Phosphorus-Ligand Redox Cooperative Catalysis: Unraveling Four-Electron Dioxygen Reduction Pathways and Reactive Intermediates.

The reduction of dioxygen to water is crucial in biology and energy technologies, but it is challenging due to the inertness of triplet oxygen and complex mechanisms. Nature leverages high-spin transition metal complexes for this, whereas main-group compounds with their singlet state and limited redox capabilities exhibit subdued reactivity. We present a novel phosphorus complex capable of four-electron dioxygen reduction, facilitated by unique phosphorus-ligand redox cooperativity. Spectroscopic and computational investigations attribute this cooperative reactivity to the unique electronic structure arising from the geometry of the phosphorus complex bestowed by the ligand. Mechanistic study via spectroscopic and kinetic experiments revealed the involvement of elusive phosphorus intermediates resembling those in metalloenzymes. Our result highlights the multielectron reactivity of phosphorus compound emerging from a carefully designed ligand platform with redox cooperativity. We anticipate that the work described expands the strategies in developing main-group catalytic reactions, especially in small molecule fixations demanding multielectron redox processes.

Arthroscopic assessment for lateral collateral ligament complex deficiency of the elbow: a cadaveric study.

PURPOSE: To evaluate whether elbow instability due to lateral collateral ligament complex injury can be assessed reliably through arthroscopy. METHODS: Eight fresh human cadaveric elbows were placed in a simulated lateral decubitus position. The radiocapitellar joint (RCJ) gap and ulnohumeral joint (UHJ) gap (mm) were measured with different sizes of probes from the posterolateral viewing portal. The elbow was 90 degrees flexed with neutral forearm rotation for RCJ gap measurement and 30 degrees flexed with full supination for UHJ gap measurement. Sequential testing was performed from Stage 0 to Stage 3 (Stage 0: intact; Stage 1: the release of the anterior 1/3 LCL complex; Stage 2: the release of the anterior two thirds of the LCL complex; and Stage 3: the release of the entire LCL complex) on each specimen. The mean gap of RCJ and lateral UHJ was used for the comparison between stages with the intact elbow. RESULTS: The mean RCJ gap distance in Stage 2 and Stage 3 was significantly increased compared to that in Stage 0 (Stage 0 vs. Stage 2: P = .008; Stage 0 vs. Stage 3: P = .010). The mean UHJ gap distance of Stage 1, Stage 2, and Stage 3 was significantly increased compared to that in Stage 0 (Stage 0 vs. Stage 1: P = 0.025; Stage 0 vs. Stage 2: P = .010; Stage 0 vs. Stage 3: P = .011). In contrast, the release of the anterior 1/3 of the LCL complex (Stage 1) was not significantly increased compared to the mean joint gap distance of RCJ (P = .157). CONCLUSION: Arthroscopic measurement of joint gap widening in RCJ and UHJ is a reliable assessment method to detect LCL complex deficiency that involves the anterior two thirds or more.

Biomechanical impact of elbow motion in elbow stiffness.

BACKGROUND: A mechanical block in the elbow due to osteophytes in the olecranon fossa is a common clinical symptom for elbow stiffness. PURPOSE/HYPOTHESIS: This study aims to understand the biomechanical characteristics or changes in the stiff elbow in the resting (or neutral) and swing position of the arm using a cadaveric model. The hypotheses included the following: (1) a difference exists in the articular contact pressure of the elbow by comparing the non-stiff and stiff models in in vivo studies; (2) the degree of stiffness would affect the increase of the joint loading of the elbow. STUDY DESIGN: Controlled laboratory study, cadaveric study. METHODS: Eight fresh-frozen specimens from individuals of both sexes were included in the biomechanical study. The specimen was mounted on a custom-designed jig system with gravity-assisted muscle contracture to mimic the elbow in a standing position. The elbow was tested in two conditions (the resting and passive swing). Contact pressure was recorded for three seconds in the resting position, which was the neutral position of the humerus. By dropping the forearm from 90° of the elbow flexion, the passive swing was performed. The specimens were tested sequentially in three stages of stiffness (stage 0, no stiffness; stage 1, 30° of extension limitation; and stage 2, 60° of extension limitation). After data collection was completed in stage 0, a stiff model was sequentially created for each stage. The stiff model of the elbow was created by blocking the olecranon by inserting a 2.0 K-wire into the olecranon fossa horizontally with the intercondylar axis. RESULTS: The mean contact pressures were 279 ± 23, 302 ± 6, and 349 ± 23 kPa in stages 0, 1, and 2, respectively. The increases in the mean contact pressure in stages 2 versus 0 were significant (P < 0.0001). The mean contact pressures were 297 ± 19, 310 ± 14, and 326 ± 13 kPa in stages 0, 1, and 2, respectively. The peak contact pressures were 420 ± 54, 448 ± 84, and 500 ± 67 kPa in stages 0, 1, and 2, respectively. The increases in mean contact pressure in stage 2 versus 0 were significant (P = 0.039). The increases in peak contact pressure in stages 0 versus 2 were significant (P = 0.007). CONCLUSIONS: The elbow bears the load created by gravity and muscle contracture in the resting and swing motion. Moreover, extension limitation of stiff elbow increases the load bearing in the resting position and swing motion. Careful surgical management should be considered for meticulous clearance of bony spur around olecranon fossa to resolve the extension limitation of the elbow.

