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International audience; A porous Ru nanomaterial exhibits high electrocatalytic performance and excellent durability for the hydrogen evolution reaction (HER) under both acidic and neutral conditions. It displays a low overpotential of 83 mV at a current density of 10 mA cm-2 and an excellent durability up to 12 h in 0.5 M H2SO4.

A RuII-pentadentate polypyridyl complex [RuII(κ-N5-bpy2PYMe)Cl]+ (1+, bpy2PYMe = 1-(2-pyridyl)-1,1-bis(6–2,2′-bipyridyl)ethane) and its aqua derivative [RuII(κ-N5-bpy2PYMe)(H2O)]2+ (22+) were synthesized and characterized by experimental and computational methods. In MeOH, 1+ exists as two isomers in different proportions, cis (70%) and trans (30%), which are interconverted under thermal and photochemical conditions by a sequence of processes: chlorido decoordination, decoordination/recoordination of a pyridyl group, and chlorido recoordination. Under oxidative conditions in dichloromethane, trans-12+ generates a [RuIII(κ-N4-bpy2PYMe)Cl2]+ intermediate after the exchange of a pyridyl ligand by a Cl– counterion, which explains the trans/cis isomerization observed when the system is taken back to Ru(II). On the contrary, cis-12+ is in direct equilibrium with trans-12+, with absence of the κ-N4-bis-chlorido RuIII-intermediate. All these equilibria were modeled by density functional theory calculations. Inter...

The classical recommendation for paramedian approaches is needle insertion 1-2 cm paramedian and an angle of 10°-15° medial-cephalad to the plane of the back, but contact with vertebrae is frequent. A mathematical approach to individualizing punctures is proposed on the basis of skin-dural sac distance (d): Optimal angle ∼ inverse cosine [d/ √(1+d^2) ] and the distance covered by the needle ∼ √(1+d^2) for 1 cm paramedian punctures. The inferred angles were compared to optimal angles leading to the central dorsal part of the dural sac from 1 to 2 cm paramedian, measured by Magnetic Resonance Imaging (MRI) in seven cases and in a short stature volunteer (1.58 m, Body Mass Index (BMI) 23.2), to study supine and fetal positions using both closed MR and ultrasound. The average (d) decreased rostrally [6.8 cm (L4-L5)-4.3 cm (T11-T12)] while the mean optimal incidence angles increased [8.3°-16.5° (L4-L5) to 12.7°-24.1° (T11-T12) at 1-2 cm paramedian, respectively] and coincided with the estimated angles with a correlation coefficient = 0.98. In the volunteer, the optimal lateromedial angles increased from 14.4° to 26.7° (L3-L4) to 17.1°-30.3° (T11-T12) for a (d) = 3.7 cm (L3-L4)-3.1 cm (T11-T12) and increased ≤3.7° and ≤5.1° at 1 and 2 cm paramedian, respectively, in fetal positions in MR. Ultrasound yielded comparable figures. The range of possible angles for dural punctures is wider at 1 cm paramedian in lower approaches in lateral decubitus [from 3.6° at T12L1 (12.2°-15.8°) to 9° at L3L4 (8.8°-18.7°)]. The classically recommended angles of 10°-15° differ from the optimal angles, particularly in small patients, suggesting the need for ultrasound guidance or for inferring angles prior to spinal anesthesia. Clin. Anat. 29:1046-1052, 2016. © 2016 Wiley Periodicals, Inc.

Resumen Objetivos La artroplastia total de rodilla (ATR) presenta una elevada tasa transfusional. En nuestro protocolo, indicamos el empleo del recuperador de drenajes postoperatorios (RDPO) en los pacientes con contraindicacion al acido tranexamico. Analizamos el efecto de los RDPO respecto la tasa transfusional y sus costes en pacientes intervenidos de ATR. Material y metodos Se incluyeron prospectivamente 518 pacientes. De ellos, 434 recibieron acido tranexamico y en 84 se contraindico. Calculamos la masa eritrocitaria, el volumen sanguineo y el porcentaje de volumen sanguineo perdido. Controlamos las incidencias asociadas al uso del recuperador y la tasa de transfusion. Realizamos un analisis de costes asociados a los metodos de prevencion de transfusion alogenica. Resultados En 10 de los 84 pacientes no candidatos a acido tranexamico no colocamos el RDPO. En los 74 en los que colocamos un RDPO, reinfundimos 158 ± 72 ml de masa eritrocitaria. La tasa de transfusion alogenica fue del 36%, y en los que no se coloco, del 52%. Con el empleo de RDPO el riesgo relativo de transfusion se situo en el 0,69 (0,41-1,16), con una reduccion de riesgo absoluto del 16% (−8,-40%). El numero de pacientes a tratar para evitar una transfusion alogenica fue de 7. Los costes tangibles directos para evitar una transfusion alogenica se situo en 1.610 €. No observamos complicaciones asociadas a la reinfusion de la sangre recuperada. Conclusiones El empleo de RDPO tras ATR precisa de su empleo en 7 pacientes para evitar una transfusion alogenica, con un coste mas de 10 veces superior al del concentrado alogenico.

