Do mobile phone surfaces carry SARS-CoV-2 virus? A systematic review warranting the inclusion of a "6th" moment of hand hygiene in healthcare.

BACKGROUND: Mobile phones, used in billions throughout the world, are high-touch devices subject to a dynamic contamination of microorganisms and rarely considered as an important fomite to sanitise systematically. The emergence of SARS-CoV-2 resulted in the COVID-19 pandemic, arguably the most impactful pandemic of the 21st century with millions of deaths and disruption of all facets of modern life globally. AIM: To perform a systematic review of the literature exploring SARS-CoV-2 presence as a contaminant on mobile phones. METHODS: A systematic search (PubMed and Google Scholar) of literature was undertaken from December 2019 to March 2023 identifying English language studies. Studies included in this review specifically identified or tested for the contamination of the SARS-CoV-2 virus or genome on mobile phones while studies testing for SARS-COV-2 in environments and/or other fomites samples than but not mobile phones were excluded. RESULTS: A total of 15 studies with reports of SARS-CoV-2 contamination on mobile phones between 2020 and 2023 were included. Amongst all studies, which encompassed ten countries, 511 mobile phones were evaluated for the presence of SARS-CoV-2 contamination and 45% (231/511) were positive for SARS-CoV-2. All studies were conducted in the hospital setting and two studies performed additional testing in residential isolation rooms and a patient's house. Four studies (3 in 2020 and one in 2021) reported 0% contamination while two other studies (in 2020 and 2022) reported 100% of mobile phone contamination with SARS-COV-2. All other studies report mobile phones positive for the virus within a range of 4-77%. CONCLUSION: A total of 45% of mobile phones are contaminated with SARS-CoV-2 virus. These devices might be an important fomite vector for viral dissemination worldwide. Competent health authorities are advised/recommended to start a global implementation of mobile phone decontamination by introducing regulations and protocols in public health and health care settings such as the 6th moment of hand washing.

Ultraviolet-C-Based Mobile Phone Sanitisation for Global Public Health and Infection Control.

INTRODUCTION: Mobile phones act as fomites that pose a global public health risk of disseminating microorganisms, including highly pathogenic strains possessing antimicrobial resistances. The use of ultraviolet-C (UV-C) to sanitise mobile phones presents an alternative means to complement basic hand hygiene to prevent the cross-contamination and dissemination of microorganisms between hands and mobile phones. AIM: This study aimed to evaluate the germicidal efficacy of the Glissner CleanPhone UV-C phone sanitiser (Glissner) device. METHODS: Two experimental trials were performed for the evaluation of the CleanPhone (Glissner). The first was a controlled trial, where the germicidal efficacy of the CleanPhone was evaluated against six different microorganism species that were inoculated onto mobile phones. The second was a field trial evaluating the germicidal efficacy of the CleanPhone on 100 volunteer mobile phones. Efficacy was determined based on colony counts of microorganisms on Columbia sheep blood agar before and after UV-C treatment. RESULTS: In the controlled trial, reduction in growth was observed for all microorganisms after UV-C treatment with ST131 Escherichia coli showing the highest growth reduction at 4 log10 CFU/mL followed by C. albicans and ATCC E. coli at 3 log10 CFU/mL. An overall reduction in microorganism growth after UV-C treatment was also observed for the field trial, with an average growth reduction of 84.4% and 93.6% in colony counts at 24 h and 48 h post-incubation, respectively. CONCLUSION: The findings demonstrated the capability of the CleanPhone (Glissner) to rapidly sanitise mobile phones, thereby providing a means to reduce the potential dissemination of microorganisms, including highly pathogenic strains with antimicrobial resistance.

Mobile phones as fomites for pathogenic microbes: A cross-sectional survey of perceptions and sanitization habits of health care workers in Dubai, United Arab Emirates.

