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.

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.

Effect of detector geometry and surface finish on Cerenkov based time estimation in monolithic BGO detectors.

Objective.Time-of-flight positron emission tomography based on bismuth germanate (BGO) detectors is made possible due to fast emission of Cerenkov light. Only around 17 Cerenkov photons are produced per 511 keV photoelectric event, making high photon collection efficiency crucial for obtaining good time-of-flight capabilities. In this study, we investigate how different lateral and back surface finishes affect the photon collection efficiency and Cerenkov based timing performance in monolithic BGO.Approach.The study is performed using GATE for gamma and optical photon modeling, with surface reflections of photons simulated by the LUT Davis model. We compare for different detector configurations (regarding size and surface finishes) the photon collection efficiency, detection delays of the first few optical photons and coincidence time resolution estimations obtained by modeling the SiPM signals and performing leading edge discrimination. An additional comparison is made to LYSO scintillators and pixelated detectors.Main results.Although Cerenkov photon emission is directional, many high incidence angle Cerenkov photons are emitted due to electron scattering in the crystal. Substituting a polished back (photodetector side) surface for a rough surface increases the collection efficiency of these high angle of incidence photons. Results show that for a monolithic 50 × 50 × 12 mm3BGO detector with reflective side surfaces, this leads to an overall increase in photon collection efficiency of 34%. Cerenkov photon collection efficiency is also improved, resulting in a reduction of the photon detection delays (and the variation therein) of the first few optical photons. This leads to a better coincidence time resolution, primarily achieved by a shortening of the tails in the time-of-flight kernel, with an 18% reduction in full width at tenth maximum.Significance.This study shows the importance of the photon collection efficiency for timing performance in Cerenkov based monolithic detectors, and how it can be improved with different surface finishes.

ATR-FTIR Biosensors for Antibody Detection and Analysis.

Quality control of drug products is of paramount importance in the pharmaceutical world. It ensures product safety, efficiency, and consistency. In the case of complex biomolecules such as therapeutic proteins, small variations in bioprocess parameters can induce substantial variations in terms of structure, impacting the drug product quality. Conditions for obtaining highly reproducible grafting of 11-mercaptoundecanoic acid were determined. On that basis, we developed an easy-to-use, cost effective, and timesaving biosensor based on ATR-FTIR spectroscopy able to detect immunoglobulins during their production. A germanium crystal, used as an internal reflection element (IRE) for FTIR spectroscopy, was covalently coated with immunoglobulin-binding proteins. This thereby functionalized surface could bind only immunoglobulins present in complex media such as culture media or biopharmaceutical products. The potential subsequent analysis of their structure by ATR-FTIR spectroscopy makes this biosensor a powerful tool to monitor the production of biotherapeutics and assess important critical quality attributes (CQAs) such as high-order structure and aggregation level.

Photochemical vapor generation for germanium: synergistic effect from cobalt/chloride ions and air-liquid interfaces.

Photochemical vapor generation (PVG) of germanium (Ge) was first reported in this work. The synergistic effect from cobalt/chloride ions and air-liquid interfaces was found for the PVG of Ge. No obvious signal response was observed from the standard solution of Ge in 10% (v/v) formic acids (FAs) under UV irradiation. The addition of 300 mg L-1 of Co2+ and 30 mmol L-1 of Cl- resulted in enhanced photochemical reduction for Ge, and the introduction of air-liquid interfaces proceeding and succeeding the sample solution caused another 4.6 folds of enhancement in signal response of Ge. Under the selected condition, the limit of detection (LOD, 3σ, n = 11) was obtained to be 0.008 ng mL-1 with inductively coupled plasma mass spectrometry (ICP MS) measurement. A good precision, expressed as a relative standard deviation (RSD, n = 7) of 2.0%, was found from replicated measurements of 2 ng mL-1 of Ge. The generation efficiency was found to be no better than 9 ± 2%. The PVG mechanism of Ge was investigated in this work. The new finding is useful for understanding the principle of PVG, and further exploring the analytical and environmental application of PVG.

