticles obtained in this way are readily dispersed in organic solvents, long-term colloidally stable, and are perfect prerequisites for thin-film preparation. This gives these nanomaterials a future in surface-dependent optical applications, as shown for the halide-terminated nanoparticles.

The role of germanium in diseases: exploring its important biological effects.

With the development of organic germanium and nanotechnology, germanium serves multiple biological functions, and its potential value in biochemistry and medicine has increasingly captured the attention of researchers. In recent years, germanium has gradually gained significance as a material in the field of biomedicine and shows promising application prospects. However, there has been a limited amount of research conducted on the biological effects and mechanisms of germanium, and a systematic evaluation is still lacking. Therefore, the aim of this review is to systematically examine the application of germanium in the field of biomedicine and contribute new insights for future research on the functions and mechanisms of germanium in disease treatment. By conducting a comprehensive search on MEDLINE, EMBASE, and Web of Science databases, we systematically reviewed the relevant literature on the relationship between germanium and biomedicine. In this review, we will describe the biological activities of germanium in inflammation, immunity, and antioxidation. Furthermore, we will discuss its role in the treatment of neuroscience and oncology-related conditions. This comprehensive exploration of germanium provides a valuable foundation for the future application of this element in disease intervention, diagnosis, and prevention.

Development of a new integrated IN-VIVO counting system at the QST.

A new in-vivo counting system that functions as both a whole-body counter (WBC) and a lung counter (LC) was developed at the QST to enhance its dose assessment capability. This paper presents an overview of this system and the results of its performance tests. For use of the system as a WBC, three high purity germanium (HPGe) detectors installed in a 20-cm-thick iron shielding chamber are linearly arrayed over a subject lying on the bed, whereas two of the three HPGe detectors are placed over the subject's chest from side to side when using the system as an LC. The new in-vivo system was calibrated using three de-facto phantoms owned by the QST: an adult-male BOttle Manikin ABsorption (BOMAB) phantom, a Lawrence Livermore National Laboratory (LLNL) phantom and a Japan Atomic Energy Research Institute (JAERI) phantom. Monte Carlo simulations were also performed to determine an optimum location for the three detector array in the WBC mode and revealed that the peak efficiency for the BOMAB phantom (662 keV) was little varied as long as the middle detector was placed above the thorax and abdomen parts of the phantom. The calculated peak efficiencies agreed well with the observed peak efficiencies for photons with energies over 100 keV. For lung counting, a tentative Minimum Detectable Activity of 241Am was evaluated as 9.5 Bq for a counting time of 30 minutes, and a Japanese male subject with an average chest wall thinness (2.27 cm). The developed system is now ready for use.

Improved sub-milimeter range-verification method for proton therapy using a composite hadron tumour marker (HTM).

Objective.The results of a follow-up experiment investigating a novel method for sub-milimetre range verification (RV) in proton therapy (PT) are presented.Approach.The method consists of implanting a hadron tumour marker (HTM) near the planned treatment volume, and measuring theγ-ray signals emitted as a result of activation by the proton beam. These signals are highly correlated with the energy of the beam impinging on the HTM and can provide an absolute measurement of the range of the beam relative to the position of the HTM, which is independent of any uncertainties in beam delivery.Main results.Three candidate HTM materials were identified and combined into a single composite HTM, which makes use of the strongest reaction in each material. The setup of the previous experiment was improved on by using high-purity germanium detectors to measure theγ-ray signal with a higher resolution than was previously achieved. A PMMA phantom was also used to simulate theγ-ray background from tissue activation. HTM RV using the data collected in this study yielded range measurements whose average deviation from the expected value was 0.13(22)mm.Significance.Range uncertainty in PT limits the prescribed treatment plan for cancer patients with large safety margins and constrains the direction of the proton beam in relation to any organ at risk. The sub-milimetre range uncertainty achieved in this study using HTM RV, if implemented clinically, would allow for a reduction in the size of safety margins, increasing the therapeutic window for PT.