BACKGROUNDS: In 2022, smartphone use continues to expand with the number of smartphone subscriptions surpassing 6 billion and forecasted to grow to 7.5 billion by 2026. The necessity of these 'high touch' devices as essential tools in professional healthcare settings carries great risks of cross-contamination between mobile phones and hands. Current research emphasises mobile phones as fomites enhancing the risk of nosocomial disease dissemination as phone sanitisation is often overlooked. To assess and report via a large-scale E-survey the handling practices and the use of phones by healthcare workers. METHODS: A total of 377 healthcare workers (HCWs) participated in this study to fill in an E-survey online consisting of 14 questions (including categorical, ordinal, and numerical data). Analysis of categorical data used non-parametric techniques such as Pearson's chi-squared test. RESULTS: During an 8-h shift, 92.8% (n/N = 350/377) use their phone at work with 84.6% (n/N = 319/377) considering mobile phones as an essential tool for their job. Almost all HCWs who participated in this survey believe their mobile phones could potentially harbour microorganisms (97.1%; n/N = 366/377). Fifty-seven respondents (15.1%) indicated that they use their phones while wearing gloves and 10.3% (n/N = 39/377) have never cleaned their phones. The majority of respondents (89.3%; n/N = 337/377) agreed that contaminated mobile phones could contribute to dissemination of SARS-CoV-2. CONCLUSION: Mobile phone use is now almost universal and indispensable in healthcare. Medical staff believe mobile phones can act as fomites with a potential risk for dissemination of microbes including SARS-COV-2. There is an urgent call for the incorporation of mobile phone sanitisation in infection prevention protocol. Studies on the use of ultraviolet-C based phone sanitation devices in health care settings are needed.

Healthcare Derived Smart Watches and Mobile Phones are Contaminated Niches to Multidrug Resistant and Highly Virulent Microbes.

Background: As high touch wearable devices, the potential for microbial contamination of smart watches is high. In this study, microbial contamination of smart watches of healthcare workers (HCWs) was assessed and compared to the individual's mobile phone and hands. Methods: This study was part of a larger point prevalence survey of microbial contamination of mobile phones of HCWs at the emergency unit of a tertiary care facility. Swabs from smart watches, mobile phones and hands were obtained from four HCWs with dual ownership of these digital devices. Bacterial culture was carried out for all samples and those from smart watches and mobile phones were further assessed using shotgun metagenomic sequencing. Results: Majority of the participants were females (n/N = 3/4; 75%). Although they all use their digital devices at work and believe that these devices could harbour microbes, cleaning in the preceding 24 hours was reported by one individual. Predominant organisms identified on bacterial culture were multidrug resistant Staphylococcus hominis and Staphylococcus epidermidis. At least one organism identified from the hands was also detected on all mobile phones and two smart watches. Shotgun metagenomics analysis demonstrated greater microbial number and diversity on mobile phones compared to smart watches. All devices had high signatures of Pseudomonas aeruginosa and associated bacteriophages and antibiotic resistance genes. Almost half of the antibiotic resistance genes (n/N = 35/75;46.6%) were present on all devices and majority were related to efflux pumps. Of the 201 virulence factor genes (VFG) identified, majority (n/N = 148/201;73%) were associated with P. aeruginosa with 96% (n/N = 142/148) present on smart watches and mobile phones. Conclusion: This first report on microbial contamination of smart watches using metagenomics next generation sequencing showed similar pattern of contamination with microbes, VFG and antibiotic resistance genes across digital devices. Further studies on microbial contamination of wearable digital devices are urgently needed.

Mobile phones are hazardous microbial platforms warranting robust public health and biosecurity protocols.

Advancements in technology and communication have revolutionised the twenty-first century with the introduction of mobile phones and smartphones. These phones are known to be platforms harbouring microbes with recent research shedding light on the abundance and broad spectrum of organisms they harbour. Mobile phone use in the community and in professional sectors including health care settings is a potential source of microbial dissemination. To identify the diversity of microbial genetic signature present on mobile phones owned by hospital medical staff. Twenty-six mobile phones of health care staff were swabbed. DNA extraction for downstream next generation sequencing shotgun metagenomic microbial profiling was performed. Survey questionnaires were handed to the staff to collect information on mobile phone usage and users' behaviours. Each of the 26 mobile phones of this study was contaminated with microbes with the detection of antibiotic resistance and virulent factors. Taken together the sum of microbes and genes added together across all 26 mobile phones totalised 11,163 organisms (5714 bacteria, 675 fungi, 93 protists, 228 viruses, 4453 bacteriophages) and 2096 genes coding for antibiotic resistance and virulent factors. The survey of medical staff showed that 46% (12/26) of the participants used their mobile phones in the bathroom. Mobile phones are vectors of microbes and can contribute to microbial dissemination and nosocomial diseases worldwide. As fomites, mobile phones that are not decontaminated may pose serious risks for public health and biosecurity.