Controlling amphipathic peptide adsorption by smart switchable germanium interfaces.

The in situ control of reversible protein adsorption to a surface is a critical step towards biofouling prevention and finds utilisation in bioanalytical applications. In this work, adsorption of peptides is controlled by employing the electrode potential induced, reversible change of germanium (100) surface termination between a hydrophobic, hydrogen terminated and a hydrophilic, hydroxyl terminated surface. This simple but effective 'smart' interface is used to direct adsorption of two peptides models, representing the naturally highly abundant structural motifs of amphipathic helices and coiled-coils. Their structural similarity coincides with their opposite overall charge and hence allows the examination of the influence of charge and hydrophobicity on adsorption. Polarized attenuated total reflection infrared (ATR-IR) spectroscopy at controlled electrode potential has been used to follow the adsorption process at physiological pH in deuterated buffer. The delicate balance of hydrophobic and electrostatic peptide/surface interactions leads to two different processes upon switching that are both observed in situ: reversible adsorption and reversible reorientation. Negatively charged peptide adsorption can be fully controlled by switching to the hydrophobic interface, while the same switch causes the positively charged, helical peptide to tilt down. This principle can be used for 'smart' adsorption control of a wider variety of proteins and peptides and hence find application, as e.g. a bioanalytical tool or functional biosensor.

Investigation on tribological behaviors of biodegradable pure Zn and Zn-X (Li, Cu, Ge) binary alloys.

As a potential biodegradable implant material, zinc (Zn) alloys have attracted increasing attention due to their good biocompatibility and moderate degradation rate. Zn and its alloys are expected to become candidate materials for medical devices. The metals implanted in the human body will inevitably undergo friction in the human body before it is completely degraded. Friction and wear are essential factors which may cause medical devices' service failure. However, there are still few studies on the friction and wear properties of biodegradable Zn-based alloys in the human body, and most studies just focus on the mechanical properties, degradation properties and biocompatibility of the alloys. Thus, it is crucial to study the friction and wear properties of Zn and its alloys. In the present work, we investigated the tribological properties of biodegradable pure Zn and Zn-X (Li, Cu, Ge) alloys. Our study found that under simulated body fluid and dry friction conditions, the addition of alloying elements Li and Cu can improve the friction properties of Zn. Among the four metals, Zn-0.5Li alloy has the lowest friction coefficient and the best wear resistance. Hank's solution has lubricating and corrosive effects. That is to say, when the alloy is rubbed in Hank's solution, it can not only be protected by the lubrication of the solution, but also tribocorrosion will occur as well.

Cyclic Analogs of Desferrioxamine E Siderophore for 68Ga Nuclear Imaging: Coordination Chemistry and Biological Activity in Staphylococcus aureus.

As multidrug-resistant bacteria are an emerging problem and threat to humanity, novel strategies for treatment and diagnostics are actively sought. We aim to utilize siderophores, iron-specific strong chelating agents produced by microbes, as gallium ion carriers for diagnosis, applying that Fe(III) can be successfully replaced by Ga(III) without losing biological properties of the investigated complex, which allows molecular imaging by positron emission tomography (PET). Here, we report synthesis, full solution chemistry, thermodynamic characterization, and the preliminary biological evaluation of biomimetic derivatives (FOX) of desferrioxamine E (FOXE) siderophore, radiolabeled with 68Ga for possible applications in PET imaging of S. aureus. From a series of six biomimetic analogs, which differ from FOXE with cycle length and position of hydroxamic and amide groups, the highest Fe(III) and Ga(III) stability was determined for the most FOXE alike compounds-FOX 2-4 and FOX 2-5; we have also established the stability constant of the Ga-FOXE complex. For this purpose, spectroscopic and potentiometric titrations, together with the Fe(III)-Ga(III) competition method, were used. [68Ga]Ga-FOXE derivatives uptake and microbial growth promotion studies conducted on S. aureus were efficient for compounds with a larger cavity, i.e., FOX 2-5, 2-6, and 3-5. Even though showing low uptake values, Fe-FOX 2-4 seems to be also a good Fe-source to support the growth of S. aureus. Overall, proposed derivatives may hold potential as inert and stable carrier agents for radioactive Ga(III) ions for diagnostic medical applications or interesting starting compounds for further modifications.