The anatomic - magnetic resonance imaging study of distal triceps brachii tendon.

PURPOSE: The study aimed to describe the distal triceps brachii insertion on the olecranon and to correlate the findings with those seen in normal MR (Magnetic Resonance) anatomy of the triceps brachii insertion. MATERIALS AND METHODS: 14 un-paired fresh frozen elbows were included according to the institution guidelines and dissected. Histologic examination was performed to the distal triceps brachii insertion. The dimension of the distal triceps brachii tendon insertion was measured and defined based on its layer. The measurement of distal triceps brachii insertion was performed with image processing program (Image J, National Institute of Health, Bethesda, Maryland). T1-weighted elbow MR images (3.0 T) of a 102 patients were acquired and analyzed according to its sagittal plane. RESULTS: All specimens shows that distal triceps brachii tendon is with three distinct insertional areas in the olecranon which are: (1) capsular, (2) deep muscular, (3) superficial tendinous insertion with the areas of 80.7 mm2, 56.4 mm2, and 175.2 mm2, respectively. The superficial tendinous insertion was observed with a thickened portion, the "central cord" with 0.5 occupation ratio. MR analysis showed that 30% (31/102) of the distal biceps brachii insertion was with a cleft between the bipartite insertion of the superficial tendinous and the deep muscular insertion on olecranon which designated as the "lacuna" which was also found in 35% (5/14) of the specimens. CONCLUSIONS: The distal triceps brachii has three distinct insertion on the olecranon. The superficial tendinous layer was separated with the deep muscular layer by a cleft in one third of the cases. Knowledge of this anatomy will help surgeon to understand the partial triceps injury and to avoid iatrogenic injury to the distal triceps tendon during surgery.

Bicipital origin and the course of the plantaris muscle.

The plantaris muscle (PM) has a small fusiform muscle belly and a long slender tendon sandwiched between the soleus (SM) and gastrocnemius muscle (GM). During routine dissection for research, an additional PM in the popliteal region of a 75-year-old Korean female was discovered. Two distinct PMs were present, the superior PM (sPM) and inferior PM (iPM). While the sPM originates from the lower lateral supracondylar ridge and the knee capsule, the iPM originates from the femoral condyle and sPM tendon splitting into two parts at the distal belly. The lateral side of the iPM tendon travels between GM and SM and ends at the calcaneal tendon. sPM and the medial side of the iPM tendon run along with the sPM tendon and inserts at the fascia at the inner surface of proximal 1/3 of the medial head of GM. This case report introduces a new variation of the PM that should be taken into consideration.

Unsupervised Monocular Depth Estimation for Colonoscope System Using Feedback Network.

A colonoscopy is a medical examination used to check disease or abnormalities in the large intestine. If necessary, polyps or adenomas would be removed through the scope during a colonoscopy. Colorectal cancer can be prevented through this. However, the polyp detection rate differs depending on the condition and skill level of the endoscopist. Even some endoscopists have a 90% chance of missing an adenoma. Artificial intelligence and robot technologies for colonoscopy are being studied to compensate for these problems. In this study, we propose a self-supervised monocular depth estimation using spatiotemporal consistency in the colon environment. It is our contribution to propose a loss function for reconstruction errors between adjacent predicted depths and a depth feedback network that uses predicted depth information of the previous frame to predict the depth of the next frame. We performed quantitative and qualitative evaluation of our approach, and the proposed FBNet (depth FeedBack Network) outperformed state-of-the-art results for unsupervised depth estimation on the UCL datasets.