Metagenomic Sequencing and Reverse Transcriptase PCR Reveal That Mobile Phones and Environmental Surfaces Are Reservoirs of Multidrug-Resistant Superbugs and SARS-CoV-2.

Background: Mobile phones of healthcare workers (HCWs) can act as fomites in the dissemination of microbes. This study was carried out to investigate microbial contamination of mobile phones of HCWs and environmental samples from the hospital unit using a combination of phenotypic and molecular methods. Methods: This point prevalence survey was carried out at the Emergency unit of a tertiary care facility. The emergency unit has two zones, a general zone for non-COVID-19 patients and a dedicated COVID-19 zone for confirmed or suspected COVID-19 patients. Swabs were obtained from the mobile phones of HCWs in both zones for bacterial culture and shotgun metagenomic analysis. Metagenomic sequencing of pooled environmental swabs was conducted. RT-PCR for SARS-CoV-2 detection was carried out. Results: Bacteria contamination on culture was detected from 33 (94.2%) mobile phones with a preponderance of Staphylococcus epidermidis (n/N = 18/35), Staphylococcus hominis (n/N = 13/35), and Staphylococcus haemolyticus (n/N = 7/35). Two methicillin-sensitive and three methicillin-resistant Staphylococcus aureus, and one pan-drug-resistant carbapenemase producer Acinetobacter baumannii were detected. Shotgun metagenomic analysis showed high signature of Pseudomonas aeruginosa in mobile phone and environmental samples with preponderance of P. aeruginosa bacteriophages. Malassezia and Aspergillus spp. were the predominant fungi detected. Fourteen mobile phones and one environmental sample harbored protists. P. aeruginosa antimicrobial resistance genes mostly encoding for efflux pump systems were detected. The P. aeruginosa virulent factor genes detected were related to motility, adherence, aggregation, and biofilms. One mobile phone from the COVID-19 zone (n/N = 1/5; 20%) had positive SARS-CoV-2 detection while all other phone and environmental samples were negative. Conclusion: The findings demonstrate that mobile phones of HCWs are fomites for potentially pathogenic and highly drug-resistant microbes. The presence of these microbes on the mobile phones and hospital environmental surfaces is a concern as it poses a risk of pathogen transfer to patients and dissemination into the community.

A pilot metagenomic study reveals that community derived mobile phones are reservoirs of viable pathogenic microbes.

There is increasing attention focussed on the risks associated with mobile phones possibly serving as 'Trojan Horse' fomites for microbial transmission in healthcare settings. However, little is reported on the presence of microbes on community derived mobile phones which in 2021, numbered in the billions in circulation with majority being used on a daily basis. Identify viable microbial organisms swabbed from smartphones on a university campus. Entire surfaces of 5 mobile phones were swabbed and examined for their microbial content using pre-agar-based growths followed by downstream DNA metagenomic next-generation sequencing analysis. All phones were contaminated with viable microbes. 173 bacteria, 8 fungi, 8 protists, 53 bacteriophages, 317 virulence factor genes and 41 distinct antibiotic resistant genes were identified. While this research represents a pilot study, the snapshot metagenomic analysis of samples collected from the surface of mobile phones has revealed the presence of a large population of viable microbes and an array of antimicrobial resistant factors. With billions of phones in circulation, these devices might be responsible for the rise of community acquired infections. These pilot results highlight the importance of public health authorities considering mobile phones as 'Trojan Horse' devices for microbial transmission and ensure appropriate decontamination campaigns are implemented.

Mobile phones of paediatric hospital staff are never cleaned and commonly used in toilets with implications for healthcare nosocomial diseases.

