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Advocates of blockchain claim widespread impact will be forthcoming shortly. However, the path of innovation in blockchain is uncharted. Investors will assess where blockchain innovation will profit first and most. The timing and impact of each blockchain innovation is a key consideration for business managers. Link, Ruhm, and Siegel (2014) suggest private equity investments forecast which innovations are likely to succeed. Previous research on private equity gives insight on why that ownership structure is especially successful. Private equity investments are collected for two periods and categorized according to basic blockchain components, basic cryptocurrency payment components, and decentralized applications, particularly applications in financial services. The results suggest investors have acted prudently, investing strongly in building blocks, payment systems and fundamental applications, showing a primary emphasis on refining blockchain and realizing standard blockchain protocols before investing in highly complex applications. Further, financial services applications dominate, suggesting investors see financial services as far and away the most likely industry for imminent deconstruction.

The preparation of valuable and industrially relevant organophosphorus compounds currently depends on indirect multistep procedures involving difficult-to-handle white phosphorus as a common P atom source. Herein, we report a practical and versatile method for the synthesis of a variety of monophosphorus compounds directly from the bench-stable allotrope red phosphorus (Pred). The relatively inert Pred was productively functionalised by using the cheap and readily available radical reagent tri-n-butyltin hydride, and subsequent treatment with electrophiles yields useful P1 compounds. Remarkably, these transformations require only modest inert-atmosphere techniques and use only reagents that are inexpensive and commercially available, making this a convenient and practical methodology accessible in most laboratory settings.

The synthesis and characterisation of [Co2(η4 P2C2tBu2)2(µ:η4:η4-P2C2tBu2)] (1) is described, featuring two cobalt atoms and three diphosphacyclobutadiene ligands. This compound is the first triple-decker sandwich complex which exclusively contains cyclobutadiene ligands.

Sphingosine-1-phosphate (S1P) is a versatile signaling lipid involved in the regulation of numerous cellular processes. S1P regulates cellular proliferation, migration, and apoptosis as well as the function of immune cells. S1P is generated from sphingosine (Sph), which derives from the ceramide metabolism. In particular, high concentrations of S1P are present in the blood. This originates mainly from erythrocytes, endothelial cells (ECs), and platelets. While erythrocytes function as a storage pool for circulating S1P, platelets can rapidly generate S1P de novo, store it in large quantities, and release it when the platelet is activated. Platelets can thus provide S1P in a short time when needed or in the case of an injury with subsequent platelet activation and thereby regulate local cellular responses. In addition, platelet-dependently generated and released S1P may also influence long-term immune cell functions in various disease processes, such as inflammation-driven vascular diseases. In this review, the metabolism and release of platelet S1P are presented, and the autocrine versus paracrine functions of platelet-derived S1P and its relevance in various disease processes are discussed. New pharmacological approaches that target the auto- or paracrine effects of S1P may be therapeutically helpful in the future for pathological processes involving S1P.

Phosphorus analogues of the ubiquitous cyclopentadienyl (Cp) are a rich and diverse family of compounds, which have found widespread use as ligands in organometallic complexes. By contrast, phospholes incorporating heaviear group 14 elements (Si, Ge, Sn, and Pb) are hardly known. Here, we demonstrate the isolation of the first metal complexes featuring heavy cyclopen-tadienyl anions (SnP4)2─ and (PbP4)2─. The complexes [(η4-tBu2C2P2)2Co2(μ,η5:η5-P4Tt)] [Tt = Sn (6), Pb (7)] are formed by reaction of white phosphorus (P4) with cyclooctadiene cobalt complexes [Ar′TtCo(η4-P2C2tBu2)(η4-COD)] [Sn (2), Pb (3), Ar′ = C6H3-2,6{C6H3¬-2,6-iPr2}2, COD = cycloocta-1,5-diene] and Tt{Co(η4-P2C2tBu2)(COD)}2 [Tt = Sn (4), Pb (5)]. While the (SnP4)2− complex 6 was isolated as a pure and stable compound, compound 7 eliminates Pb(0) below room temper-ature to afford [(η4-tBu2C2P2)2Co2(μ,η4:η4-P4) (8), which is a rare example of a tripledecker complex with a (P4)2─ middle deck. The electronic structures of 6-8 are analysed using theoretical methods, including an analysis of intrinsic bond orbitals and magnetic response theory. Thereby the aromatic nature of (P5)− and (SnP4)2− was confirmed, while for (P4)2− a specific type of symmetry-induced weak paramagnetism was found which is distinct from conventional antiaromatic species.

Organophosphorus compounds (OPCs) are highly important chemicals, finding numerous applications in both academia and industry. Herein we describe a simple photocatalytic method for the stannylation of white phosphorus (P4) using a cheap, commercially-available distannane, (Bu3Sn)2, and anthraquinone as a simple photocatalyst. Subsequent ‘one pot’ transformation of the resulting stannylated monophosphine intermediate (Bu3Sn)3P provides direct, convenient and versatile access to valuable OPCs such as acylated phosphines and tetraalkylphosphonium salts.