Capturing the Complete Reaction Profile of a C-H Bond Activation.

The activation of C-H bonds requires the generation of extremely reactive species, which hinders the study of this reaction and its key intermediates. To overcome this challenge, we synthesized an iron(III) chloride-pyridinediimine complex that generates a chlorine radical proximate to reactive C-H bonds upon irradiation with light. Transient spectroscopy confirms the formation of a Cl·|arene complex, which then activates C-H bonds on the PDI ligand to yield HCl and a carbon-centered radical as determined by photocrystallography. First-principles molecular dynamics-density functional theory calculations reveal the trajectory for the formation of a Cl·|arene intermediate. Together, these experimental and computational results show the complete reaction profile for the preferential activation of a C-H bond in the solid state.

Anatomic, histologic, and ultrasound analyses of the dorsum of the hand for volumetric rejuvenation.

BACKGROUND: Volumetric rejuvenation of the dorsum of the hand with fat grafting or injectable fillers has increased in popularity in recent years. It has become widely accepted that the dorsum of the hand contains three fatty laminae: superficial, intermediate, and deep laminae. The dorsal venous plexus and dorsal cutaneous nerves are known to reside in the dorsal intermediate lamina. However, the superficial vein and cutaneous nerve might not be located in the same layer of subcutaneous tissue, as is the case in other body regions. MATERIALS AND METHODS: Eight hands were dissected in a layer-by-layer fashion from the skin to the extensor tendons. In another 13 hands from among 21 investigated cadavers, samples from the dorsum of the hand were harvested and stained using trichrome stains for histologic analysis. B-mode ultrasound was also performed for identifying structures of the dorsum of the hand. RESULTS: Anatomic dissection and histologic analysis of the dorsum of the hand revealed the presence of an unknown fascia in addition to the three known fascial layers. The additional fascia was located in the dorsal intermediate lamina and separated it into two compartments: one containing the dorsal venous plexus superficially and the other containing the dorsal cutaneous nerves deeply. Ultrasound showed corresponding structures including three hyperechoic fascial layers, three hypoechoic laminae, and additional hyperechoic fascia in dorsal intermediate lamina. CONCLUSIONS: Accurate anatomic knowledge of the dorsum of the hand will help practitioners determine the optimal and safe locations for performing fat grafting and injecting dermal fillers.

Enthalpy-Controlled Insertion of a "Nonspectator" Tricoordinate Phosphorus Ligand into Group 10 Transition Metal-Carbon Bonds.

Insertion of a tricoordinate phosphorus ligand into late metal-carbon bonds is reported. Metalation of a P^P-chelating ligand (L1), composed of a nontrigonal phosphorous (i.e., P(III)) triamide moiety, P(N(o-N(Ar)C6H4)2, tethered by a phenylene linker to a -PiPr2 anchor, with group 10 complexes L2M(Me)Cl (M = Ni, Pd) results in insertion of the nontrigonal phosphorus site into the metal-methyl bond. The stable methylmetallophosphorane compounds thus formed are characterized spectroscopically and crystallographically. Metalation of L1 with (cod)PtII(Me)(Cl) does not lead to a metallophosphorane but rather to the standard bisphosphine chelate (κ2-L1)Pt(Me)(Cl). These divergent reactivities within group 10 are rationalized by reference to periodic variation in M-C bond enthalpies.

High-Frequency and -Field EPR (HFEPR) Investigation of a Pseudotetrahedral CrIV Siloxide Complex and Computational Studies of Related CrIVL4 Systems.