An ever-increasing number of medical staff use mobile phones as a work aid, yet this may pose nosocomial diseases. To assess and report via a survey the handling practices and the use of phones by paediatric wards healthcare workers. 165 paediatric healthcare workers and staff filled in a questionnaire consisting of 14 questions (including categorical, ordinal and numerical data). Analysis of categorical data used non-parametric techniques such as the Chi-squared test. Although 98% of respondents (165 in total) report that their phones may be contaminated, 56% have never cleaned their devices. Of the respondents that clean their devices, 10% (17/165) had done so with alcohol swabs or disinfectant within that day or week; and an additional 12% respondents (20/165) within that month. Of concern, 52% (86/165) of the respondents use their phones in the bathroom, emphasising the unhygienic environments in which mobile phones/smartphones are constantly used. Disinfecting phones is a practice that only a minority of healthcare workers undertake appropriately. Mobile phones, present in billions globally, are therefore Trojan Horses if contaminated with microbes and potentially contributing to the spread and propagation of micro-organisms as per the rapid spread of SARS-CoV-2 virus in the world.

The role of mobile phones as a possible pathway for pathogen movement, a cross-sectional microbial analysis.

INTRODUCTION: Mobile phones are used the world over, including in healthcare settings. This study aimed to investigate the viable microbial colonisation of mobile phones used by healthcare personnel. METHODS: Swabs collected on the same day from 30 mobile phones belonging to healthcare workers from three separate paediatric wards of an Australian hospital were cultured on five types of agar plate, then colonies from each phone were pooled, extracted and sequenced by shotgun metagenomics. Questionnaires completed by staff whose phones were sampled assisted in the analysis and interpretation of results. RESULTS AND DISCUSSION: All phones sampled cultured viable bacteria. Overall, 399 bacterial operational taxonomic units were identified from 30 phones, with 1432 cumulative hits. Among these were 58 recognised human pathogenic and commensal bacteria (37 Gram-negative, 21 Gram-positive). The total number of virulence factor genes detected was 347, with 1258 cumulative hits. Antibiotic resistance genes (ARGs) were detected on all sampled phones and overall, 133 ARGs were detected with 520 cumulative hits. The most important classes of ARGs detected encoded resistance to beta-lactam, aminoglycoside and macrolide antibiotics and efflux pump mediated resistance mechanisms. CONCLUSION: Mobile phones carry viable bacterial pathogens and may act as fomites by contaminating the hands of their users and indirectly providing a transmission pathway for hospital-acquired infections and dissemination of antibiotic resistance. Further research is needed, but meanwhile adding touching mobile phones to the five moments of hand hygiene is a simple infection control strategy worth considering in hospital and community settings. Additionally, the implementation of practical and effective guidelines to decontaminate mobile phone devices would likely be beneficial to the hospital population and community at large.

Mobile phones represent a pathway for microbial transmission: A scoping review.

BACKGROUND: Mobile phones have become an integral part of modern society. As possible breeding grounds for microbial organisms, these constitute a potential global public health risk for microbial transmission. OBJECTIVE: Scoping review of literature examining microbial's presence on mobile phones in both health care (HC) and community settings. METHODS: A search (PubMed&GoogleScholar) was conducted from January 2005-December 2019 to identify English language studies. Studies were included if samples from mobile phones were tested for bacteria, fungi, and/or viruses; and if the sampling was carried out in any HC setting, and/or within the general community. Any other studies exploring mobile phones that did not identify specific microorganisms were excluded. RESULTS: A total of 56 studies were included (from 24 countries). Most studies identified the presence of bacteria (54/56), while 16 studies reported the presence of fungi. One study focused solely on RNA viruses. Staphylococcus aureus, and Coagulase-Negative Staphylococci were the most numerous identified organisms present on mobile phones. These two species and Escherichia coli were present in over a third of studies both in HC and community samples. Methicillin-resistant S. aureus, Acinetobacter sp., and Bacillus sp. were present in over a third of the studies in HC settings. CONCLUSIONS: While this scoping review of literature regarding microbial identification on mobile phones in HC and community settings did not directly address the issue of SARS-CoV-2 responsible for COVID-19, this work exposes the possible role of mobile phones as a 'Trojan horse' contributing to the transmission of microbial infections in epidemics and pandemics.

Changes in peripapillary blood vessel density in Graves' orbitopathy after orbital decompression surgery as measured by optical coherence tomography angiography.