Objectives Total knee arthroplasty (TKA) has a high transfusion rate. In our protocol, the use of postoperative cell salvage is indicated in patients with contraindications to tranexamic acid (TA). An analysis was performed on the effect of post-operative cell salvage (POCS) regarding transfusion rate and costs in patients undergoing TKA. Material and methods A prospective analysis was conducted on 518 patients, of whom 434 received TA, and 84 were contraindicated. The red cell mass, blood volume, and the percentage of lost blood volume were calculated. Incidents associated with the use of post-operative re-perfusion of drained blood and the rate of transfusion were recorded. An analysis was performed on the costs associated with allogeneic transfusion prevention methods. Results A POCS drain was not inserted in 10 out of the 84 patients not candidates for TA. In the 74 in which it was placed, 158 ± 72 ml of red cell mass was reinfused. The allogeneic transfusion rate was 36%, and was 52% in those with no drain inserted. Relative risk of transfusion using POCS was 0.69 (0.41 to 1.16) with an absolute risk reduction of 16% (−8 to 40%). The number needed to treat to avoid allogeneic transfusion was 7. The direct costs to avoid allogeneic transfusion were €1610. No complications associated with blood re-infusion were observed. Conclusions The use of POCS would be required in 7 patients after TKA to avoid one allogeneic transfusion with a cost over 10 times that of a transfusion of red cell concentrates.

GDP per capita and household survey means present conflicting pictures of the rate of economic development in emerging countries. One of the areas in which the national accounts–household surveys debate is key is the measurement of developing world poverty. We propose a data-driven method to assess the relative quality of GDP per capita and survey means by comparing them to the evolution of satellite-recorded nighttime lights. Our main assumption, which is robust to a variety of specification checks, is that the measurement error in nighttime lights is unrelated to the measurement errors in either national accounts or survey means. We obtain estimates of weights on national accounts and survey means in an optimal proxy for true income; these weights are very large for national accounts and very modest for survey means. We conclusively reject the null hypothesis that the optimal weight on surveys is greater than the optimal weight on national accounts, and we generally fail to reject the null hypothesis that the optimal weight on surveys is zero. Additionally, we provide evidence that national accounts are good indicators of desirable outcomes for the poor (such as longer life expectancy, better education and access to safe water), and we show that surveys appear to perform worse in developing countries that are richer and that are growing faster. Therefore, we interpret our results as providing support for estimates of world poverty that are based on national accounts.

To the Editor We read with great interest the brief technical report by Elsharkawy et al [1][1] titled ‘Cervical erector spinae plane block: a cadaver study’. The authors elegantly described the spread of Indian ink into C5-7 brachial ventral roots after injections C6-7 transverse process (TP)

There is an urgent need to transition from fossil fuels to solar fuels — not only to lower CO2 emissions that cause global warming but also to ration fossil resources. Splitting H2O with sunlight emerges as a clean and sustainable energy conversion scheme that can afford practical technologies in the short-to-mid-term. A crucial component in such a device is a water oxidation catalyst (WOC). These artificial catalysts have been developed mainly over the past two decades, which is in contrast to nature’s WOCs, which have featured in its photosynthetic apparatus for more than a billion years. Recent times have seen the development of increasingly active molecular WOCs, the study of which affords an understanding of catalytic mechanisms and decomposition pathways. This Perspective offers a historical description of the landmark molecular WOCs, particularly ruthenium systems, that have guided research to our present degree of understanding. Water oxidation catalysts are key components in water-splitting devices that synthesize fuels by using energy, including that from sunlight. This Perspective presents historical developments in molecular water oxidation catalysis, emphasizing studies of ruthenium complexes that have taught us how to design optimal catalysts.

The fascia iliaca compartment is the compartment confined by the fascia iliaca (FI) and a muscular layer formed by the iliac- and psoas muscle. This compartment creates a virtual tunnel that contains the femoral nerve (FN), the obturator nerve (ON), and the lateral femoral cutaneous nerve (LFCN) of the lumbar plexus. In this pilot study, we aimed to determine the suggested volume needed to reach the three target nerves of the lumbar plexus (FN, ON, and LFCN) with a single-injection ultrasound-guided supra-inguinal fascia iliaca compartment (S-FICB). A computer tomography (CT scan)-guided step-up/step-down sequence was used to determine the suggested injection volume to target all three nerves. Subsequently, an anatomist blinded for the injected volume and CT findings, dissected the cadavers, and evaluated the spread of dye underneath the fascia iliaca. In total, seven pelvic areas of four cadavers were evaluated on CT scan and dissected. Distribution of dye underneath the FI in relation to the FN, ON, and the LFCN was recorded in all dissected cadavers. Combining CT and dissection findings, the suggested volume to reach the FN, ON, and LFCN with an S-FICB was 40 mL. ispartof: Journal of Anesthesia vol:32 issue:6 pages:1-6 ispartof: location:Japan status: Published online

To the editor, We read with great interest the article of Magazzeni et al [1][1] concerning ultrasound-guided selective block of the medial brachial cutaneous and the intercostobrachial nerve described to improve tourniquet tolerance. This is a classic indication in regional anesthesia to

To the Editor, We have recently described and evaluated a new marker to study the spread of an injected solution in neural compartments after simulating a routine ultrasound-guided anesthetic block.[1][1] This marker is diluted heparanized blood (DHB) that does not migrate through the epimysium

Cobalt nanoparticles (NPs) have been prepared by hydrogenation of the organometallic complex [Co(η 3 -C 8 H 13 )(η 4 -C 8 H 12 )] in 1-heptanol in the absence of any other stabilizer and then transformed into Co 3 O 4 NPs using mild oxidative reaction conditions. After deposition onto glassy carbon rotating disk electrodes, the electrocatalytic performance of the Co 3 O 4 NPs in water oxidation has been tested in 1M NaOH. The activity has been benchmarked with that of state-of-the-art Co 3 O 4 NPs through electrochemically-active surface area (ECSA) and specific current density measurements. Furthermore, the covalent grafting of photosensitive polypyridyl-based Ru II complexes onto the surface of Co 3 O 4 NPs afforded hybrid nanostructured materials able to photo-oxidize water into O 2 , while steady-state and time-resolved spectroscopic measurements gave some further insight into kinetics and pertinent reaction steps following excitation. These first-row transition metal oxide hybrid nanocatalysts display better catalytic performance than simple mixtures of non-grafted photosensitizers and Co 3 O 4 NPs, thus evidencing the advantage of the direct coupling between the two entities for the photo-induced water oxidation reaction.