AIEgen-Based Lifetime-Probes for Precise Furin Quantification and Identification of Cell Subtypes.

Biochemical sensing probes based on aggregation-induced-emission luminogens (AIEgens) are widely used in biological imaging and therapy, chemical sensing, and material sciences. However, it is still a great challenge to quantify the targets through fluorescence intensity of AIEgen probes due to their undesirable aggregations. Here, a PyTPA-ZGO probe with three lifetime signals for precise quantification of furin is constructed: the lifetime signal 1 and signal 2 comes from AIEgen PyTPA-P (τPn ) and inorganic nanoparticles Zn2 GeO4 :Mn2+ -NH2 (τZn ), respectively, while the lifetime signal 3 is marked as the composite dual-lifetime signal (CDLSn , C D L S n = τ Z n τ P n ). In contrast, the fluorescence intensity signal of PyTPA-P shows defectively quantitative performance. Furthermore, it is found that the CDLSn exhibits higher significant differences than the two other lifetime signals (τPn and τZn ) thanks to its wide range between the maximum and minimum signal values and small standard deviation. Therefore, CDLSn is further used to accurately identify cell subtypes based on the specific concentration of furin in each subtype. The lifetime criterion can realize precise quantification, and it should be a promising direction of AIEgen-based quantitative analysis in the future.

Enhanced biocompatibility and osteogenic differentiation of mesenchymal stem cells of titanium by Sr-Ga clavate double hydroxides.

To improve in vivo osseointegration of pure titanium implant, Sr-Ga clavate double hydroxide (CDH) coating was grown in situ on a titanium (Ti) substrate with simple hydrothermal and calcination treatments at 500 °C. The obtained coating on the Ti substrate (Ti-CDH and Ti-CDH500) was researched by scanning electron microscopy (SEM), X-ray diffraction (XRD), and energy dispersive spectroscopy (EDS). Ti-CDH exhibited a sustained release profile of metal ions and maintained a slightly alkaline environment. The CDH coating was beneficial for osteogenic differentiation of mesenchymal stem cells (MSCs), which were reflected by the results of cellular assays, including alkaline phosphatase activity (ALP), cell mineralization capability (ARS), and osteogenesis-related gene expression. Besides, Ti-CDH could effectively improve the autophagic levels in MSCs, which further promoted osteogenic differentiation of MSCs. Hence, the Ti surface with Sr-Ga CDH modification supplied a simple and effective strategy to design biomaterials for bone generation.

Photonic crystal fibre as a potential medium for radiotherapy dosimetry.

Present study concerns the key thermoluminescence (TL) properties of photonic crystal fibres (PCFs), seeking development of alternatively structured TL materials that are able to offer a advantages over existing passive dosimeters. In terms of their internal structure and light guiding properties the PCFs, collapsed and structured, differ significantly from that of conventional optical fibres. To investigate the dosimetric parameters of the PCFs use was made of a linear accelerator producing a 6 MV photon beam, delivering doses ranging from 0.5 Gy to 8 Gy. The parameters studied included TL response, linearity index, glow curves, relative sensitivity and TL signal fading, the results being compared against those obtained using TLD-100 chips. At 4 Gy photon dose the Ge-doped collapsed PCFs were found to provide a response 27 × that of structured PCF, also giving a TL yield similar to that of standard TLD-100 chips. Over post-irradiation periods of 15 and 30 days collapsed PCF TL signal fading were 8% and 17% respectively, with corresponding values of 37% and 64% for the structured PCF. Trapping parameters including the order of kinetics (b), activation energy (E) and frequency factor (s-1) were assessed with Chen's peak shape method. Lifetime of trapping centre was found to be (2.36 E+03) s and (9.03 E +01) s regarding the collapsed and structured PCF respectively with 6 Gy of photon beam. For the Ge-doped collapsed PCF, the high TL yield, sensitivity and low fading provide the basis of a highly promising system of TLD for radiotherapy applications.