Chromium species are the active sites in a variety of heterogeneous catalysts, such as the Phillips catalyst, which is composed of Cr ions supported by SiO2 and is used to produce polyethylene. Among the catalytically relevant oxidation states of chromium is CrIV. Families of neutral, homoleptic, four-coordinate complexes, CrL4, with a variety of monoanionic, monodentate ligands, such as L = alkyls, aryls, amides, ketimides (R2C = N-), alkoxides, and siloxides, are available and can provide information regarding Cr sites in heterogeneous materials. For example, the previously reported siloxide, Cr(DTBMS)4, where DTBMS = -OSiMe tBu2 (di- tert-butylmethylsiloxide), may be considered a molecular analogue of CrIV supported by SiO2. Such CrL4 complexes can have either a singlet ( S = 0) or triplet ( S = 1) spin ground state, and the spin state preferences of such complexes are not fully understood. A truly tetrahedral d2 S = 1 complex would exhibit no zero-field splitting (zfs), and the zfs is indeed small and observable by X-band EPR for several CrR4 and Cr(OR)4 complexes. In contrast, Cr(DTBMS)4 has zfs beyond the range amenable to X-band EPR so that high-frequency and high-field EPR (HFEPR) is appropriate. HFEPR of Cr(DTBMS)4 in the solid state shows the presence of three very similar triplet species with the major component having D = +0.556 cm-1. Classical ligand-field theory (LFT) and quantum chemical theory (QCT), including ab initio methods, use EPR and electronic absorption spectra to give a complete picture of the electronic structure of Cr(DTBMS)4, and other complexes of formula Cr(ER n)4, E = C, n = 3; E = N, n = 2; E = O, n = 1; E = F, n = 0. Computations show the importance of ligand steric bulk and of π-bonding in controlling the subtleties of electronic structure of CrL4 species. These electronic structure results, including zfs, which is a measure of excited state accessibility, for both triplet and singlet excited states, might be related to the catalytic activity of paramagnetic Cr species.

Transnasal Placement of a Balloon-Expandable Metallic Stent: Human Cadaver Study of the Eustachian Tube.

PURPOSE: To investigate the technical feasibility of stent placement in the cartilaginous portion of the Eustachian tube (ET). MATERIALS AND METHODS: Twelve ETs of 6 cadavers were used. Two different-sized stents were placed on either the right (2.5 mm in diameter) or left (3.5 mm in diameter) side of the ET. The procedural feasibility was assessed by subtraction Eustachian tubography, computed tomography before and after the procedure, and fluoroscopic and endoscopic images. The stent location, inner luminal diameter of the stented ET, radiation dose, procedural time, and fluoroscopy time were analyzed. RESULTS: Stent placement was successful in 11 of 12 cadaveric specimens without procedure-related complications. In the 1 specimen, the balloon catheter with crimped stent was passed into the bony canal of the ET without any resistance. The distal end of the stent was located in the middle ear cavity. Stents were located within the cartilaginous portion of the ET (n = 1), the proximal tip bridging the nasopharyngeal orifice of the ET (n = 5), or the proximal end of the stent protruded from the tubal orifice (n = 5). The mean luminal diameter in the outer segment was significantly smaller than in the middle (P < .001) and inner (P < .001) segments. The mean procedure time was 128 ± 37 seconds. The mean radiation dose and fluoroscopy time of each cadaver were 3235.4 ± 864.8 cGy/cm2 and 139 ± 49 seconds, respectively. CONCLUSIONS: Stent placement of the ET under endoscopic and fluoroscopic guidance is technically feasible in a human cadaver model.

Anatomical popliteal artery entrapment syndrome.

PURPOSE: The aim of this study was to analyze anatomical popliteal artery entrapment syndrome (PAES) and to individualize the treatment of this condition according to the anatomical status of the artery and the adjacent structure. METHODS: A total of 35 anatomical PAES legs in 23 consecutive patients treated within the Asan Medical Center, Seoul, Korea between 1995 and 2011 were analyzed retrospectively. Anatomical PAES was diagnosed by MRI and/or CT scans of the knee joint, and CT or conventional transfemoral arteriography of the lower extremities. RESULTS: We noted a type II gastrocnemius medial head (GNM) anomaly, a type III GNM anomaly, or an aberrant plantaris muscle in 51.4%, 20%, and 28.6% of PAES legs, respectively. In assessments of the arterial lesions, popliteal or tibial artery occlusion was noted in 19 of 26 symptomatic PAES legs. For cases without popliteal artery lesions, myotomy of the anatomically deranged muscle was performed in 5 of 7 symptomatic and 4 of 9 asymptomatic PAES legs. For occluded popliteal arteries, we performed ten direct repairs of the pathological popliteal artery and 4 femoro-below the knee popliteal bypass surgeries. As a result of the arterial Surgery, 9 direct procedures with myotomy yielded a patent artery, while 3 graft failures were noted in the bypass group. The median follow-up period was 84 months (range, 12-206 months). CONCLUSION: We recommend that treatment of PAES should be individualized based on pathology, symptoms, and various imaging studies.

Halogen Photoelimination from SbV Dihalide Corroles.