Introduction: Ambulatory surgery is associated with lower costs, but there is lack of evidence of the safety for ambulatory vascular access surgery. The objective of this study is to substantiate the safety and effectiveness of performing vascular access surgery in an ambulatory setting. Methods: A review of our prospectively maintained database including all vascular access open surgeries (creations and repairs) performed by our Vascular Access Unit between 2013 and 2017 was compiled. Patient comorbidities, surgery details, hospital admission conditions, and 1-week and 1-month follow-up patency and complications (death, infection, bleeding, and readmission/reintervention) were scrutinized. Results: In the last 5 years, 1414 vascular access procedures were performed (67.8% access creations, 32.2% previous access repairs) in 1012 patients. Most surgeries were performed under local anesthesia (59.2%) or axillary plexus block (38.4%) and mainly in an ambulatory setting, without overnight hospital stays (90.9%). During the first postoperative week follow-up, 9 cases (0.6%) needed readmission or reintervention; significant infection materialized in 11 (0.8%) and 10 cases (0.7%) showed noteworthy hematoma or bleeding, only three (0.2%) requiring reintervention. The primary composite endpoint of 24-h death and 1 week readmission, reintervention, infection, or bleeding was 1.9% (27 cases); 1-month access failure was 6.2%. After univariate analysis, ambulatory settings were not related to higher rates of complications or readmissions. Conclusion: Arteriovenous access surgery can be safely performed in an ambulatory setting, in spite of complex cases, comorbidities, or the increasing implementation of axillary plexus blocks. Surgical results and patency are good, and complications necessitating readmission remain very low.

Recent anatomical discoveries indicate the importance of identifying membranes and compartments surrounding peripheral nerves into which local anesthetic agents can be injected and continuous nerve block catheters placed during regional anesthetic procedures. However, current markers used in anatomical studies have multiple drawbacks, specifically extravasation into noninjected locations, which can result in inadequate treatment. We studied a readily-available new marker, heparinized blood solution (HBS), which is easy to identify by microscopy and can remain in the nerve compartment into which it is deposited without distorting the tissue. We collected blood from 22 patients and prepared it as HBS. This was then injected into four fresh cadavers as in routine clinical practice for ultrasound-guided nerve blocks to form a so-called "doughnut" by "hydro-dissecting" at 32 sites. All samples, including nerves and neighboring tissues, were then prepared and examined by light microscopy. Although no deliberate intraneural injection was attempted, the marker was identified inside all the nerve compartments except the fascicles. Apart from leaking through the needle entry site in some instances, there was no extravasation of the HBS into neighboring nerve compartments in either direction. The tissues were not distorted and the erythrocytes did not form a thrombus. Nerve membranes and compartments could be clearly identified with routine staining. This technique enabled us to study the longitudinal and circumferential spread in all nerve compartments and to collect data for better interpretation of factors influencing an anesthetic nerve block and situations in which complications could possibly arise. HBS seemed superior to other markers because it did not leave the compartments into which it had been injected, did not distort the tissue, and was easily visible under the light microscope. Clin. Anat., 31:1050-1057, 2018. © 2018 Wiley Periodicals, Inc.

In this work we lay out design guidelines for catalytically more efficient organic photocathodes achieving stable hydrogen production in neutral pH. We propose an organic photocathode architecture employing a NiO hole selective layer, a PCDTBT:PCBM bulk heterojunction, a compact TiO2 electron selective contact and a RuO2 nanoparticle catalyst. The role of each layer is discussed in terms of durability and function. With this strategically designed organic photocathode we obtain stable photocurrent densities for over 5 h and discuss routes for further performance improvement.

The Ru complex [RuII (bda-κ-N2 O2 )(N-NH2 )2 ] (1; bda2- =2,2'-bipyridine-6,6'-dicarboxylate, N-NH2 =4-(pyridin-4-yl)aniline) was used as a synthetic intermediate to prepare new RuII and RuIII bda complexes that contain NO+ , MeCN, or H2 O ligands. In acidic solution complex 1 reacts with an excess of NO+ (generated in situ from sodium nitrite) to form a new Ru complex in which the aryl amine ligand N-NH2 is transformed into a diazonium salt [N-N2+ =4-(pyridin-4-yl)benzenediazonium)] together with the formation of a new Ru(NO) moiety in the equatorial zone, to generate [RuII (bda-κ-N2 O)(NO)(N-N2 )2 ]3+ (23+ ). Here the bda2- ligand binds in a κ-N2 O tridentate manner with a dangling carboxylate group. Similarly, complex 1 can also react with a coordinating solvent, such as MeCN, at room temperature to give [RuII (bda-κ-N2 O)(MeCN)(N-NH2 )2 ] (3). In acidic aqueous solutions, a related reaction occurs in which solvent water coordinates to the Ru center to form {[RuII {bda-κ-(NO)3 }(H2 O)(N-NH3 )2 ](H2 O)n }2+ (42+ ) and is strongly hydrogen-bonded with additional water molecules in the second coordination sphere. Furthermore, under acidic conditions the aniline ligands are also protonated to form the corresponding anilinium cationic ligands N-NH3+ . Additionally, the one-electron oxidized complex {[RuIII {bda-κ-(NO)3.5 }(H2 O)(N-NH3 )2 ](H2 O)n }3+ (53+ ) was characterized, in which the fractional value in the κ notation indicates the presence of an additional contact to the pseudo-octahedral geometry of the Ru center. The coordination modes of the complexes were studied in the solid state and in solution through single-crystal XRD, X-ray absorption spectroscopy, variable-temperature NMR spectroscopy, and DFT calculations. While κ-N2 O is the main coordination mode for 23+ and 3, an equilibrium that involves isomers with κ-N2 O and κ-NO2 coordination modes and neighboring hydrogen-bonded water molecules is observed for 42+ and 53+ .

