Hydrogen Peroxide Versus Hydrogen Generation at Bipolar Pd/Au Nano-catalysts Grown into an Intrinsically Microporous Polyamine (PIM-EA-TB)

Binding of PdCl42− into the polymer of intrinsic microporosity PIM-EA-TB (on a Nylon mesh substrate) followed by borohydride reduction leads to uncapped Pd(0) nano-catalysts with typically 3.2 ± 0.2 nm diameter embedded within the microporous polymer host structure. Spontaneous reaction of Pd(0) with formic acid and oxygen is shown to result in the competing formation of (i) hydrogen peroxide (at low formic acid concentration in air; with optimum H2O2 yield at 2 mM HCOOH), (ii) water, or (iii) hydrogen (at higher formic acid concentration or under argon). Next, a spontaneous electroless gold deposition process is employed to attach gold (typically 10- to 35-nm diameter) to the nano-palladium in PIM-EA-TB to give an order of magnitude enhanced production of H2O2 with high yields even at higher HCOOH concentration (suppressing hydrogen evolution). Pd and Au work hand-in-hand as bipolar electrocatalysts. A Clark probe method is developed to assess the catalyst efficiency (based on competing oxygen removal and hydrogen production) and a mass spectrometry method is developed to monitor/optimise the rate of production of hydrogen peroxide. Heterogenised Pd/Au@PIM-EA-TB catalysts are effective and allow easy catalyst recovery and reuse for hydrogen peroxide production. Graphical abstract

CALCITE U-Pb DATING UNRAVELS THE AGE AND HYDROTHERMAL HISTORY OF THE GIANT SHUIYINDONG CARLIN-TYPE GOLD DEPOSIT IN THE GOLDEN TRIANGLE, SOUTH CHINA

The ages of Carlin-type gold deposits in the Golden Triangle of South China have long been questioned due to the general lack of minerals unequivocally linked to gold deposition that can be precisely dated using conventional radiogenic isotope techniques. Recent advances in U-Pb methods show that calcite can be used to constrain the ages of hydrothermal processes, but few studies have been applied to ore deposits. Herein, we show that this approach can be used to constrain the timing of hydrothermal activity that generated and overprinted the giant Shuiyindong Carlin-type gold deposit in the Golden Triangle. Three stages of calcite (Cal-1, Cal-2, and Cal-3) have been recognized in this deposit based on crosscutting relationships, cathodoluminescence colors, and chemical (U, Pb, and rare earth element [REE]) and isotope (C, O, Sr) compositions. Cal-1 is texturally associated with ore-stage jasperoid and disseminated Au-bearing arsenian pyrite in hydrothermally altered carbonate rocks, which suggests it is synmineralization. Cal-2 fills open spaces and has a distinct orange cathodoluminescence, suggesting that it precipitated during a second fluid pulse. Cal-1 and Cal-2 have similar carbonate rock-buffered chemical and isotopic compositions. Cal-3 occurs in veins that often contain realgar and/or orpiment and are chemically (low U, Pb, and REE) and isotopically (higher δ13C, lower δ18O and Sri values) distinct from Cal-1 and Cal-2, suggesting that it formed from a third fluid. U-Pb isotope analyses, by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) for U-rich Cal-1 and Cal-2 and by LA-multicollector (MC)-ICP-MS for U-poor Cal-3, yield well-defined age constraints of 204.3 to 202.6, 191.9, and 139.3 to 137.1 Ma for Cal-1, Cal-2, and Cal-3, respectively. These new ages suggest that the Shuiyindong gold deposit formed in the late Triassic and was overprinted by hydrothermal events in the early Jurassic and early Cretaceous. Given the association of Cal-3 with orpiment and realgar, and previous geochronologic studies of several other major gold deposits in the Golden Triangle, we infer that the latest stage of calcite may be associated with an early Cretaceous regional gold metallogenic event. Combined with existing isotopic ages in the region, these new ages lead us to propose that Carlin-type gold deposits in the Golden Triangle formed during two metallogenic episodes in extensional settings, associated with the late Triassic Indochina orogeny and early Cretaceous paleo-Pacific plate subduction. This study shows that the calcite U-Pb method can be used to constrain the timing of Carlin-type gold deposits and successive hydrothermal events.