Controllable high-performance memristors based on 2D Fe2GeTe3oxide for biological synapse imitation.

Memristors are an important component of the next-generation artificial neural network, high computing systems, etc. In the past, two-dimensional materials based memristors have achieved a high performance and low power consumption, though one at the cost of the other. Furthermore, their performance can not be modulated frequently once their structures are fixed, which remains the bottleneck in the development. Herein, a series of forming free memristors are fabricated with the same Cu/Fe3GeTe2oxide/Fe3GeTe2/Al structure, yet the On/Off ratio and set voltage is modulated continuously by varying the oxidation time during fabrication. With an optimal oxidation time, a large On/Off ratio (1.58 × 103) and low set voltage (0.74 V) is achieved in a single device. The formation and rapture of Al conductive filaments are found to be responsible for the memristors, and the filaments density and the cross-section area increase with the increase of current compliance, which achieves a higher On/Off ratio. The memristor can imitate basic biological synaptic functions using voltage pulses, demonstrating the potential for low-power consuming neuromorphic computing applications.

Quantum Simulation of the Silicene and Germanene for Sensing and Sequencing of DNA/RNA Nucleobases.

Over the last decade, we have been witnessing the rise of two-dimensional (2D) materials. Several 2D materials with outstanding properties have been theoretically predicted and experimentally synthesized. 2D materials are good candidates for sensing and detecting various biomolecules because of their extraordinary properties, such as a high surface-to-volume ratio. Silicene and germanene are the monolayer honeycomb structures of silicon and germanium, respectively. Quantum simulations have been very effective in understanding the interaction mechanism of 2D materials and biomolecules and may play an important role in the development of effective and reliable biosensors. This article focuses on understanding the interaction of DNA/RNA nucleobases with silicene and germanane monolayers and obtaining the possibility of using silicene and germanane monolayers as a biosensor for DNA/RNA nucleobases' sequencing using the first principle of Density Functional Theory (DFT) calculations with van der Waals (vdW) correction and nonequilibrium Green's function method. Guanine (G), Cytosine (C), Adenine (A), Thymine (T), and Uracil (U) were examined as the analytes. The strength of adsorption between the DNA/RNA nucleobases and silicene and germanane is G > C > A > T > U. Moreover, our recent work on the investigation of Au- and Li-decorated silicene and germanane for detection of DNA/RNA nucleobases is presented. Our results show that it is possible to get remarkable changes in transmittance due to the adsorption of nucleobases, especially for G, A, and C. These results indicate that silicene and germanene are both good candidates for the applications in fast sequencing devices for DNA/RNA nucleobases. Additionally, our present results have the potential to give insight into experimental studies and can be valuable for advancements in biosensing and nanobiotechnology.

Bis(µ-Tartrato)Di(µ-Hydroxy) Germanate (IV) Triethanolammonium as a Mononuclear Alkaline Phospholipase A2 Inhibitor.

It was established that the administration of an aqueous solution of bis(µ-tartrato)di(µ-hydroxy) germanate (IV) triethanolammonium to animals daily for 2 months at a dose of the active substance of 10 mg/kg of the animal's weight leads to inhibition of the total activity of the alkaline phospholipase A2 of mononuclear cells. The results of the study can be used to correct lipid metabolism in the development of disorders in hyperlipidemia. This makes it possible to expand the scope of use of the studied substance and create new pharmaceuticals based on bis(µ-tartrato)di(µ-hydroxy) germanate (IV) triethanolammonium prevent and inhibit the development of hyperlipidemia.