The purpose is to evaluate the utility of optical coherence tomography (OCT) angiography in the evaluation of Graves' orbitopathy (GO) and response to orbital decompression in patients with and without dysthyroid optic neuropathy (DON). This was a single-center, prospective case series in a cohort of 12 patients (24 orbits) with GO and ±DON, (6 orbits) who underwent bilateral orbital decompression. All patients underwent pre- and postoperative OCT angiography of the peripapillary area. Vessel density indices were calculated in a 4.5 mm × 4.5 mm ellipsoid centered on the optic disk using split-spectrum amplitude decorrelation angiography algorithm, producing the vessel density measurements. Mean change in vessel density indices was compared between pre- and postoperative sessions and between patients with and without DON. Patient 1, a 34-year-old male with GO and unilateral DON OD, showed a significant reduction in blood vessel density indices oculus dexter (OD) (DON eye) after decompression while a more modest reduction was found oculus sinister (OS) with the greatest change noted intrapapillary. Patient 2, a 50-year-old male with DON OU, showed worsening neuropathy following decompression OD that was confirmed by angiographic density indices. Patient 3, a 55-year-female with DON, showed a reduction in blood vessel density OD and increased density OS. Patients without DON showed overall less impressive changes in indices as compared to those with DON. Using OCT angiography, response to surgical treatment in GO orbits, more so in orbits with DON, can be demonstrated and quantified using vessel density indices with reproducibility.

Supply and demand: How does variation in atmospheric oxygen during development affect insect tracheal and mitochondrial networks?

Atmospheric oxygen is one of the most important atmospheric component for all terrestrial organisms. Variation in atmospheric oxygen has wide ranging effects on animal physiology, development, and evolution. This variation in oxygen has the potential to affect both respiratory systems (the supply side) and mitochondrial networks (the demand side) in animals. Insect respiratory systems supplying oxygen to tissues in the gas phase through blind ended tracheal systems are particularly susceptible to this variation. While the large conducting tracheae have previously been shown to respond developmentally to changes in rearing oxygen, the effect of oxygen on the tracheolar network has been relatively unexplored, especially in adult insects. Similarly, mitochondrial networks that meet energy demand in insects and other animals are dynamic and their enzyme activities have been shown to vary in the presence of oxygen. These two systems together should be under selective pressure to meet the aerobic metabolic requirements of insects. To test this hypothesis, we reared Mito-YFP Drosophila under three different oxygen concentrations hypoxia (12%), normoxia (21%), and hyperoxia (31%) and imaged their tracheolar and mitochondrial networks within their flight muscle using confocal microscopy. In terms of oxygen supply, hypoxia increased mean (mid-length) tracheolar diameters, tracheolar tip diameters, the number of tracheoles per main branch and affected tracheal branching patterns, while the opposite was observed in hyperoxia. In terms of oxygen demand, hypoxia increased mitochondrial investment and mitochondrial to tracheolar volume ratios; while the opposite was observed in hyperoxia. Generally, hypoxia had a stronger effect on both systems than hyperoxia. These results show that insects are capable of developmentally changing investment in both their supply and demand networks to increase overall fitness.

Studies on the Activation and Hydrosilylation Catalysis of RhCl3(Bu2S)3.

RhCl3(Bu2S)3 is an industrial precatalyst utilized in the curing of some solventless silicone-release coatings formulations. The catalyst requires no additional inhibitor, in contrast to typical Pt formulations, and so questions arose about how fast the catalyst could trigger curing if it were used in a more activated form. Studies on the activation of RhCl3(Bu2S)3 revealed multiple intermediates, of which [RhCl(Bu2S)2]2 and [RhHCl(SiMe(OSiMe3)2) (Bu2S)2]2 were isolated. [RhHCl(SiMe(OSiMe3)2)(Bu2S)2]2 is the most activated form of the precatalyst, showing a brief induction period. Various experiments were performed to analyze the nature of the catalyst, including Hg poisoning, addition of poison ligands, and comparisons versus Rh nanoparticles. The data tend to be more consistent with a molecular catalyst than Rh nanoparticles. Data are also provided that support the active catalyst containing a RhxClx(Bu2S)2x fragment, although the exact identity of the active catalyst is not yet determined.