Our objective was to define the positions of the nerves around the brachial artery and, secondarily, to assess the risk of intraneural injection during dual guided axillary block. Sixty ultrasound-guided axillary blocks were performed. The locations of the musculocutaneous, median, ulnar, and radial nerves relative to the brachial artery were determined. The position of the ulnar nerve was defined in relation to that of the brachial vein, and the position of the musculocutaneous nerve in relation to the coracobrachialis muscle. The locations were confirmed by neurostimulation and injection of local anesthetic was avoided when the current intensities were below 0.3 mA. The incidences of intraneural injection and postblock neurological injury were recorded. The median nerve was located in the upper external quadrant in 89% of cases and the ulnar nerve in the upper internal quadrant (95%), superficial (19%), or deep (81%) to the brachial vein. The radial nerve was located in the lower internal quadrant in 97% of cases, and the musculocutaneous nerve in the lower external quadrant in 85%. Its disposition differed depending on its proximity to the artery (106 ± 26°) or whether it was inside the coracobrachialis muscle (119 ± 15°; P = 0.023). Three intraneural injections were observed (0.5%, one in the median and two in the radial nerves) and no patient had postblock neuropathy. Our study evidences slight anatomical variability among the neural structures in the axillary region and confirms the safety of the axillary technique with double monitoring, using ultrasound to monitor the approach of the needle to the nerve and nerve stimulation at currents 0.3 mA to reduce the incidence of intraneural injection. Clin. Anat., 2018. © 2018 Wiley Periodicals, Inc. 2018.

To the Editor, Transmission and scanning electron microscopy have allowed the detailed study of the structure of human peripheral nerves, the non-neural connective tissue layers forming it, and other structures inside the nerve.[1][1] The minimum anatomical structure of a nerve is traditionally

Background and Objectives The costoclavicular space (CCS), which is located deep and posterior to the midpoint of the clavicle, may be a better site for infraclavicular brachial plexus block than the traditional lateral paracoracoid site. However, currently, there is paucity of data on the anatomy of the brachial plexus at the CCS. We undertook this cadaver anatomic study to define the anatomy of the cords of the brachial plexus at the CCS and thereby establish the anatomic basis for ultrasound-guided infraclavicular brachial plexus block at this proximal site. Methods The anatomy and topography of the cords of the brachial plexus at the CCS was evaluated in 8 unembalmed (cryopreserved), thawed, fresh adult human cadavers using anatomic dissection, and transverse anatomic and histological sections, of the CCS. Results The cords of the brachial plexus were located lateral and parallel to the axillary artery at the CCS. The topography of the cords, relative to the axillary artery and to one another, in the transverse (axial) plane was also consistent at the CCS. The lateral cord was the most superficial of the 3 cords and it was always anterior to both the medial and posterior cords. The medial cord was directly posterior to the lateral cord but medial to the posterior cord. The posterior cord was the lateral most of the 3 cords at the CCS and it was immediately lateral to the medial cord but posterolateral to the lateral cord. Conclusions The cords of the brachial plexus are clustered together lateral to the axillary artery, and share a consistent relation relative to one another and to the axillary artery, at the CCS.

A new bis-facial dinuclear ruthenium complex, {[RuII(bpy)]2(μ-bimp)(μ-Cl)}2+, 22+, containing a hexadentate pyrazolate- bridging ligand (Hbimp) and bpy as auxiliary ligands has been synthesized and fully characterized in solution by spectrometric, spectroscopic, and electrochemical techniques. The new compound has been tested with regard to its capacity to oxidize water and alkenes. The in situ generated bis-aqua complex, {[RuII(bpy)(H2O)]2(μ-bimp)}3+, 33+, is an excellent catalyst for the epoxidation of a wide range of alkenes. High turnover numbers (TN), up to 1900, and turnover frequencies (TOF), up to 73 min−1, are achieved using PhIO as oxidant. Moreover, 33+ presents an outstanding stereospecificity for both cis and trans olefins toward the formation of their corresponding epoxides due to specific interactions transmitted by its ligand scaffold. A mechanistic analysis of the epoxidation process has been performed based on density functional theory (DFT) calculations in order to better understand the putative cooperative effects within this dinuclear catalyst Support form MINECO (Grants CTQ2011-26440, CTQ-2013-49075-R and CTQ2010-21532-C02-02) and the DFG (Grant Me1313/9-1) is gratefully acknowledged. J.A. is grateful for the award of a PIF doctoral grant from UAB. A.P. thanks the Spanish MINECO for the project CTQ2014-59832-JIN and the European Commission for a Career Integration Grant (No.CIG09-GA-2011-293900)

Research faces the challenge of harmonizing entrepreneurship research and the role of entrepreneurship and innovations as engines of territorial performance.

