Efficacy of Wolbachia-based mosquito control: Predictions of a spatially discrete mathematical model.

Wolbachia is an endosymbiont bacterium present in many insect species. When Wolbachia-carrying male Aedes aegypti mosquitoes mate with non-carrier females, their embryos are not viable due to cytoplasmic incompatibility. This phenomenon has been exploited successfully for the purpose of controlling mosquito populations and the spread of mosquito-borne illnesses: Wolbachia carriers are bred and released into the environment. Because Wolbachia is not harmful to humans, this method of mosquito control is regarded as a safer alternative to pesticide spraying. In this article, we introduce a mathematical framework for exploring (i) whether a one-time release of Wolbachia carriers can elicit a sustained presence of carriers near the release site, and (ii) the extent to which spatial propagation of carriers may allow them to establish fixation in other territories. While some prior studies have formulated mosquito dispersal models using advection-reaction-diffusion PDEs, the predictive power of such models requires careful ecological mapping: advection and diffusion coefficients exhibit significant spatial dependence due to heterogeneity of resources and topography. Here, we adopt a courser-grained view, regarding the environment as a network of discrete, diffusively-coupled "habitats"-distinct zones of high mosquito density such as stagnant ponds. We extend two previously published single-habitat mosquito models to multiple habitats, and calculate rates of migration between pairs of habitats using dispersal kernels. Our primary results are quantitative estimates regarding how the success of carrier fixation in one or more habitats is determined by: the number of carriers released, sizes of habitats, distances between habitats, and the rate of migration between habitats. Besides yielding sensible and potentially useful predictions regarding the success of Wolbachia-based control, our framework applies to other approaches (e.g., gene drives) and contexts beyond the realm of insect pest control.

Evaluating artificial intelligence software for delineating hemorrhage extent on CT brain imaging in stroke: AI delineation of ICH on CT.

BACKGROUND: The extent and distribution of intracranial hemorrhage (ICH) directly affects clinical management. Artificial intelligence (AI) software can detect and may delineate ICH extent on brain CT. We evaluated e-ASPECTS software (Brainomix Ltd.) performance for ICH delineation. METHODS: We qualitatively assessed software delineation of ICH on CT using patients from six stroke trials. We assessed hemorrhage delineation in five compartments: lobar, deep, posterior fossa, intraventricular, extra-axial. We categorized delineation as excellent, good, moderate, or poor. We assessed quality of software delineation with number of affected compartments in univariate analysis (Kruskall-Wallis test) and ICH location using logistic regression (dependent variable: dichotomous delineation categories 'excellent-good' versus 'moderate-poor'), and report odds ratios (OR) and 95 % confidence intervals (95 %CI). RESULTS: From 651 patients with ICH (median age 75 years, 53 % male), we included 628 with assessable CTs. Software delineation of ICH extent was 'excellent' in 189/628 (30 %), 'good' in 255/628 (41 %), 'moderate' in 127/628 (20 %), and 'poor' in 57/628 cases (9 %). The quality of software delineation of ICH was better when fewer compartments were affected (Z = 3.61-6.27; p = 0.0063). Software delineation of ICH extent was more likely to be 'excellent-good' quality when lobar alone (OR = 1.56, 95 %CI = 0.97-2.53) but 'moderate-poor' with any intraventricular (OR = 0.56, 95 %CI = 0.39-0.81, p = 0.002) or any extra-axial (OR = 0.41, 95 %CI = 0.27-0.62, p<0.001) extension. CONCLUSIONS: Delineation of ICH extent on stroke CT scans by AI software was excellent or good in 71 % of cases but was more likely to over- or under-estimate extent when ICH was either more extensive, intraventricular, or extra-axial.

Accuracy of artificial intelligence software for CT angiography in stroke.