The new era hypothesis of coastal degradation: G(s) elements-gallium, gadolinium, and germanium.

Mining of precious metals contributes to environmental pollution, especially in coastal areas, and conventional treatment methods are not always effective in removing metal contaminants. Some of these metals, such as gadolinium, germanium and gallium, have caused increasing concern worldwide, as little is known about their current concentrations in the aquatic environment and their biological significance. Therefore, the aim of this study was to determine for the first time the variation of average G(s) concentrations (gallium, gadolinium and germanium) by month/season/site differences along the coast of Istanbul. The ecological risk index was calculated to assess the contamination of seawater and to serve as a diagnostic tool for the mitigation of water pollution. The average distribution G(s) in seawater was in the following order: Ga > Gd > Ge. In addition, the potential ecological risk in the sampling areas ranged from 68 to 1049. Of the three metals, Gd poses the highest ecological risk (grade III). In the spatial distribution of ecological risks, Gd mainly originated from discharges from wastewater treatment plants. Therefore, the sources of the anthropogenic Gd anomaly in wastewater should be identified, as this indicates the possibility of human exposure to potentially harmful anthropogenic compounds.

Recovery technologies for indium, gallium, and germanium from end-of-life products (electronic waste) - A review.

Advanced high-tech applications for communication, renewable energy, and display, heavily rely on technology critical elements (TCEs) such as indium, gallium, and germanium. Ensuring their sustainable supply is a pressing concern due to their high economic value and supply risks in the European Union. Recovering these elements from end-of-life (EoL) products (electronic waste: e-waste) offers a potential solution to address TCEs shortages. The review highlights recent advances in pre-treatment and hydrometallurgical and biohydrometallurgical methods for indium, gallium, and germanium recovery from EoL products, including spent liquid crystal displays (LCDs), light emitting diodes (LEDs), photovoltaics (PVs), and optical fibers (OFs). Leaching methods, including strong mineral and organic acids, and bioleaching, achieve over 95% indium recovery from spent LCDs. Recovery methods emphasize solvent extraction, chemical precipitation, and cementation. However, challenges persist in separating indium from other non-target elements like Al, Fe, Zn, and Sn. Promising purification involves solid-phase extraction, electrochemical separation, and supercritical fluid extraction. Gallium recovery from spent GaN and GaAs LEDs achieves 99% yield via leaching with HCl after annealing and HNO3, respectively. Sustainable gallium purification techniques include solvent extraction, ionic liquid extraction, and nanofiltration. Indium and gallium recovery from spent CIGS PVs achieves over 90% extraction yields via H2SO4 with citric acid-H2O2 and alkali. Although bioleaching is slower than chemical leaching (several days versus several hours), indirect bioleaching shows potential, achieving 70% gallium extraction yield. Solvent extraction and electrolysis exhibit promise for pure gallium recovery. HF or alkali roasting leaches germanium with a high yield of 98% from spent OFs. Solvent extraction achieves over 90% germanium recovery with minimal silicon co-extraction. Solid-phase extraction offers selective germanium recovery. Advancements in optimizing and implementing these e-waste recovery protocols will enhance the circularity of these TCEs.

Orange-red luminescence of samarium-doped bismuth-germanium-borate glass for light-emitting devices.

Samarium (Sm3+ )-doped glass has sparked a rising interest in demonstrating a noticeable emission in the range of 400-700, which is advantageous in solid-state lasers in the visible region, colour displays, undersea communication, and optical memory devices. This study reports the fabrication of Sm3+ -doped bismuth-germanium-borate glasses were established using a standard melt-quenching technique and inspection by absorption, steady-state luminescence, and transient studies. The typical peaks of Sm3+ ions were detected in the visible range under 403 nm excitation. A strong emission band was detected at 599 nm that resembles the 4 G5/2 →6 H7/2 transition of Sm3+ ions for BGBiNYSm0.5 glass. Furthermore, a reddish-orange (coral) luminescence at 646 nm that resembles the 4 G5/2 →6 H9/2 transition was also perceived. The stimulated emission cross-section of 4 G5/2 level for BGBiNYSm0.5 glass was 0.39 × 10-22  cm2 . Lifetime of the 4 G5/2 level was enhanced for the BGBiNYSm0.5 glass and decreased with an increase in active ion concentrations. The lifetime quenching of ions at the metastable state was because of energy transfer among Sm3+ ions by cross-relaxation channels. Commission Internationale de l'Éclairage (CIE) coordinates were evaluated from the emission spectra. Moreover, all the findings recommend these glass as light-emitting materials in the coral region at 599 nm for solid-state lighting applications.