Multiple emission bands NIR-persistent luminescence mSiO2@Zn0.6Ca0.4Ga2O4:Cr3+,Yb3+ nanoparticles for biological applications.

Persistent luminescence nanoparticles (PLNPs) emitting in the NIR window (700-1700 nm) have shown great promise in the field of fluorescence imaging due to their unique properties, including the absence of in situ excitation and low optical scattering in tissues. However, they are still facing some challenges, such as irregular shape, wide size distribution and poor persistent luminescence performance. Here, we report a facile mesoporous template method for synthesizing mSiO2@Zn0.6Ca0.4Ga2O4:Cr3+,Yb3+ (mSiO2@ZCGO) persistent luminescent nanoparticles, which show a regular morphology and a size of about 69 nm. In addition, these nanocrystals exhibit persistent luminescence in multi-NIR windows, the first infrared window (∼696 nm of Cr3+ emission) and second infrared window (∼1000 nm of Yb3+ emission). Under illumination of a 254 nm UV lamp for 10 min, the persistent time of Cr3+ ions and Yb3+ ions lasted more than 120 min and 10 min, respectively. In particular, the NIR persistent emission of mSiO2@ZCGO could be stimulated by soft X-ray, which is beneficial to long-term imaging in deep tissues. The optical penetration length of Yb3+ ions persistent luminescence was evaluated to be 2.8 mm. These results demonstrate the great promise of mSiO2@ZCGO for deep-tissue bio-imaging.

Tribological, biocompatibility, and antibiofilm properties of tungsten-germanium coating using magnetron sputtering.

In this study, borosilicate glass and 316 L stainless steel were coated with germanium (Ge) and tungsten (W) metals using the Magnetron Sputtering System. Surface structural, mechanical, and tribological properties of uncoated and coated samples were examined using SEM, X-ray diffraction (XRD), energy-dispersive spectroscopy, and tribometer. The XRD results showed that WGe2 chemical compound observed in (110) crystalline phase and exhibited a dense structure. According to the tribological analyses, the adhesion strength of the coated deposition on 316 L was obtained 32.8 N, and the mean coefficient of friction was around 0.3. Biocompatibility studies of coated metallic biomaterials were analyzed on fibroblast cell culture (Primary Dermal Fibroblast; Normal, Human, Adult (HDFa)) in vitro. Hoescht 33258 fluorescent staining was performed to investigate the cellular density and chromosomal abnormalities of the HDFa cell line on the borosilicate glasses coated with germanium-tungsten (W-Ge). Cell viabilities of HDFa cell line on each surface (W-Ge coated borosilicate glass, uncoated borosilicate glass, and cell culture plate surface) were analyzed by using (3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) cytotoxicity assay. The antibiofilm activity of W-Ge coated borosilicate glass showed a significant reduction effect on Staphylococcus aureus (ATCC 25923) and Pseudomonas aeruginosa (ATCC 27853) adherence compared to control groups. In the light of findings, tungsten and germanium, which are some of the most common industrial materials, were investigated as biocompatible and antimicrobial surface coatings and recommended as bio-implant materials for the first time.

First Characterization of the Formation of Anthocyanin-Ge and Anthocyanin-B Complexes through UV-Vis Spectroscopy and Density Functional Theory Quantum Chemical Calculations.