A family of Ru complexes based on the pentadentate ligand t5a(3-) ((2,5-bis(6-carboxylatopyridin-2-yl)pyrrol-1-ide) and pyridine (py) that includes \Ru-II(Ht5a-kappa-(NO)-O-2)(py)(3)\ (1H(II)(kappa-(NO)-O-2)), \Ru-III(t5a-kappa-(NO1.5)-O-3)(py)(2)\ (2(III)(kappa-(NO1.5)-O-3)), and \Ru-IV(t5a-kappa-(NO2)-O-3)(py)(2)\(+) (\2(IV)(kappa-(NO2)-O-3)\(+)) has been prepared and thoroughly characterized. Complexes 1H(II)(kappa-(NO)-O-2), 2(III)(kappa-(NO1.5)-O-3), and \2(IV)(kappa-(NO2)-O-3)\(+) have been investigated in solution by spectroscopic methods (NMR, UV-vis) and in the solid state by single-crystal X-ray diffraction analysis and complemented by density functional theory (DFT) calculations. The redox properties of complex 2(III)(kappa-(NO1.5)-O-3) have been studied by electrochemical methods (CV and DPV), showing its easy access to high oxidation states, thanks to the trianionic nature of the t5a(3-) ligand. Under neutral to basic conditions complex \2(IV)(kappa-(NO2)-O-3)\(+) undergoes aquation, generating \Ru-IV(OH)(t5a-kappa-(NO)-O-2)(py)(2)\ (2(IV)(OH)(kappa-(NO)-O-2)). Further oxidation of the complex forms \Ru-V(O)(t5a-kappa-(NO)-O-2)(py)(2)\ (2(V)(O)(kappa-(NO)-O-2)), which is a very efficient water oxidation catalyst, reaching a TOFMAX value of 9400 s(-1) at pH 7.0, as measured via foot of the wave analysis. The key to fast kinetics for the catalytic oxidation of water to dioxygen by 2(V)(O)(kappa-(NO)-O-2) is due not only to the easy access to high oxidation states but also to the intramolecular hydrogen bonding provided by the noncoordinated dangling carboxylate at the transition state, as corroborated by DFT calculations.

A hybrid photoanode based on a molecular water oxidation precatalyst was prepared from TiO

Concerns about the quality of China’s official GDP statistics have been a perennial question in understanding its economic dynamics. We use data on satellite-recorded nighttime lights as an independent benchmark for comparing various published indicators of the state of the Chinese economy. Using the methodology of Pinkovskiy and Sala-i-Martin (2016a and b), we exploit nighttime lights to compute the optimal weights for various Chinese economic indicators in a best unbiased predictor of Chinese growth rates. Our computations of Chinese growth based on optimal weightings of various combinations of economic indicators provide evidence against the hypothesis that the Chinese economy contracted precipitously in late 2015, and are consistent with the rate of Chinese growth being higher than is reported in the official statistics.

Background and Objectives This study aimed to describe in detail the relevant sonoanatomy, technique, and block dynamics of an ultrasound-guided costoclavicular brachial plexus block (BPB). Methods Thirty patients scheduled for hand or forearm surgery under a BPB underwent transverse ultrasound imaging of the medial infraclavicular fossa to identify the cords of the brachial plexus at the costoclavicular space (CCS). An ultrasound-guided BPB was then performed at the CCS with 20 mL of 0.5% ropivacaine. Sensory-motor blockade of the ipsilateral median, radial, ulnar, and musculocutaneous nerves were assessed at regular intervals for 30 minutes after the injection. Successful block was defined as being able to complete surgery under the BPB. Results The CCS was visualized as a well-defined intermuscular space lying deep and posterior to the mid-point of the clavicle. The cords of the brachial plexus were clustered together lateral to the axillary artery within the CCS. The costoclavicular BPB was successfully performed in all patients, and the median onset time for sensory and motor blockade of all the 4 nerves was 5 [5–15] and 5 [5–10] minutes, respectively. Complete sensory blockade of all the 4 nerves was achieved in 30 [20–30] minutes, and the BPB was successful in 29 (97%) of 30 patients. There were no complications directly related to the technique or the local anesthetic injection. Conclusions This report describes a novel technique of infraclavicular BPB at the costoclavicular space that produces rapid onset of BPB. Future research should compare the safety and efficacy of this new technique with the traditional lateral sagittal infraclavicular BPB.

A new tetradentate dinucleating ligand [1,1'-(4-methyl-1H-pyrazole-3,5-diyl)bis(1-(pyridin-2-yl)ethanol)] (Hpbl) containing an O/N mixed donor set of atoms has been synthesized and characterized by analytical and spectroscopic techniques. The Ru-Cl and Ru-aqua complexes containing this ligand of general formula [(RuX)-X-II(Hpb1)-(trpy)](Y+) (trpy = 2,2':6',2''-terpyridine; X = Cl, y = 1; X = H2O, y = 2) have been prepared and thoroughly characterized by spectroscopic and electrochemical techniques. The Ru aqua complex 2 undergoes N -> O linkage isomerization as observed electrochemically, and the related thermodynamic and kinetic parameters are extracted from cyclic voltammetry experiments together with DIGISIM, a CV simulation package. Under basic conditions an additional isomer is observed where the pyrazolyl group in the Hpbl ligand is replaced by the geminal pyridyl group. Further structural and electronic characterization of all the isomers has been carried out by means of DFT calculations Support from MINECO (CTQ2011-26440, CTQ-2013-49075-R, and CTQ2011-23156-C02-02) is gratefully acknowledged. L.F. is grateful for the award of a PIF doctoral grant from UAB. A.P. is grateful to the European Commission (CIG09-GA-2011-293900) and the Spanish MINECO (Ramon y Cajal contract RYC-2009-05226)