Copper Ion-Modified Germanium Phosphorus Nanosheets Integrated with an Electroactive and Biodegradable Hydrogel for Neuro-Vascularized Bone Regeneration.

Severe bone defects accompanied by vascular and peripheral nerve injuries represent a huge orthopedic challenge and are often accompanied by the risk of infection. Thus, biomaterials with antibacterial and neurovascular regeneration properties are highly desirable. Here, a newly designed biohybrid biodegradable hydrogel (GelMA) containing copper ion-modified germanium-phosphorus (GeP) nanosheets, which act as neuro-vascular regeneration and antibacterial agents, is designed. The copper ion modification process serves to improve the stability of the GeP nanosheets and offers a platform for the sustained release of bioactive ions. Study findings show that GelMA/GeP@Cu has effective antibacterial properties. The integrated hydrogel can significantly boost the osteogenic differentiation of bone marrow mesenchymal stem cells, facilitate angiogenesis in human umbilical vein endothelial cells, and up-regulate neural differentiation-related proteins in neural stem cells in vitro. In vivo, in the rat calvarial bone defect mode, the GelMA/GeP@Cu hydrogel is found to enhance angiogenesis and neurogenesis, eventually contributing to bone regeneration. These findings indicate that in the field of bone tissue engineering, GelMA/GeP@Cu can serve as a valuable biomaterial for neuro-vascularized bone regeneration and infection prevention.

Germanium Complexes with ONO Tridentate Ligands: O-H Bond Activation Control According to DFT Calculations.

Polydentate ligands are used for thermodynamic stabilization of tetrylenes-low-valent derivatives of Group 14 elements (E = Si, Ge, Sn, Pb). This work shows by DFT calculations how the structure (the presence or absence of substituents) and type (alcoholic, Alk, or phenolic, Ar) of tridentate ligands 2,6-pyridinobis(1,2-ethanols) [AlkONOR]H2 and 2,6-pyridinobis(1,2-phenols) [ArONOR]H2 (R = H, Me) may affect the reactivity or stabilization of tetrylene, indicating the unprecedented behavior of Main Group elements. This enables the unique control of the type of the occurring reaction. We found that unhindered [ONOH]H2 ligands predominantly led to hypercoordinated bis-liganded {[ONOH]}2Ge complexes, where an E(+2) intermediate was inserted into the ArO-H bond with subsequent H2 evolution. In contrast, substituted [ONOMe]H2 ligands gave [ONOMe]Ge: germylenes, which may be regarded as kinetic stabilized products; their transformation into E(+4) species is also thermodynamically favorable. The latter reaction is more probable for phenolic [ArONO]H2 ligands than for alcoholic [AlkONO]H2. The thermodynamics and possible intermediates of the reactions were also investigated.

Biodegradable germanium nanoparticles as contrast agents for near-infrared-II photoacoustic imaging.