Nanoparticle Delivery in Prostate Tumors Implanted in Mice Facilitated by Either Local or Whole-Body Heating

This work discusses in vivo experiments that were performed to evaluate whether local or whole-body heating to 40 °C reduced interstitial fluid pressures (IFPs) and enhanced nanoparticle delivery to subcutaneous PC3 human prostate cancer xenograft tumors in mice. After heating, 0.2 mL of a previously developed nanofluid containing gold nanoparticles (10 mg Au/mL) was injected via the tail vein. The induced whole-body hyperthermia led to increases in tumor and mouse body blood perfusion rates of more than 50% and 25%, respectively, while the increases were much smaller in the local heating group. In the whole-body hyperthermia groups, the IFP reduction from the baseline at the tumor center immediately after heating was found to be statistically significant when compared to the control group. The 1 h of local heating group showed IFP reductions at the tumor center, while the IFPs increased in the periphery of the tumor. The intratumoral gold nanoparticle accumulation was quantified using inductively coupled plasma mass spectrometry (ICP-MS). Compared to the control group, 1 h or 4 h of experiencing whole-body hyperthermia resulted in an average increase of 51% or 67% in the gold deposition in tumors, respectively. In the 1 h of local heating group, the increase in the gold deposition was 34%. Our results suggest that 1 h of mild whole-body hyperthermia may be a cost-effective and readily implementable strategy for facilitating nanoparticle delivery to PC3 tumors in mice.

Role of the Environment in the Placement of Apocarbonate Gold Mineralization Chakylkalyan Megablock (Southern Uzbekistan)

Analysis of the available information and the results of many years of research on gold deposits in Uzbekistan made it possible to identify the main unconventional types of deposits. Among them, the most interesting are apocarbonate, crustal, sulfide-carbonaceous and apovolcanogenic quartzite (Upper-Kattakashkasai ore occurrence). The apocarbonate type is widespread in Uzbekistan, has been studied in sufficient detail and information is provided on it in this article. The article examines the existence, distribution and genesis of ores of Karlin type gold deposits. The generalizing characteristics of the Karlin type gold mineralization are given. The issues of geochemical specialization of the Paleozoic strata of the Chakylkalyan megablock are considered, the most favorable stratolevel for the localization of mineralized zones is determined, and the features of carbonate rocks in the process of gold deposition during reactions with silicic solutions are characterized. Based on the materials of regional geochemical profiling, the behavior of the main ore-forming elements in the rocks of both carbonate and volcanogenic-terrigenous strata is analyzed. As a result of the analysis, subclarkic contents of the main ore-forming elements (As, Co, Ni, Pb, Cu, Ag, V, Cr, Sc) were revealed, which create increased concentrations in gold-bearing pyrites of both apocarbonate gold mineralization and related formations.

Hybrid Nanoparticles Based on Cobalt Ferrite and Gold: Preparation and Characterization

During the past few decades, hybrid nanoparticles (HNPs) based on a magnetic material and gold have attracted interest for applications in catalysis, diagnostics and nanomedicine. In this paper, magnetic CoFe2O4/Au HNPs with an average particle size of 20 nm, decorated with 2 nm gold clusters, were prepared using methionine as a reducer and an anchor between CoFe2O4 and gold. The methionine was used to grow the Au clusters to a solid gold shell (up to 10 gold deposition cycles). The obtained nanoparticles (NPs) were studied by X-Ray diffraction (XRD), transmission electron microscopy (TEM), Fourier-transform infrared (FT-IR) spectroscopy, X-Ray photoelectron spectroscopy (XPS) and UV-vis spectroscopy techniques. The TEM images of the obtained HNPs showed that the surface of cobalt ferrite was covered with gold nanoclusters, the size of which slightly increased with an increase in the number of gold deposition cycles (from 2.12 ± 0.15 nm after 1 cycle to 2.46 ± 0.13 nm after 10 cycles). The density of the Au clusters on the cobalt ferrite surface insignificantly decreased during repeated stages of gold deposition: 21.4 ± 2.7 Au NPs/CoFe2O4 NP after 1 cycle, 19.0 ± 1.2 after 6 cycles and 18.0 ± 1.4 after 10 cycles. The magnetic measurements showed that the obtained HNPs possessed typical ferrimagnetic behavior, which corresponds to that of CoFe2O4 nanoparticles. The toxicity evaluation of the synthesized HNPs on Chlorella vulgaris indicated that they can be applied to biomedical applications such as magnetic hyperthermia, photothermal therapy, drug delivery, bioimaging and biosensing.