The occurrence of anthocyanin (ACN) and metal (Me) complexes has been widely supported by many research works while the possibility that ACNs bind to metalloids (Mds) is yet to be proven. Here, metalloids (H3BO3 for B; GeO2 for Ge) were added to cyanidin-based solutions at pH 5, 6, and 7 and ACN-Md stoichiometric ratios of 1:1, 1:10, 1:100, and 1:500, and UV-vis transmittance spectroscopy as well as density functional theory (DFT) calculations were performed to test this hypothesis. Ge and B addition caused bathochromic and hyperchromic shifts on ACN UV-vis spectra, particularly pronounced at pH 5 and a 1:500 (ACN:Md) ratio. ACN-Me complexation reactions have been evaluated where Ge showed a higher capability to bind to ACNs than B. Among the complexes envisioned, those labeled as b1, b2, and b3 feature UV-vis spectra compatible with experiments. The combination of experimental and computational data offers for the first time evidence of the formation of ACN-Md complexes.

Synthesis and preliminary evaluation of a PET-FI bimodal imaging agent targeting estrogen receptor.

Estrogen receptor is an attractive target for the diagnosis and treatment of breast cancer. This article reports for the first time a dual-modality imaging agent targeting estrogen receptor that can use PET imaging to diagnose breast cancer and utilize fluorescence imaging to achieve intraoperative navigation. Fluorescence experiments show that [natGa] 1 has typical aggregate induced emission characteristics. Above the critical concentration, [natGa] 1 can form biocompatible nanomicelles. [natGa] 1 can quickly light up estrogen receptor positive MCF-7 cells. Cell uptake experiments show that [68Ga] 1 is mediated by estrogen receptor. Therefore, [nat/68Ga] 1 shows the characteristics of highly sensitive diagnosis and visualization of breast cancer, and can be used as a lead compound for the development of a novel PET-FI bimodal imaging agent targeting the estrogen receptor.

Examination of metallic impurities of 68Ge/68Ga generators used for radioactive labeling of peptides in clinical PET applications.

BACKGROUND/AIM: Especially suitable for PET due to its nuclear physical and radiochemical properties, the positron emitter Gallium-68 (Ga) occurs by electron capture from Germanium-68 (Ge). In such a radionuclide generator, the germanium is bound to an insoluble, inert column matrix and forms a secular radioactive balance with 68Ga obtained in the hour. As a result of the limited radiochemical selectivity of the elution process, the eluate obtained is basically contaminated with the main nuclide traces, so that the eluate becomes a mixture of Ga and Ge radionuclides. Also, the generator eluate contains a number to metal cations that reduce specific radioactivity and can compete with 68Ga. The presence of toxic metal that can be found in the eluate carries the risks of contamination at every step from the production of generators to radiopharmaceutical production. MATERIALS AND METHOD: In our study, by collecting the eluate of the Ge/Ga generators used with different identities in different centers in Turkey, we report comparative analysis of metal contamination in the generator eluate. The eluates of 68Ge/68Ga generators to five different identities were collected. Eluates were analyzed by inductively coupled plasma-mass spectrometry. RESULTS AND CONCLUSION: As a result, each generator contains metallic impurities different from its certificate.

Quantitative assessment of the interactions between the organogermanium compound and saccharides using an NMR reporter molecule.

Poly-trans-[(2-carboxyethyl)germasesquioxane], Ge-132, is a water-soluble organogermanium compound reported to have physiological effects such as immunostimulatory and antiviral effects. The hydrolysate of Ge-132, 3-(trihydroxygermyl)propanoic acid (THGP), can interact with diols; therefore, it likely can interact with diol-containing sugars in sugar chains, glycoproteins, and glycolipids, which have important physiological functions. In this study, we quantitatively assessed the ability of THGP to interact with saccharides using nuclear magnetic resonance (NMR) spectroscopy and THGP derivatives. THGP was complexed by binding its trihydroxy group with saccharides in aqueous solutions via the cis-diol group rather than the trans-diol group. The spectra of THGP and monosaccharides indicated that THGP has a higher affinity for ketose than aldose. Moreover, the complexation ability between THGP and saccharides was influenced by the number of cis-diol groups on the saccharide structure. Thus, interactions of THGP with important biological sugars might be involved in the physiological functions of Ge-132.