OBJECTIVE: Software developed using artificial intelligence may automatically identify arterial occlusion and provide collateral vessel scoring on CT angiography (CTA) performed acutely for ischemic stroke. We aimed to assess the diagnostic accuracy of e-CTA by Brainomix™ Ltd by large-scale independent testing using expert reading as the reference standard. METHODS: We identified a large clinically representative sample of baseline CTA from 6 studies that recruited patients with acute stroke symptoms involving any arterial territory. We compared e-CTA results with masked expert interpretation of the same scans for the presence and location of laterality-matched arterial occlusion and/or abnormal collateral score combined into a single measure of arterial abnormality. We tested the diagnostic accuracy of e-CTA for identifying any arterial abnormality (and in a sensitivity analysis compliant with the manufacturer's guidance that software only be used to assess the anterior circulation). RESULTS: We include CTA from 668 patients (50% female; median: age 71 years, NIHSS 9, 2.3 h from stroke onset). Experts identified arterial occlusion in 365 patients (55%); most (343, 94%) involved the anterior circulation. Software successfully processed 545/668 (82%) CTAs. The sensitivity, specificity and diagnostic accuracy of e-CTA for detecting arterial abnormality were each 72% (95% CI = 66-77%). Diagnostic accuracy was non-significantly improved in a sensitivity analysis excluding occlusions from outside the anterior circulation (76%, 95% CI = 72-80%). INTERPRETATION: Compared to experts, the diagnostic accuracy of e-CTA for identifying acute arterial abnormality was 72-76%. Users of e-CTA should be competent in CTA interpretation to ensure all potential thrombectomy candidates are identified.

The influence of alloying on slip intermittency and the implications for dwell fatigue in titanium.

Dwell fatigue, the reduction in fatigue life experienced by titanium alloys due to holds at stresses as low as 60% of yield, has been implicated in several uncontained jet engine failures. Dislocation slip has long been observed to be an intermittent, scale-bridging phenomenon, similar to that seen in earthquakes but at the nanoscale, leading to the speculation that large stress bursts might promote the initial opening of a crack. Here we observe such stress bursts at the scale of individual grains in situ, using high energy X-ray diffraction microscopy in Ti-7Al-O alloys. This shows that the detrimental effect of precipitation of ordered Ti3Al is to increase the magnitude of rare pri〈a〉 and bas〈a〉 slip bursts associated with slip localisation. By contrast, the addition of trace O interstitials is beneficial, reducing the magnitude of slip bursts and promoting a higher frequency of smaller events. This is further evidence that the formation of long paths for easy basal plane slip localisation should be avoided when engineering titanium alloys against dwell fatigue.

External Validation of e-ASPECTS Software for Interpreting Brain CT in Stroke.

OBJECTIVE: The purpose of this study was to test e-ASPECTS software in patients with stroke. Marketed as a decision-support tool, e-ASPECTS may detect features of ischemia or hemorrhage on computed tomography (CT) imaging and quantify ischemic extent using Alberta Stroke Program Early CT Score (ASPECTS). METHODS: Using CT from 9 stroke studies, we compared software with masked experts. As per indications for software use, we assessed e-ASPECTS results for patients with/without middle cerebral artery (MCA) ischemia but no other cause of stroke. In an analysis outside the intended use of the software, we enriched our dataset with non-MCA ischemia, hemorrhage, and mimics to simulate a representative "front door" hospital population. With final diagnosis as the reference standard, we tested the diagnostic accuracy of e-ASPECTS for identifying stroke features (ischemia, hyperattenuated arteries, and hemorrhage) in the representative population. RESULTS: We included 4,100 patients (51% women, median age = 78 years, National Institutes of Health Stroke Scale [NIHSS] = 10, onset to scan = 2.5 hours). Final diagnosis was ischemia (78%), hemorrhage (14%), or mimic (8%). From 3,035 CTs with expert-rated ASPECTS, most (2084/3035, 69%) e-ASPECTS results were within one point of experts. In the representative population, the diagnostic accuracy of e-ASPECTS was 71% (95% confidence interval [CI] = 70-72%) for detecting ischemic features, 85% (83-86%) for hemorrhage. Software identified more false positive ischemia (12% vs 2%) and hemorrhage (14% vs <1%) than experts. INTERPRETATION: On independent testing, e-ASPECTS provided moderate agreement with experts and overcalled stroke features. Therefore, future prospective trials testing impacts of artificial intelligence (AI) software on patient care and outcome are required before widespread implementation of stroke decision-support software. ANN NEUROL 2022;92:943-957.

Evaluation of Spin in the Abstracts of Systematic Reviews and Meta-analyses Covering Treatments for Achilles Tendon Ruptures.