The Role of the Molecular Hydrogen Formation in the Process of Metal-Ion Reduction on Multicrystalline Silicon in a Hydrofluoric Acid Matrix

Metal deposition on silicon in hydrofluoric acid (HF) solutions is a well-established process for the surface patterning of silicon. The reactions behind this process, especially the formation or the absence of molecular hydrogen (H2), are controversially discussed in the literature. In this study, several batch experiments with Ag+, Cu2+, AuCl4– and PtCl62– in HF matrix and multicrystalline silicon were performed. The stoichiometric amounts of the metal depositions, the silicon dissolution and the molecular hydrogen formation were determined analytically. Based on these data and theoretical considerations of the valence transfer, four reasons for the formation of H2 could be identified. First, H2 is generated in a consecutive reaction after a monovalent hole transfer (h+) to a Si–Si bond. Second, H2 is produced due to a monovalent hole transfer to the Si–H bonds. Third, H2 occurs if Si–Si back bonds of the hydrogen-terminated silicon are attacked by Cu2+ reduction resulting in the intermediate species HSiF3, which is further degraded to H2 and SiF62–. The fourth H2-forming reaction reduces oxonium ions (H3O+) on the silver/, copper/ and gold/silicon contacts via monovalent hole transfer to silicon. In the case of (cumulative) even-numbered valence transfers to silicon, no H2 is produced. The formation of H2 also fails to appear if the equilibrium potential of the 2H3O+/H2 half-cell does not reach the energetic level of the valence bands of the bulk or hydrogen-terminated silicon. Non-hydrogen-forming reactions in silver, copper and gold deposition always occur with at least one H2-forming process. The PtCl62– reduction to Pt proceeds exclusively via even-numbered valence transfers to silicon. This also applies to the reaction of H3O+ at the platinum/silicon contact. Consequently, no H2 is formed during platinum deposition.

Hybrid Nanoparticles Based on Cobalt Ferrite and Gold: Preparation and Characterization

During the past few decades, hybrid nanoparticles (HNPs) based on a magnetic material and gold have attracted interest for applications in catalysis, diagnostics and nanomedicine. In this paper, magnetic CoFe2O4/Au HNPs with an average particle size of 10–20 nm decorated with 2-nm gold clusters were prepared using methionine as a reducer and an anchor between CoFe2O4 and gold. The obtained nanoparticles were studied by X-Ray diffraction (XRD), transmission electron microscopy (TEM), Fourier-transform infrared (FT-IR) spectroscopy and X-Ray photoelectron spectroscopy (XPS) and UV-Vis spectroscopy techniques. The TEM images of the HNPs obtained after one, six and ten gold deposition cycles showed that the surface of cobalt ferrite was covered with gold nanoclusters, which slightly increased with an increase in the number of gold deposition cycles (from 2.12 ± 0.15 nm after one cycle to 2.46 ± 0.13 nm after ten cycles) without any change in surface density. The magnetic measurements showed that the obtained HNPs possessed typical ferrimagnetic behaviour, which corresponds to that of CoFe2O4 nanoparticles. The toxicity evaluation of the synthesised HNPs on Chlorella vulgaris indicated that they can be applied to biomedical applications such as magnetic hyperthermia, photothermal therapy, drug delivery, bioimaging and biosensing.