A new family of Ru–Hbpp dinuclear complexes containing the positively charged terpyridine derivative ligand 4-(-p-(pyridin-1-ylmethyl)phenyl)-2,2′:6′,2′-terpyridine of general formula {[Ru(L1+)]2(μ-bpp)(L-L)}m+ (L-L = μ-Cl, μ-acetato, or (H2O)2; m = 4 or 5) have been synthesized and fully characterized, both in the solid state (X-ray diffraction) and in solution (1D and 2D NMR spectroscopy, UV–vis spectroscopy and electrochemical techniques). New hybrid materials have been prepared by the electrostatic interaction of these complexes with several oxidatively rugged solid supports such as SiO2, FTO–TiO2 and FTO–Nafion®. These new hybrid materials were prepared and catalytically evaluated with regard to their capacity to chemically and electrochemically oxidize water to dioxygen.

Much attention has been paid to heterocyclic N-containing ligands due to their applicability as bridging ligands in the synthesis of redox active dinuclear metal complexes. With this aim, we report the synthesis and full characterization of a novel phthalazine-triazole ligand (1,4-bis(1-methyl-1H-1, 2,3-triazol-4-yl)phthalazine). Moreover, we show that the phthalazine nitrogen atoms of this N-heterocyclic ligand are more reactive towards alkylating agents than the triazole groups. New ruthenium (ii) complexes containing this ligand have been obtained and characterized both structurally and electrochemically. The geometry imposed by the ligand allows the placement of two ruthenium centers in very close proximity so that efficient through-space interactions take place, a concept of crucial importance for electron transfer processes. Science Foundation Ireland MINECO

Background: The AmbuAuraGain is a new single-use supraglottic airway device with gastric channel designed to facilitate intubation. The aim of the study was to assess the anatomic position and the performance of the AuraGain in fresh cadavers compared to that of the Intersurgical i-gel and LMA Supreme New Cuff. Methods: The 3 devices were inserted in random order in 7 fresh cadavers without difficult airway criteria. The assessed items were: Insertion time, number of attempts and ease of insertion, airway seal pressure, ease of gastric tube insertion, endoscopic view of vocal cords, efficacy of guided tracheal intubation through the AuraGain and i-gel, and anatomic fit by lateral X-ray and neck dissections. Results: All devices were successfully inserted within 3 attempts, except for one case of the LMA Supreme. Adjusting manoeuvres were often required to accomplish correct insertion. A 16 G gastric tube was easily advanced through all AuraGain and LMA Supreme devices. Fiberoptic tracheal intubation was effectively achieved through all AuraGain and i-gel devices in less than 60 s. Lateral X-ray and neck dissections confirmed optimal alignment of all devices with the respiratory and digestive tracts. Conclusions: Insertion of the new AmbuAuraGain required adjusting manoeuvres in some cases, as observed with the other two devices, and achieved similar airway seal pressures. Passage of a large bore gastric tube was as fast as with the LMA Supreme and ease of guided intubation was similar to that of the i-gel.

Resumen Objetivos Describir la distribucion de los nervios terminales del plexo braquial a nivel axilar para definir patrones de distribucion a partir de su observacion mediante ultrasonidos. Material y metodo Cincuenta voluntarios a quienes se practico bilateralmente una exploracion ecografica axilar. Se determino la distribucion en grados de circunferencia de los nervios en relacion con la arteria (que seria el punto central), la distancia de la arteria a cada uno de los nervios y la disposicion del nervio cubital respecto a la vena humeral. Resultados El nervio mediano se hallo en el cuadrante superoexterno a −29 ± 40° y a una distancia de 2,1 ± 0,9 mm (85%). El nervio cubital se situo en el cuadrante superointerno (90%), a 53 ± 26° y a una distancia de 4,2 ± 2,1 mm. Se situo superficial a la vena en el 46% de los casos y profundo en el 54%. El nervio radial se localizo en el cuadrante inferointerno (86%), a 122 ± 38°, y a una distancia de 3,3 ± 1,7 mm de la arteria. El nervio musculocutaneo se hallo a −103 ± 22° y a una distancia de 9,3 ± 5,6 mm. En el 90% de los casos se situo en el cuadrante inferoexterno (−110 ± 12°) y a una distancia de 10,0 ± 5,6 mm, mientras que en el 10% restante se hallo en el cuadrante superoexterno (−55 ± 16°), siendo la distancia en estos casos de 4,8 ± 2,7 mm. No hubo diferencias significativas en base a la lateralidad, al sexo, ni a la obesidad. Conclusiones Nuestro estudio define 4 patrones anatomicos, 2 basados en la posicion del nervio musculocutaneo respecto a la arteria humeral y musculo coracobraquial, y 2 basados en la disposicion del nervio cubital respecto a la vena humeral. Los nervios mediano y radial presentan una disposicion muy homogenea. En nuestro estudio estos patrones no se vieron influidos por la lateralidad, el sexo, ni el sobrepeso.