BACKGROUND: Approximately 18 in every 100 000 people have experienced a ruptured Achilles tendon. Despite the prevalence of this condition, treatment options remain contested. HYPOTHESIS/PURPOSE: The objective of this study was to evaluate the use of spin-reporting practices that may exaggerate benefit or minimize harm-in abstracts of systematic reviews related to Achilles tendon repair. We also evaluated whether particular study characteristics were associated with spin. STUDY DESIGN: Cross-sectional. METHODS: We developed a search strategy for Ovid MEDLINE and Ovid Embase for systematic reviews focused on Achilles tendon treatment. Following title and abstract screening of these search returns, these reviews were evaluated for spin (according to a previously developed classification scheme) and received AMSTAR-2 (A Measurement Tool to Assess Systematic Reviews-2) appraisals by 2 investigators in a masked, duplicate manner. Study characteristics for each review were also extracted in duplicate. RESULTS: Our systematic search returned 251 articles of which 43 systematic reviews and meta-analyses were eligible for data extraction. We found that 65.1% of included studies contained spin (28/43). Spin type 3 was the most common type, occurring in 53.5% (23/43) of abstracts. Spin types 5, 6, 1, and 4 occurred in 16.3% (7/43), 9.3% (4/43), 7% (3/43), and 5.3% (1/43), respectively. Spin types 2, 7, 8, and 9 did not occur. AMSTAR-2 appraised 32.6% (14/43) of the studies as "moderate" quality, 32.6% (14/43) as "low" quality, and 34.9% (15/43) as "critically low" quality. No systematic reviews were rated as "high" quality. There was no significant association between the presence of spin and the following study characteristics: intervention type, article discussing Preferred Reporting Items for Systematic reviews and Meta-Analyses (PRISMA) adherence, journal recommending PRISMA adherence, funding sources, journal 5-year impact factor, year the review was received for publication, or AMSTAR-2 critical appraisals. CONCLUSION: Spin was present in abstracts of systematic reviews and meta-analyses-covering Achilles tendon tear treatment. Steps should be taken to improve the reporting quality of abstracts on Achilles tendon treatment as well as other common orthopedic conditions. CLINICAL RELEVANCE: In order to avoid negative patient outcomes, articles should be free of spin within the abstract.

Femtosecond quantification of void evolution during rapid material failure.

Understanding high-velocity impact, and the subsequent high strain rate material deformation and potential catastrophic failure, is of critical importance across a range of scientific and engineering disciplines that include astrophysics, materials science, and aerospace engineering. The deformation and failure mechanisms are not thoroughly understood, given the challenges of experimentally quantifying material evolution at extremely short time scales. Here, copper foils are rapidly strained via picosecond laser ablation and probed in situ with femtosecond x-ray free electron (XFEL) pulses. Small-angle x-ray scattering (SAXS) monitors the void distribution evolution, while wide-angle scattering (WAXS) simultaneously determines the strain evolution. The ability to quantifiably characterize the nanoscale during high strain rate failure with ultrafast SAXS, complementing WAXS, represents a broadening in the range of science that can be performed with XFEL. It is shown that ultimate failure occurs via void nucleation, growth, and coalescence, and the data agree well with molecular dynamics simulations.

Predicting dwell fatigue life in titanium alloys using modelling and experiment.

Fatigue is a difficult multi-scale modelling problem nucleating from localised plasticity at the scale of dislocations and microstructure with significant engineering safety implications. Cold dwell fatigue is a phenomenon in titanium where stress holds at moderate temperatures lead to substantial reductions in cyclic life, and has been implicated in service failures. Using discrete dislocation plasticity modelling complemented by transmission electron microscopy, we successfully predict lifetimes for 'worst case' microstructures representative of jet engine spin tests. Fatigue loading above a threshold stress is found to produce slip in soft grains, leading to strong dislocation pile-ups at boundaries with hard grains. Pile-up stresses generated are high enough to nucleate hard grain basal dislocations, as observed experimentally. Reduction of applied cyclic load alongside a temperature excursion during the cycle lead to much lower densities of prism dislocations in soft grains and, sometimes, the elimination of basal dislocations in hard grains altogether.

Real-world Independent Testing of e-ASPECTS Software (RITeS): statistical analysis plan.