Photoacoustic (PA) imaging using contrast agents with strong near-infrared-II (NIR-II, 1000-1700 nm) absorption enables deep penetration into biological tissue. Besides, biocompatibility and biodegradability are essential for clinical translation. Herein, we developed biocompatible and biodegradable germanium nanoparticles (GeNPs) with high photothermal stability as well as strong and broad absorption for NIR-II PA imaging. We first demonstrate the excellent biocompatibility of the GeNPs through experiments, including the zebrafish embryo survival rates, nude mouse body weight curves, and histological images of the major organs. Then, comprehensive PA imaging demonstrations are presented to showcase the versatile imaging capabilities and excellent biodegradability, including in vitro PA imaging which can bypass blood absorption, in vivo dual-wavelength PA imaging which can clearly distinguish the injected GeNPs from the background blood vessels, in vivo and ex vivo PA imaging with deep penetration, in vivo time-lapse PA imaging of a mouse ear for observing biodegradation, ex vivo time-lapse PA imaging of the major organs of a mouse model for observing the biodistribution after intravenous injection, and notably in vivo dual-modality fluorescence and PA imaging of osteosarcoma tumors. The in vivo biodegradation of GeNPs is observed not only in the normal tissue but also in the tumor, making the GeNPs a promising candidate for clinical NIR-II PA imaging applications.

Redox flexibility in a germanium hydride manifold: hydrogen shuttling via oxidative addition and reductive elimination.

We report the synthesis of a trimetallic mixed-valence Ge(I)/Ge(II)/Ge(III) trihydride, which presents a structural novel motif among systems of the type (XMH)n (M = group 14 metal). In terms of reactivity (ArNiPr2)GeGe(ArNiPr2)(H)Ge(ArNiPr2)(H)2 can act as a source of both the Ge(II) and Ge(IV) hydrides via Ge-H reductive elimination from the central metal centre involving two different regiochemistries.

Characterization of a 4παß(LS)-γ(HPGe) prototype system for low-background measurements.

A ground-level prototype system for low-background measurements was developed and tested. The system consists of a high-purity germanium (HPGe) detector used for detecting γ rays and coupled to a liquid scintillator (LS) used for detecting α and ß particles. Both detectors are surrounded by shielding materials and anti-cosmic detectors ("veto") used to suppress background events. The energy and timestamp of detected α, ß and γ emissions are recorded event-by-event and analyzed offline. By requiring timing coincidence between the HPGe and LS detectors, background events originating from outside the volume of the measured sample can be effectively rejected. The system performance was evaluated using liquid samples containing known activities of an α emitter (241Am) or a ß emitter (60Co) whose decays are accompanied by γ rays. The LS detector was found to provide a solid angle of almost 4π for α and ß particles. Compared to the traditional γ-singles mode, operating the system in coincidence mode (i.e., α-γ or ß-γ) reduced the background counts by a factor of ∼100. Consequently, the minimal detectable activity for 241Am and 60Co was improved by a factor of 9, being 4 mBq and 1 mBq for an 11-d measurement, respectively. Furthermore, by applying a spectrometric cut in the LS spectrum that corresponds to α emission from 241Am, a background reduction factor of ∼2400 (compared to γ-singles mode) was achieved. Beyond low-background measurements, this prototype exhibits additional compelling features, such as the ability to focus on certain decay channels and study their properties. This concept for a measurement system may be of interest to laboratories that monitor environmental radioactivity, studies involving environmental measurements and/or trace-level radioactivity.

Optimisation of gamma spectrometry measurements in atmosphere during nuclear emergencies.

During emergencies following a major nuclear accident a prompt and accurate characterisation of the radioactive cloud is one of the main task of any radioactivity monitoring system. This task is usually performed by means of γ-spectrometry High Purity Germanium (HPGe) measurements on atmospheric particulate samples gathered by means of high-volume pumps. The key parameters describing the performances of a monitoring system are the Minimum Detectable Activities (MDAs) of the most relevant radionuclides. These parameters depend on a number of factors related to the efficiency of the available germanium detector, the volume of air filtered by the sampling devices and the γ-decay scheme of each radionuclides as well. Besides the MDAs, another very important characteristic of a monitoring system, especially during an evolving emergency, is its capability of giving reliable results at a given and constant pace. It is therefore important to define the time resolution of the monitoring system, i.e. the minimum time needed to produce the data, namely the activity concentrations of the radionuclides in the atmosphere. The optimization of the measurements procedures are discussed in this work: in particular it is demonstrated that, being t the time resolution of the monitoring system, the lowest MDAs can be achieved with a sampling time given by (2/3)·t and a counting time of (1/3)·t. Finally, the MDAs achievable for a standard monitoring system based on a 30% HPGe detector are calculated for all the most important fission products.