Reaction of Aryl Diazonium Salts and Diiron(I) Dithiolato Carbonyls: Evidence for Radical Intermediates.

Treatment of Fe(2)(pdt)(CO)(4)(dppv) (1) with aryldiazonium salts affords the 34e(-) adducts [Fe(2)(pdt)(µ-N(2)Ar)(CO)(4)(dppv)](+) (pdt(2-) = 1,3-propanedithiolate, dppv = cis-C(2)H(2)(PPh(2))(2)). Under some conditions, the same reaction gave substantial amounts of [1](+), the product of electron-transfer. Consistent with the influence of electron transfer in the reactions of some electrophiles with Fe(I)Fe(I) dithiolates, the reaction of [Me(3)S(2)](+) and Fe(2)(pdt)(CO)(4)(dppbz) was found to give [Fe(2)(pdt)(CO)(4)(dppbz)](+) as well as Me(2)S and Me(2)S(2) (dppbz = 1,2-bis(diphenylphosphino)benzene).

EPR/ENDOR, Mössbauer, and quantum-chemical investigations of diiron complexes mimicking the active oxidized state of [FeFe]hydrogenase.

Understanding the catalytic process of the heterolytic splitting and formation of molecular hydrogen is one of the key topics for the development of a future hydrogen economy. With an interest in elucidating the enzymatic mechanism of the [Fe(2)(S(2)C(2)H(4)NH)(CN)(2)(CO)(2)(µ-CO)] active center uniquely found in [FeFe]hydrogenases, we present a detailed spectroscopic and theoretical analysis of its inorganic model [Fe(2)(S(2)X)(CO)(3)(dppv)(PMe(3))](+) [dppv = cis-1,2-bis(diphenylphosphino)ethylene] in two forms with S(2)X = ethanedithiolate (1edt) and azadithiolate (1adt). These complexes represent models for the oxidized mixed-valent Fe(I)Fe(II) state analogous to the active oxidized "H(ox)" state of the native H-cluster. For both complexes, the (31)P hyperfine interactions were determined by pulse electron paramagnetic resonance and electron nuclear double resonance (ENDOR) methods. For 1edt, the (57)Fe parameters were measured by electron spin-echo envelope modulation and Mössbauer spectroscopy, while for 1adt, (14)N and selected (1)H couplings could be obtained by ENDOR and hyperfine sublevel correlation spectroscopy. The spin density was found to be predominantly localized on the Fe(dppv) site. This spin distribution is different from that of the H-cluster, where both the spin and charge densities are delocalized over the two Fe centers. This difference is attributed to the influence of the "native" cubane subcluster that is lacking in the inorganic models. The degree and character of the unpaired spin delocalization was found to vary from 1edt, with an abiological dithiolate, to 1adt, which features the authentic cofactor. For 1adt, we find two (14)N signals, which are indicative for two possible isomers of the azadithiolate, demonstrating its high flexibility. All interaction parameters were also evaluated through density functional theory calculations at various levels.

Stereochemistry of electrophilic attack at 34e⁻ dimetallic complexes: the case of diiron dithiolato carbonyls + MeS⁺.

Experimental and computational experiments show that the electrophile MeS(+) attacks a single Fe center in Fe(2)(propanedithiolate)(CO)(4)(PMe(3))(2) followed by isomerization of this terminal thiolato complex to the corresponding µ-SMe derivative.

Role of the azadithiolate cofactor in models for [FeFe]-hydrogenase: novel structures and catalytic implications.