Background: Artificial intelligence-based software may automatically detect ischaemic stroke lesions and provide an Alberta Stroke Program Early CT score (ASPECTS) on CT, and identify arterial occlusion and provide a collateral score on CTA. Large-scale independent testing will inform clinical use, but is lacking. We aim to test e-ASPECTS and e-CTA (Brainomix, Oxford UK) using CT scans obtained from a range of clinical studies. Methods: Using prospectively collected baseline CT and CTA scans from 10 national/international clinical stroke trials or registries (total >6600 patients), we will select a large clinically representative sample for testing e-ASPECTS and e-CTA compared to previously acquired independent expert human interpretation (reference standard). Our primary aims are to test agreement between software-derived and masked human expert ASPECTS, and the diagnostic accuracy of e-ASPECTS for identifying all causes of stroke symptoms using follow-up imaging and final clinical opinion as diagnostic ground truth. Our secondary aims are to test when and why e-ASPECTS is more or less accurate, or succeeds/fails to produce results, agreement between e-CTA and human expert CTA interpretation, and repeatability of e-ASPECTS/e-CTA results. All testing will be conducted on an intention-to-analyse basis. We will assess agreement between software and expert-human ratings and test the diagnostic accuracy of software.  Conclusions: RITeS will provide comprehensive, robust and representative testing of e-ASPECTS and e-CTA against the current gold-standard, expert-human interpretation.

Ti and its alloys as examples of cryogenic focused ion beam milling of environmentally-sensitive materials.

Hydrogen pick-up leading to hydride formation is often observed in commercially pure Ti (CP-Ti) and Ti-based alloys prepared for microscopic observation by conventional methods, such as electro-polishing and room temperature focused ion beam (FIB) milling. Here, we demonstrate that cryogenic FIB milling can effectively prevent undesired hydrogen pick-up. Specimens of CP-Ti and a Ti dual-phase alloy (Ti-6Al-2Sn-4Zr-6Mo, Ti6246, in wt.%) were prepared using a xenon-plasma FIB microscope equipped with a cryogenic stage reaching -135 °C. Transmission electron microscopy (TEM), selected area electron diffraction, and scanning TEM indicated no hydride formation in cryo-milled CP-Ti lamellae. Atom probe tomography further demonstrated that cryo-FIB significantly reduces hydrogen levels within the Ti6246 matrix compared with conventional methods. Supported by molecular dynamics simulations, we show that significantly lowering the thermal activation for H diffusion inhibits undesired environmental hydrogen pick-up during preparation and prevents pre-charged hydrogen from diffusing out of the sample, allowing for hydrogen embrittlement mechanisms of Ti-based alloys to be investigated at the nanoscale.

Segregation mediated heterogeneous structure in a metastable ß titanium alloy with a superior combination of strength and ductility.

In ß titanium alloys, the ß stabilizers segregate easily and considerable effort has been devoted to alleviate/eliminate the segregation. In this work, instead of addressing the segregation problems, the segregation was utilized to develop a novel microstructure consisting of a nanometre-grained duplex (α+ß) structure and micrometre scale ß phase with superior mechanical properties. An as-cast Ti-9Mo-6W alloy exhibited segregation of Mo and W at the tens of micrometre scale. This was subjected to cold rolling and flash annealing at 820 oC for 2 and 5 mins. The solidification segregation of Mo and W leads to a locally different microstructure after cold rolling (i.e., nanostructured ß phase in the regions rich in Mo and W and plate-like martensite and ß phase in regions relatively poor in Mo and W), which play a decisive role in the formation of the heterogeneous microstructure. Tensile tests showed that this alloy exhibited a superior combination of high yield strength (692 MPa), high tensile strength (1115 MPa), high work hardening rate and large uniform elongation (33.5%). More importantly, the new technique proposed in this work could be potentially applicable to other alloy systems with segregation problems.

Data on a new beta titanium alloy system reinforced with superlattice intermetallic precipitates.

The data presented in this article are related to the research article entitled "a new beta titanium alloy system reinforced with superlattice intermetallic precipitates" (Knowles et al., 2018) [1]. This includes data from the as-cast alloy obtained using scanning electron microscopy (SEM) and x-ray diffraction (XRD) as well as SEM data in the solution heat treated condition. Transmission electron microscopy (TEM) selected area diffraction patterns (SADPs) are included from the alloy in the solution heat treated condition, as well as the aged condition that contained < 100 nm B2 TiFe precipitates [1], the latter of which was found to exhibit double diffraction owing to the precipitate and matrix channels being of a similar width to the foil thickness (Williams and Carter, 2009) [2]. Further details are provided on the macroscopic compression testing of small scale cylinders. Of the micropillar deformation experiment performed in [1], SEM micrographs of focused ion beam (FIB) prepared 2 µm micropillars are presented alongside those obtained at the end of the in-situ SEM deformation as well as videos of the in-situ deformation. Further, a table is included that lists the Schmidt factors of all the possible slip systems given the crystal orientations and loading axis of the deformed micropillars in the solution heat treated and aged conditions.