Potential Ecological Risk Assessment of Critical Raw Materials: Gallium, Gadolinium, and Germanium.

In recent years, the demand for critical raw materials such as gallium, gadolinium and germanium (G(s)) has steadily increased in various industries. However, treatment or recycling rates of these elements are extremely low, which can lead to environmental pollution. An assessment of the ecological risks was also not possible until now, as there were no calculated toxicity coefficients for G(s). In this study, a well-known method, the so-called potential ecological risk index (PERI), was used for the first time to calculate the toxicity coefficients of these elements using data from recent literature studies on G(s) elements. The toxicity coefficient of each of the three elements was determined as five (5). The results show that G(s) have the same toxicity coefficient as Cu and Pb and are higher than that of Cr. The ecological risk index results varied from 4 to 414, 0.98 to 25.98 and 2.50 to 284.64 for Ga, Gd and Ge, respectively. The results show that Ga and Ge pose high ecological risk while the Eri of Gd is low. The toxicity coefficients of these elements have been calculated for the first time in the literature and provide a practical use for calculating the potential ecological risk index.

Electrochemical Behavior of Reduced Graphene Oxide Supported Germanium Oxide, Germanium Nitride, and Germanium Phosphide as Lithium-Ion Battery Anodes Obtained from Highly Soluble Germanium Oxide.

Germanium and germanium-based compounds are widely used in microelectronics, optics, solar cells, and sensors. Recently, germanium and its oxides, nitrides, and phosphides have been studied as active electrode materials in lithium- and sodium-ion battery anodes. Herein, the newly introduced highly soluble germanium oxide (HSGO) was used as a versatile precursor for germanium-based functional materials. In the first stage, a germanium-dioxide-reduced graphene oxide (rGO) composite was obtained by complete precipitation of GeO2 nanoparticles on the GO from an aqueous solution of HSGO and subsequent thermal treatment in argon at low temperature. The composition of the composite, GeO2-rGO (20 to 80 wt.% of crystalline phase), was able to be accurately determined by the HSGO to GO ratio in the initial solution since complete deposition and precipitation were achieved. The chemical activity of germanium dioxide nanoparticles deposited on reduced graphene oxide was shown by conversion to rGO-supported germanium nitride and phosphide phases. The GeP-rGO and Ge3N4-rGO composites with different morphologies were prepared in this study for the first time. As a test case, composite materials with different loadings of GeO2, GeP, and Ge3N4 were evaluated as lithium-ion battery anodes. Reversible conversion-alloying was demonstrated in all cases, and for the low-germanium loading range (20 wt.%), almost theoretical charge capacity based on the germanium content was attained at 100 mA g-1 (i.e., 2595 vs. 2465 mAh g-1 for Ge3N4 and 1790 vs. 1850 mAh g-1 for GeP). The germanium oxide was less efficiently exploited due to its lower conversion reversibility.

Organogermanium Analogues of Alkenes, Alkynes, 1,3-Dienes, Allenes, and Vinylidenes.

In this review, the latest achievements in the field of multiply bonded organogermanium derivatives, mostly reported within the last two decades, are presented. The isolable Ge-containing analogues of alkenes, alkynes, 1,3-dienes, allenes, and vinylidenes are discussed, and for each class of unsaturated organogermanium compounds, the most representative examples are given. The synthetic approaches toward homonuclear multiply bonded combinations solely consisting of germanium atoms, and their heteronuclear variants containing germanium and other group 14 elements, both acyclic and cyclic, are discussed. The peculiar structural features and nonclassical bonding nature of the abovementioned compounds are discussed based on their spectroscopic and structural characteristics, in particular their crystallographic parameters (double bond length, trans-bending at the doubly bonded centers, and twisting about the double bond). The prospects for the practical use of the title compounds in synthetic and catalytic fields are also briefly discussed.