Main-group p-block metals are ideally suited for mediating two-electron reactions because they cycle between M n and M n+2 redox states, as the one-electron state is thermodynamically unstable. Here, we report the synthesis and structure of an SbIII corrole and its SbVX2 (X = Cl, Br) congeners. SbIII sits above the corrole ring, whereas SbV resides in the corrole centroid. Electrochemistry suggests interconversion between the SbIII and SbVX2 species. TD-DFT calculations indicate a HOMO → LUMO+2 parentage for excited states in the Soret spectral region that have significant antibonding character with respect to the Sb-X fragment. The photochemistry of 2 and 3 in THF is consistent with the computational results, as steady-state photolysis at wavelengths coincident with the Soret absorption of SbVX2 corrole lead to its clean conversion to the SbIII corrole. This ability to photoactivate the Sb-X bond reflects the proclivity of the pnictogens to rely on the PnIII/V couple to drive the two-electron photochemistry of M-X bond activation, an essential transformation needed to develop HX-splitting cycles.

Fluoroscopic subtraction Eustachian tubography: initial feasibility test in a cadaver model.

OBJECTIVES: To evaluate the technical feasibility of direct Eustachian tube catheterisation and subtraction Eustachian tubography in a cadaver model. METHODS: A total of 12 separate sessions were performed on both sides of the Eustachian tube (ET) in six human cadavers. Cadavers were positioned for the submentovertical view on a fluoroscopy table. Endoscopy-guided ET selection was used in the first three cadavers, whereas fluoroscopy-guided ET selection was used in the remaining three. Eustachian tubography was performed by injecting 2 ml of contrast media through a 5-Fr catheter. We recorded the success of ET selection, number of attempts, procedure time, and tubography quality using native and subtraction images (range, 0-3). RESULTS: Both endoscopy- and fluoroscopy-guided selections were successfully performed in five of six sessions (83.3%). There were no statistically significant differences between the endoscopy- and fluoroscopy-guided procedures in terms of the number of attempts, procedure time, rate of immediate contrast leak to the middle ear cavity, and quality of tubography (p > 0.05). An excellent quality of tubography was obtained in 83.3% (10 of 12 sessions) of subtraction images and in 33.3% (4 of 12 sessions) of native images. The tubography quality score was significantly higher for the subtraction images than for the native images (p = 0.04). CONCLUSION: Subtraction Eustachian tubography using direct catheterisation seems to be technically feasible. The entire ET can be well visualised; thus, this technique can be used as a simple tool for assessment of ET function and anatomy. KEY POINTS: • Direct catheterisation of the Eustachian tube is technically feasible. • The entire Eustachian tube could be well visualised by direct Eustachian tubography. • Subtraction Eustachian tubography images have better image quality than native images. • Subtraction Eustachian tubography can provide objective assessment of ET function and anatomy.

Scalable Syntheses of 4-Substituted Pyridine-Diimines.

A concise benchtop and scalable synthesis of pyridine-diimine (PDI) ligand frameworks is presented using inexpensive commercial starting materials as opposed to previous syntheses of these ligands, which have confronted long and tedious routes that employ toxic and often difficult to scale pyrophoric reagents. The streamlined synthesis is derived from the facile delivery of 4-functionalized diacetylpyridines from a Minisci reaction using pyruvic acid, silver nitrate, and persulfate. As the PDI ligand scaffold has been adopted for a range of catalytic applications, the ability to modulate the electronic properties of the ligand with facility may be useful for optimizing a variety of catalytic transformations.

Slow Magnetic Relaxation in Intermediate Spin S = 3/2 Mononuclear Fe(III) Complexes.

Magneto-structural correlation studies of mononuclear intermediate S = 3/2 Fe(III) complexes, (PMe3)2FeCl3 (1) and (PMe2Ph)2FeCl3 (2), demonstrate the influence of local symmetry on magnetic anisotropy. Symmetric compound 1 is characterized by a zero-field splitting (ZFS) parameter of D = -50(2) cm-1, leading to the observation of slow magnetic relaxation with an energy barrier of 81 cm-1 along with magnetic hysteresis up to 4 K, whereas symmetrically perturbed compound 2 displays a much reduced ZFS parameter of D = -17(1) cm-1 and energy barrier of Ueff = 46 cm-1.

Macroscopic Innervation of the Dura Mater Covering the Middle Cranial Fossa in Humans Correlated to Neurovascular Headache.