One clean alternative to fossil fuels would be to split water using sunlight. However, to achieve this goal, researchers still need to fully understand and control several key chemical reactions. One of them is the catalytic oxidation of water to molecular oxygen, which also occurs at the oxygen evolving center of photosystem II in green plants and algae. Despite its importance for biology and renewable energy, the mechanism of this reaction is not fully understood. Transition metal water oxidation catalysts in homogeneous media offer a superb platform for researchers to investigate and extract the crucial information to describe the different steps involved in this complex reaction accurately. The mechanistic information extracted at a molecular level allows researchers to understand both the factors that govern this reaction and the ones that derail the system to cause decomposition. As a result, rugged and efficient water oxidation catalysts with potential technological applications can be developed. In this Account, we discuss the current mechanistic understanding of the water oxidation reaction catalyzed by transition metals in the homogeneous phase, based on work developed in our laboratories and complemented by research from other groups. Rather than reviewing all of the catalysts described to date, we focus systematically on the several key elements and their rationale from molecules studied in homogeneous media. We organize these catalysts based on how the crucial oxygen-oxygen bond step takes place, whether via a water nucleophilic attack or via the interaction of two M-O units, rather than based on the nuclearity of the water oxidation catalysts. Furthermore we have used DFT methodology to characterize key intermediates and transition states. The combination of both theory and experiments has allowed us to get a complete view of the water oxidation cycle for the different catalysts studied. Finally, we also describe the various deactivation pathways for these catalysts.

Aim The goal is to describe the ultrastructure of normal human peripheral nerves, and to highlight key aspects that are relevant to the practice of peripheral nerve block anaesthesia. Method Using samples of sciatic nerve obtained from patients, and dural sac, nerve root cuff and brachial plexus dissected from fresh human cadavers, an analysis of the structure of peripheral nerve axons and distribution of fascicles and topographic composition of the layers that cover the nerve is presented. Myelinated and unmyelinated axons, fascicles, epineurium, perineurium and endoneurium obtained from patients and fresh cadavers were studied by light microscopy using immunohistochemical techniques, and transmission and scanning electron microscopy. Structure of perineurium and intrafascicular capillaries, and its implications in blood–nerve barrier were revised. Results Each of the anatomical elements is analyzed individually with regard to its relevance to clinical practice to regional anaesthesia. Conclusions Routine practice of regional anaesthetic techniques and ultrasound identification of nerve structures has led to conceptions, which repercussions may be relevant in future applications of these techniques. In this regard, the ultrastructural and histological perspective accomplished through findings of this study aims at enlightening arising questions within the field of regional anaesthesia.

The synthesis of new dinuclear complexes of the general formula {[Ru(II)(trpy)]2(μ-pdz-dc)(μ-(L)}(+) [pdz-dc is the pyridazine-3,6-dicarboxylate dianion; trpy is 2,2':6',2″-terpyridine; L = Cl (1(+)) or OH (2(+))] is described. These complexes are characterized by the usual analytical and spectroscopic techniques and by X-ray diffraction analysis. Their redox properties are characterized by means of cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Complex 2(+) is used as the starting material to prepare the corresponding Ru-aqua complex {[Ru(II)(trpy)(H2O)]2(μ-pdz-dc)}(2+) (3(2+)), whose electrochemistry is also investigated by means of CV and DPV. Complex 3(2+) is able to catalytically and electrocatalytically oxidize water to dioxygen with moderate efficiencies. In sharp contrast, 3(2+) is a superb catalyst for the epoxidation of alkenes. For the particular case of cis-β-methylstyrene, the catalyst is capable of carrying out 1320 turnovers with a turnover frequency of 11.0 cycles min(-1), generating cis-β-methylstyrene oxide stereospecifically.

Energy has been a central subject for human development from Homo erectus to date. The massive use of fossil fuels during the last 50 years has generated a large CO2 concentration in the atmosphere that has led to the so-called global warming. It is very urgent to come up with C-neutral energy schemes to be able to preserve Planet Earth for future generations to come and still preserve our modern societies' life style. One of the potential solutions is water splitting with sunlight (hν-WS) that is also associated with “artificial photosynthesis”, since its working mode consists of light capture followed by water oxidation and proton reduction processes. The hydrogen fuel generated in this way is named as “solar fuel”. For this set of reactions, the catalytic oxidation of water to dioxygen is one of the crucial processes that need to be understood and mastered in order to build up potential devices based on hν-WS. This tutorial describes the different important aspects that need to be considered to come up with efficient and oxidatively robust molecular water oxidation catalysts (Mol-WOCs). It is based on our own previous work and completed with essential contributions from other active groups in the field. We mainly aim at describing how the ligands can influence the properties of the Mol-WOCs and showing a few key examples that overall provide a complete view of today's understanding in this field.

Objective: To investigate the behavior of the sciatic nerve during hip rotation at subgluteal space. Materials and methods: Sonographic examination (high-resolution ultrasound machine at 5.0–14 MHZ) of the gemelli-obturator internus complex following two approaches: (1) a study on cadavers and (2) a study on healthy volunteers. The cadavers were examined in pronation, pelvis-fixed position by forcing internal and external rotations of the hip with the knee in 90° flexion. Healthy volunteers were examined during passive internal and external hip rotation (prone position; lumbar and pelvic regions fixed). Subjects with a history of major trauma, surgery or pathologies affecting the examined regions were excluded. Results: The analysis included eight hemipelvis from six fresh cadavers and 31 healthy volunteers. The anatomical study revealed the presence of connective tissue attaching the sciatic nerve to the structures of the gemellus-obturator system at deep subgluteal space. The amplitude of the nerve curvature during rotating position was significantly greater than during resting position. During passive internal rotation, the sciatic nerve of both cadavers and healthy volunteers transformed from a straight structure to a curved structure tethered at two points as the tendon of the obturator internus contracted downwards. Conversely, external hip rotation caused the nerve to relax. Conclusion: Anatomically, the sciatic nerve is closely related to the gemelli-obturator internus complex. This relationship results in a reproducible dynamic behavior of the sciatic nerve during passive hip rotation, which may contribute to explain the pathological mechanisms of the obturator internal gemellus syndrome.