Data on a Laves phase intermetallic matrix composite in situ toughened by ductile precipitates.

The data presented in this article are related to the research article entitled "Laves phase intermetallic matrix composite in situ toughened by ductile precipitates" (Knowles et al.) [1]. The composite comprised a Fe2(Mo, Ti) matrix with bcc (Mo, Ti) precipitated laths produced in situ by an aging heat treatment, which was shown to confer a toughening effect (Knowles et al.) [1]. Here, details are given on a focused ion beam (FIB) slice and view experiment performed on the composite so as to determine that the 3D morphology of the bcc (Mo, Ti) precipitates were laths rather than needles. Scanning transmission electron microscopy (S(TEM)) micrographs of the microstructure as well as energy dispersive X-ray spectroscopy (EDX) maps are presented that identify the elemental partitioning between the C14 Laves matrix and the bcc laths, with Mo rejected from the matrix into laths. A TEM selected area diffraction pattern (SADP) and key is provided that was used to validate the orientation relation between the matrix and laths identified in (Knowles et al.) [1] along with details of the transformation matrix determined.

Gating the mechanistic pathway to the elusive 4-membered ring azeteoporphyrin.

Photolysis of metalated (Cu and Ni) and free base 2-diazo-3-oxochlorins within a frozen matrix (λ = 457.9 nm, toluene, 80 K) generates a single photointermediate with a hypsochromically shifted electronic absorption spectrum relative to the starting diazochlorins. The appearance of ketene (~2131 cm(-1)) and azete (~1670 cm(-1)) vibrations in infrared absorption and Raman spectra, respectively, identifies this intermediate as resulting from the Wolff rearrangement of the diazochlorins upon N(2) loss. Computational modeling of the vibrational spectra and TDDFT simulation of the electronic transitions of potential photointermediates corroborate this assignment. Isolation and analysis of photoproducts of these diazochlorins formed within n-butanol-doped frozen toluene matrices indicate near exclusive formation of azeteoporphyrins. In sharp contrast, room temperature laser photolysis of these materials yields a mixture of photoproducts deriving from the presence of both carbene and ketene intermediates. Computational modeling of the intramolecular reactivity of the proposed sp(2) carbene intermediate shows exclusive bond insertion to the adjacent phenyl group, and no evidence of Wolff rearrangement. Computational reaction profile analyses reveal that the barrierless Wolff rearrangement proceeds via an out-of-plane carbene electronic configuration that is generated directly during the loss of N(2). The formation of out-of-plane carbene, resulting in the exclusive formation of the observed ketene photointermediate at low temperatures, is consistent with orbital symmetry considerations and by the geometric constraints imposed by the frozen matrix. Combined, this leads to a model showing that azeteoporphyrin formation via the Wolff rearrangement is dependent upon the structural disposition of the adjacent framework, and the specific reaction intermediate formed is very sensitive to this feature.

A geometric switching approach toward thermal activation of metalloenediynes.

Tetradentate metalloenediynes with strong imine and weaker thioether coordination serve as a geometrically non-rigid switch to drive thermal Bergman cyclization.

Reexamination of lead(II) coordination preferences in sulfur-rich sites: implications for a critical mechanism of lead poisoning.

Recent studies suggest that the developmental toxicity associated with childhood lead poisoning may be attributable to interactions of Pb(II) with proteins containing thiol-rich structural zinc-binding sites. Here, we report detailed structural studies of Pb(II) in such sites, providing critical insights into the mechanism by which lead alters the activity of these proteins. X-ray absorption spectroscopy of Pb(II) bound to structural zinc-binding peptides reveals that Pb(II) binds in a three-coordinate Pb(II)-S(3) mode, while Zn(II) is known to bind in a four-coordinate mode in these proteins. This Pb(II)-S(3) coordination in peptides is consistent with a trigonal pyramidal Pb(II)-S(3) model compound previously reported by Bridgewater and Parkin, but it differs from many other reports in the small molecule literature which have suggested Pb(II)-S(4) as a preferred coordination mode for lead. Reexamination of the published structures of these "Pb(II)-S(4)" compounds reveals that, in almost all cases, the coordination number of Pb is actually 5, 6, or 8. The results reported herein combined with this new review of published structures suggest that lead prefers to avoid four-coordination in sulfur-rich sites, binding instead as trigonal pyramidal Pb(II)-S(3) or as Pb(II)-S(5-8). In the case of structural zinc-binding protein sites, the observation that lead binds in a three-coordinate mode, and in a geometry that is fundamentally different from the natural coordination of zinc in these sites, explains why lead disrupts the structure of these peptides and thus provides the first detailed molecular understanding of the developmental toxicity of lead.