SULFIDE RECRYSTALLIZATION AND GOLD REMOBILIZATION DURING THE 2.0 GA STAGE OF THE MINAS OROGENY: IMPLICATIONS FOR GOLD MINERALIZATION IN THE QUADRILÁTERO FERRÍFERO AREA, BRAZIL

The historic Quadrilátero Ferrífero mining district in Brazil is a polydeformed Archean terrane recording several tectonic events. This history has hampered the accurate dating of its important gold deposits, given that most of the geochronological clocks have been affected by multiple thermal events. To determine an accurate time constraint for the mineralizing events in this region, we provide the first Re-Os dating for a gold deposit in the Quadrilátero Ferrífero, obtained from 13 mineral separates of disseminated sulfide phases (pyrrhotite, coarse-grained arsenopyrite, fine-grained arsenopyrite, and pyrite) at the recently discovered São Sebastião deposit (northwest Quadrilátero Ferrífero). Three distinct successive sulfidation stages are interpreted at the deposit. The final stage, texturally associated with gold, is marked by fine-grained arsenopyrite and pyrite (assemblage III) and is associated with high-temperature (~600°C) features. A Re-Os errorchron is obtained when considering the data of all samples collectively; however, a comprehensive Re-Os isochron age of 1987 ± 72 Ma (2σ; n = 4; IsoplotR model 3; initial 187Os/188Os = 2.1 ± 0.7) is obtained from assemblage III. A 187Re-187Osr isochron at 1988 ± 56 Ma (mean square of weighted deviates = 0.1, initial 187Osr = –0.1 ± 2.6 ppt; n = 4) is obtained if an initial 187Os/188Os composition of ca. 2.1, is used, this being consistent with the fact that the 187Os in the sulfides in assemblage III is largely radiogenic (187Osr). Earlier assemblages (I and II) individually show variable initial 187Os/188Os, indicative of disturbance to the Re-Os systematics at ~2.0 Ga. This age is considered the best estimate for the timing of gold mineralization at São Sebastião, being coincident with the waning stages of the Minas orogeny, the thermal effects of which are restricted to the southern Quadrilátero Ferrífero. Hence, we consider that the hot fluids from which assemblage III crystallized were responsible for resetting the Re-Os systematics in assemblages I and II and were central to Paleoproterozoic gold deposition in the region. This ~2.0 Ga age challenges previous notions of a late Archean, ~2.7 Ga mineralizing event in the Quadrilátero Ferrífero and makes it possible that gold remobilization occurred elsewhere in the region, particularly in areas representing deeper crustal levels.

Intrusion-Associated Gold Systems and Multistage Metallogenic Processes in the Neoarchean Abitibi Greenstone Belt

In gold-endowed greenstone belts, ore bodies generally correspond to orogenic gold systems (OGS) formed during the main deformation stage that led to craton stabilization (syntectonic period). Most OGS deposits postdate and locally overprint magmatic-hydrothermal systems, such as Au-Cu porphyry that mostly formed during the main magmatic stage (synvolcanic period) and polymetallic intrusion-related gold systems (IRGS) of the syntectonic period. Porphyries are associated with tonalite-dominated and sanukitoid plutons, whereas most IRGS are related to alkaline magmatism. As reviewed here, most intrusion-associated mineralization in the Abitibi greenstone belt is the result of complex and local multistage metallogenic processes. A new classification is proposed that includes (1) OGS and OGS-like deposits dominated by metamorphic and magmatic fluids, respectively; (2) porphyry and IRGS that may contain gold remobilized during subsequent deformation episodes; (3) porphyry and IRGS that are overprinted by OGS. Both OGS and OGS-like deposits are associated with crustal-scale faults and display similar gold-deposition mechanisms. The main difference is that magmatic fluid input may increase the oxidation state and CO2 content of the mineralizing fluid for OGS-like deposits, while OGS are characterized by the circulation of reduced metamorphic fluids. For porphyry and IRGS, mineralizing fluids and metals have a magmatic origin. Porphyries are defined as base metal and gold-bearing deposits associated with large-volume intrusions, while IRGS are gold deposits that may display a polymetallic signature and that can be associated with small-volume syntectonic intrusions. Some porphyry, such as the Côté Gold deposit, demonstrate that magmatic systems can generate economically significant gold mineralization. In addition, many deposits display evidence of multistage processes and correspond to gold-bearing or gold-barren magmatic-hydrothermal systems overprinted by OGS or by gold-barren metamorphic fluids. In most cases, the source of gold remains debated. Whether magmatic activity was essential or marginal for fertilizing the upper crust during the Neoarchean remains a major topic for future research, and petrogenetic investigations may be paramount for distinguishing gold-endowed from barren greenstone belts.