The trigeminovascular system within the cranial dura mater is a possible cause of headaches. The aim of this study is to investigate macroscopically dural innervation around the middle meningeal artery (MMA) in the middle cranial fossa. Forty-four sides of the cranial dura overlying the skull base obtained from 24 human cadavers were stained using Sihler's method. Overall, the nervus spinosus (NS) from either the maxillary or mandibular trigeminal divisions ran along the lateral wall of the middle meningeal vein rather than that of the MMA. Distinct bundles of the NS running along the course of the frontal branches of the MMA were present in 81.8% of cases (N = 36). Others did not form dominant nerve bundles, instead giving off free nerve endings along the course of the MMA or dural connective tissue. The distribution of these nerve endings was similar to that of the course of the frontal, parietal and petrosal branches of the MMA (11.4%). The others were not restricted to a perivascular plexus, crossing the dural connective tissues far from the MMA (6.8%). These findings indicate that the NS generally travels alongside the course of the frontal branches of the MMA and terminates in the vicinity of the pterion.

Stereoelectronic Effects in Cl2 Elimination from Binuclear Pt(III) Complexes.

Halogen photoelimination is the critical energy-storing step of metal-catalyzed HX-splitting photocycles. Homo- and heterobimetallic Pt(III) complexes display among the highest quantum efficiencies for halogen elimination reactions. Herein, we examine in detail the mechanism and energetics of halogen elimination from a family of binuclear Pt(III) complexes featuring meridionally coordinated Pt(III) trichlorides. Transient absorption spectroscopy, steady-state photocrystallography, and far-infrared vibrational spectroscopy suggest a halogen elimination mechanism that proceeds via two sequential halogen-atom-extrusion steps. Solution-phase calorimetry experiments of the meridional complexes have defined the thermodynamics of halogen elimination, which show a decrease in the photoelimination quantum efficiency with an increase in the thermochemically defined Pt-X bond strength. Conversely, when compared to an isomeric facial Pt(III) trichloride, a much more efficient photoelimination is observed for the fac isomer than would be predicted based on thermochemistry. This difference in the fac vs mer isomer photochemistry highlights the importance of stereochemistry on halogen elimination efficiency and points to a mechanism-based strategy for achieving halogen elimination reactions that are both efficient and energy storing.

Superior Cervical Sympathetic Ganglion: Normal Imaging Appearance on 3T-MRI.

OBJECTIVE: To identify superior cervical sympathetic ganglion (SCSG) and describe their characteristic MR appearance using 3T-MRI. MATERIALS AND METHODS: In this prospective study, we recruited 53 consecutive patients without history of head and neck irradiation. Using anatomic location based on literature review, both sides of the neck were evaluated to identify SCSGs in consensus. SCSGs were divided into definite (medial to internal carotid artery [ICA] and lateral to longus capitis muscle [LCM]) and probable SCSGs based on relative location to ICA and LCM. Two readers evaluated signal characteristics including intraganglionic hypointensity of all SCSGs and relative location of probable SCSGs. Interrater and intrarater agreements were quantified using unweighted kappa. RESULTS: Ninety-one neck sites in 53 patients were evaluated after exclusion of 15 neck sites with pathology. Definite SCSGs were identified at 66 (73%) sites, and probable SCSGs were found in 25 (27%). Probable SCSGs were located anterior to LCM in 16 (18%), lateral to ICA in 6 (7%), and posterior to ICA in 3 (3%). Intraganglionic hypointensity was identified in 82 (90%) on contrast-enhanced fat-suppressed T1-weighted images. There was no statistical difference in the relative location between definite and probable SCSGs of the right and left sides with intragnalionic hypointensity on difference pulse sequences. Interrater and intrarater agreements on the location and intraganglionic hypointensity were excellent (κ-value, 0.749-1.000). CONCLUSION: 3T-MRI identified definite SCSGs at 73% of neck sites and varied location of the remaining SCSGs. Intraganglionic hypointensity was a characteristic feature of SCSGs.

Trap-Free Halogen Photoelimination from Mononuclear Ni(III) Complexes.

Halogen photoelimination reactions constitute the oxidative half-reaction of closed HX-splitting energy storage cycles. Here, we report high-yielding, endothermic Cl2 photoelimination chemistry from mononuclear Ni(III) complexes. On the basis of time-resolved spectroscopy and steady-state photocrystallography experiments, a mechanism involving ligand-assisted halogen elimination is proposed. Employing ancillary ligands to promote elimination offers a strategy to circumvent the inherently short-lived excited states of 3d metal complexes for the activation of thermodynamically challenging bonds.