9,10-Anthracene dicarboxylate bridged complexes with M2 quadruply bonded dimetal units: [[M2(O2CtBu)3]2(mu-9,10-An(CO2)2)], where M = Mo or W.

From the reactions between [M2(O2CtBu)4] and 9,10-anthracenedicarboxylic acid in toluene, the dicarboxylate bridged complexes [[M2(O2CtBu)3]2(mu-9,10An(CO2)2)], have been obtained as microcrystalline yellow (M = Mo) and red (M = W) powders. The powders are soluble in THF forming intense red (M = Mo) and green (M = W) solutions. The electronic absorption spectra in 2-MeTHF have been recorded as a function of temperature (2-298 K) and show a small bathochromic shift on cooling. The electronic structures have been investigated by molecular orbital calculations employing density functional theory on the model compounds [(HCO2)3M2]2(mu-9,10-An(CO2)2) where the M4 unit is constrained to lie in a plane. These reveal a minimum energy, gas-phase structure wherein the plane of the anthracene is twisted by ca. 54 degrees with respect to its 9,10-carboxylate units for both Mo and W. The results of these calculations are correlated with the electronic absorption spectral data and the electrochemical measurements (CV and DPV) of the first and second oxidation waves. The EPR spectra of the radical cations formed by single-electron oxidation with [Cp2Fe](+)[PF6]- in a THF-CH2Cl2 solvent mixture show that the complexes are valence trapped at ambient temperature on the EPR timescale. These results are discussed in the light of recent studies of dicarboxylate-linked MM quadruple bonds.

Reactivity of the hydrido/nitrosyl radical MHCl(NO)(CO)(P(i)Pr(3))(2), M = Ru, Os.

The reaction of equimolar NO with the 16 electron molecule RuHCl(CO)L(2) (L = P(i)Pr(3)) proceeds, via a radical adduct RuHCl(CO)(NO) L(2), onward to form RuCl(NO)(CO)L(2) (X-ray structure determination) and RuHCl(HNO)(CO)L(2), in a 1:1 mole ratio. The HNO ligand, bound by N and trans to hydride, is rapidly degraded by excess NO. The osmium complex behaves analogously, but the adduct has a higher formation constant, permitting determination of its IR spectrum; both MHCl(CO)(NO)L(2) radicals are characterized by EPR spectroscopy, and DFT calculations on the Ru system show it to have a "half-bent" Ru-N-O unit with the spin density mainly on nitrogen. DFT (PBE) energies rule out certain possible mechanistic steps for forming the two products. A survey of the literature leads to the hypothesis that NO should generally be considered as a (neutral) Lewis base (2-electron donor) when it binds to a 16 electron complex which is resistant to oxidation or reduction, and that the resulting N-centered radical has a M-N-O angle of approximately 140 degrees, which distinguishes it from NO(-) (bent at <140 degrees ) and from NO(+) (>170 degrees ).

An electron-excessive nitrosyl complex: reactivity of a ligand-centered radical leading to coordinated HNO.

The reaction of RuHCl(CO)L(2) (L = P(i)Pr(3)) with NO initially forms a 1:1 adduct, shown by DFT calculations and EPR spectroscopy (including the RuD isotopomer) to contain a bent ( 90 degree angle Ru-N-O = 143.9 degrees ) nitrosyl where the majority of the spin density is on the nitrosyl nitrogen. This radical adduct transforms further to give equimolar RuCl(NO)(CO)L(2) and RuHCl(HNO)(CO)L(2), the latter with hydride trans to the nitroxyl ligand HN=O. This is the first observation of the synthesis of coordinated HNO from NO itself. DFT calculations lead to the proposal that this H-atom transfer is effected by free NO, and the lifetime of RuHCl(HNO)(CO)L(2) is indeed qualitatively dependent on the presence of free NO.