International audience; In this work, we describe the synthesis of a new N-heterocyclic carbene (NHC) ligand, derived from a hybrid pyrazole-imidazolium scaffold, namely 1-[2-(3,5-dimethylpyrazol-1-yl)ethyl]-3-((S)-1-phenylethyl)-3H-imidazol-2-ylidene (L). This ligand has been used as a stabilizer for the organometallic synthesis of palladium(0) nanoparticles (Pd NPs). L presents a better stabilizing effect than its pre-carbenic HLCl counterpart, allowing the formation of isolated Pd NPs while HLCl yields aggregated ones. Additionally, molecular Pd(ii) coordination compounds of L and HLCl were synthesized and characterized to better understand the coordination modes of these ligands. Both molecular and colloidal Pd systems have been further tested in catalytic C-C coupling processes. Three different types of reactions have been observed depending on the catalytic system: (i) the Suzuki-Miyaura reaction takes place with Pd molecular complexes; (ii) a secondary reaction, the dehalogenation of the substrate, is always detected and (iii) the C-C homocoupling between two molecules of bromoarenes is observed with colloidal catalysts.

A new CNNC carbene-phthalazine tetradentate ligand has been synthesised, which in the reaction with [Ru(T)Cl3] (T = trpy, tpm, bpea; trpy = 2,2′;6′,2′′-terpyridine; tpm = tris(pyrazol-1-yl)methane; bpea = N,N-bis(pyridin-2-ylmethyl)ethanamine) in MeOH or iPrOH undergoes a C–N bond scission due to the nucleophilic attack of a solvent molecule, with the subsequent formation of the mononuclear complexes cis-[Ru(PhthaPz-OR)(trpy)X]n+, [Ru(PhthaPz-OMe)(tpm)X]n+ and trans,fac-[Ru(PhthaPz-OMe)(bpea)X]n+ (X = Cl, n = 1; X = H2O, n = 2; PhthaPz-OR = 1-(4-alkoxyphthalazin-1-yl)-3-methyl-1H-imidazol-3-ium), named 1a+/2a2+ (R = Me), 1b+/2b2+ (R = iPr), 3+/42+ and 5+/62+, respectively. Interestingly, regulation of the stability regions of different Ru oxidation states is obtained by different ligand combinations, going from 62+, where Ru(III) is clearly stable and mono-electronic transfers are favoured, to 2a2+/2b2+, where Ru(III) is almost unstable with regard to its disproportionation. The catalytic performance of the Ru–OH2 complexes in chemical water oxidation at pH 1.0 points to poor stability (ligand oxidation), with subsequent evolution of CO2 together with O2, especially for 42+ and 62+. In electrochemically driven water oxidation, the highest TOF values are obtained for 2a2+ at pH 1.0. In alkene epoxidation, complexes favouring bi-electronic transfer processes show better performances and selectivities than those favouring mono-electronic transfers, while alkenes containing electron-donor groups show better performances than those bearing electron-withdrawing groups. Finally, when cis-β-methylstyrene is employed as the substrate, no cis/trans isomerization takes place, thus indicating the existence of a stereospecific process.

Background and Aims:High resolution ultrasound (HRU) permits identify small nerves, but in the clinicall setting, interostobrachial nerve(ICBN) and medial brachial cutaneous nerve (MBCN) are not identified with conventional portable ultrasound devides. The aim of this study is to identifly boyh nerves and describe their relation with specific anatomical structures that could be easely identified with ultrasound equipement available in the clinical setting.Methods:21 healthy patient were scan using HRU bilaterally in the area of the axilla located over the conjoint tendon to find the ICBN and MCBN and discribe their anatomic relations. 5 fresh cadaver were used to validate the previous anatomical findings. ICBN and MCBN ultrasound guided block was perfomed with 5 ml of methyl blue and the distribution of the injected medium was evaluated by means of a CT-scan and disecction.ResultsICBN and MCBN where identified in all cases. MCBN distance to the axillary artery was 16u00b13 mm. The average distance of the ICBN from the artery was 35u00b16 mm in males and 27u00b15 mm in females. Constant identification of the muscle-tendon junction of the LD muscle was observed with respect to the location of the branches of the ICBN nerve. Dissection and CT-Scan confirm this findings.Conclusions:HRU are a usefull tool to identified ICBN and MCBN nerves, and to described structures that can be easeIy identified with conventional portable ultrasound use in the clinicall setting.

Introduction: Axillary plexus blockade is a common technique in clinical practice with the pattern of structures around the artery well known. Historically, the proper response for radial nerve stimulation was only considered the extension of the hand and wrist. Materials and Methods: Twenty-five axillary blockades assessed by ultrasound and neurostimulation; the principal objective was to correlate the needle position over the nerve and correlate the findings with the anatomical and histological structure of the radial nerve. During the procedure, the neurostimulation needle was directed in two directions: above the axillary artery or underneath it to reach the medial or lateral margin of the nerve. Once the needle reached the nerve, the current was augmented gradually until a response was elicited. For the anatomical analysis, histological samples and eight and axillas were dissected to correlate the results with the anatomy.Results: The results obtained, showed a significant difference in the relationship with the pathway of the needle with the artery and the motor response evoked (p