This paper summarizes studies on the redox behavior of synthetic models for the [FeFe]-hydrogenases, consisting of diiron dithiolato carbonyl complexes bearing the amine cofactor and its N-benzyl derivative. Of specific interest are the causes of the low reactivity of oxidized models toward H(2), which contrasts with the high activity of these enzymes for H(2) oxidation. The redox and acid-base properties of the model complexes [Fe(2)[(SCH(2))(2)NR](CO)(3)(dppv)(PMe(3))](+) ([2](+) for R = H and [2'](+) for R = CH(2)C(6)H(5), dppv = cis-1,2-bis(diphenylphosphino)ethylene)) indicate that addition of H(2) followed by deprotonation are (i) endothermic for the mixed valence (Fe(II)Fe(I)) state and (ii) exothermic for the diferrous (Fe(II)Fe(II)) state. The diferrous state is shown to be unstable with respect to coordination of the amine to Fe, a derivative of which was characterized crystallographically. The redox and acid-base properties for the mixed valence models differ strongly for those containing the amine cofactor versus those derived from propanedithiolate. Protonation of [2'](+) induces disproportionation to a 1:1 mixture of the ammonium [H2'](+) (Fe(I)Fe(I)) and the dication [2'](2+) (Fe(II)Fe(II)). This effect is consistent with substantial enhancement of the basicity of the amine in the Fe(I)Fe(I) state vs the Fe(II)Fe(I) state. The Fe(I)Fe(I) ammonium compounds are rapid and efficient H-atom donors toward the nitroxyl compound TEMPO. The atom transfer is proposed to proceed via the hydride. Collectively, the results suggest that proton-coupled electron-transfer pathways should be considered for H(2) activation by the [FeFe]-hydrogenases.

Artificial hydrogenases.

Decades of biophysical study on the hydrogenase (H(2)ase) enzymes have yielded sufficient information to guide the synthesis of analogs of their active sites. Three families of enzymes serve as inspiration for this work: the [FeFe]-H(2)ases, [NiFe]-H(2)ases, and [Fe]-H(2)ases, all of which feature iron centers bound to both CO and thiolate. Artificial H(2)ases affect the oxidation of H(2) and the reverse reaction, the reduction of protons. These reactions occur via the intermediacy of metal hydrides. The inclusion of amine bases within the catalysts is an important design feature that is emulated in related bioinspired catalysts. Continuing challenges are the low reactivity of H(2) toward biomimetic H(2)ases.

Hydrogen activation by biomimetic diiron dithiolates.

Using the thermally stable salts of [Fe(2)(SR)(2)(CO)(3)(PMe(3))(dppv)]BAr(F)(4), we found that the azadithiolates [Fe(2)(adtR)(CO)(3)(PMe(3))(dppv)](+) react with high pressures of H(2) to give the hydride [Fe(2)(mu-H)(adtR)(CO)(3)(dppv)(PMe(3))]BAr(F)(4). The related oxadithiolate and propanedithiolate complexes are unreactive toward H(2). Molecular hydrogen is proposed to undergo heterolysis assisted by the amine followed by isomerization of an initially formed terminal hydride. Use of H(2) and D(2)O gave the deuteride as well as the hydride, implicating protic intermediates.

Aza- and oxadithiolates are probable proton relays in functional models for the [FeFe]-hydrogenases.

The dithiolate cofactor for the [FeFe]-hydrogenase models, Fe(2)(xdt)(CO)(2)(dppv)(2) (where xdt = 1,3-propanedithiolate (pdt), azadithiolate (adt), (SCH(2))(2)NH, and oxadithiolate (odt), (SCH(2))(2)O; dppv = cis-1,2-bis(diphenylphosphino)ethylene) have been probed for their functionality as proton relays enabling formation and deprotonation of terminal hydrides. Compared to the propanedithiolate derivative, the azadithiolate and oxaditiholate show enhanced rates of proton transfer between solution and the terminal site on one Fe center. The results are consistent with the heteroatom of the dithiolate serving a gating role for both protonation and deprotonation. The pK(a) of the transiently formed ammonium (pK(CD(2))(Cl(2)) 5.7-8.2) or oxonium (pK(CD(2))(Cl(2)) -4.7-1.6) regulates the proton transfer. As a consequence, only the azadithiolate is capable of yielding the terminal hydride from weak acids. The aza- and oxadithiolates manifested the advantages of proton relays: the odt derivative proved to be a faster catalyst for hydrogen evolution than the pdt derivative as indicated from cyclic voltammetry plots of i(c)/i(p) vs [H(+)]. The adt derivative was capable of proton reduction from the weak acid [HPMe(2)Ph]BF(4) (pK(CD(2))(Cl(2)) = 5.7). The proton relay function does not apply to the isomeric bridged-hydrides [Fe(2)(xdt)(mu-H)(CO)(2)(dppv)(2)](+), where the hydride is too distant and too basic to interact to be affected by the heteroatomic relay site. None of these mu-H species can be deprotonated.