Objective:To compare strategies for hospital ranking based on colon surgical-site infection (SSI) rate by combining all colon procedures versus stratifying by surgical approach (ie, laparoscopic vs open).Design:Retrospective cohort study.Methods:We identified SSIs among Medicare beneficiaries undergoing colon surgery from 2009 through 2013 using previously validated methods. We created a risk prediction model for SSI using age, sex, race, comorbidities, surgical approach (laparoscopy vs open), and concomitant colon and noncolon procedures. Adjusted SSI rates were used to rank hospitals. Subanalyses were performed for common colon procedures and procedure types for which there were both open and laparoscopic procedures. We generated ranks using only open and only laparoscopic procedures, overall and for each subanalysis. Rankings were compared using a Spearman correlation coefficient.Results:In total, 694,813 colon procedures were identified among 508,135 Medicare beneficiaries. The overall SSI rate was 7.6%. The laparoscopic approach was associated with lower SSI risk (OR, 0.5; 95% CI, 0.4–0.5), and higher SSI risk was associated with concomitant abdominal surgeries (OR, 1.4; 95% CI, 1.4–1.5) and higher Elixhauser score (OR, 1.1; 95% CI, 1.0–1.1). Hospital rankings for laparascopic procedures were poorly correlated with rankings for open procedures (r = 0.23).Conclusions:Hospital rankings based on total colon procedures fail to account for differences in SSI risk from laparoscopic vs open procedures. Stratifying rankings by surgical approach yields a more equitable comparison of surgical performance.

The divalent iron complexes trans-[FeBr2(BINC)2], [Cp*FeCl(BINC)] (Cp* = Me5C5), and [FeBr2(CNAr3NC)2] with the chelating bis(isonitrile) ligands BINC (bis(2-isocyanophenyl)phenylphosphonate) and CNAr3NC (2,2″-diisocyano-3,5,3″,5”tetramethyl-1,1′:3′,1″-terphenyl) have been prepared and characterized. Their subsequent reduction yields the di- and trinuclear compounds [Fe3(BINC)6], [Cp*Fe(BINC)]2, [Fe(CNAr3NC)2]2, and [K(Et2O)]2[Fe(CNAr3NC)2]2. The molecular structures of all new species were determined by X-ray crystallography and compared to those of related iron carbonyl complexes, demonstrating that the bidentate isonitrile ligands are capable surrogates for two CO ligands with only minimal distortion of the tetrahedral or octahedral geometry of the parent complexes. The complexes were further characterized by NMR and IR spectroscopy, and the electrochemical properties of selected compounds were analyzed by UV–vis–NIR spectroelectrochemistry.

We prove compactness of a restricted set of real-valued, compactly supported potentials V V for which the corresponding Schrödinger operators H V H_V have the same resonances, including multiplicities. More specifically, let B R ( 0 ) B_R(0) be the ball of radius R > 0 R > 0 about the origin in R d \mathbb {R}^d , for d = 1 , 3 d=1,3 . Let I R ( V 0 ) \mathcal {I}_R (V_0) be the set of real-valued potentials in C 0 ∞ ( B ¯ R ( 0 ) ; R ) C_0^\infty ( \overline {B}_R(0); \mathbb {R}) so that the corresponding Schrödinger operators have the same resonances, including multiplicities, as H V 0 H_{V_0} , for a fixed, but arbitrary, potential V 0 ∈ C 0 ∞ ( B ¯ R ( 0 ) ; R ) V_0 \in C_0^\infty ( \overline {B}_R(0); \mathbb {R}) . We prove that the set I R ( V 0 ) \mathcal {I}_R (V_0) is a compact subset of C 0 ∞ ( B ¯ R ( 0 ) ) C_0^\infty (\overline {B}_R(0)) in the C ∞ C^\infty -topology. An extension to Sobolev spaces of less regular potentials is discussed.

The first mixed phosphatetrahedranes were reported only recently and their reactivity is virtually unexplored. Herein, we present a reactivity study on di-tert-butyldiphosphatetrahedrane (1), which is the dimer of tert-butylphosphaalkyne. The (tBuCP)2 tetrahedron is activated selectively by N-heterocyclic carbene (NHC) nickel(I) and nickel(0) complexes, resulting in novel complexes featuring diverse (tBuCP)n -frameworks (n=2, 4). Release of the (tBuCP)4 framework from one of the complexes was achieved by addition of CO gas. Furthermore, 1 can be used as a source for P2 units by elimination of di-tert-butylacetylene in the coordination sphere of nickel.

Magnesium cobaltates (Arnacnac)MgCo(COD)2 (1–3) were synthesised by reacting (Arnacnac)MgI(OEt2) with K[Co(η4-COD)2] (COD = 1,5-cyclooctadiene) [Arnacnac = CH(ArNCMe)2; Ar = 2,4,6-Me3-C6H2 (Mes), 2,6-Et2-C6H3 (Dep), 2,6-iPr2-C6H3Mes (Dipp)]. Compounds 1–3 form contact ion-pairs in toluene, while solvent separated ion-pairs are formed in THF. The effect of ion-pairing on the reactivity is illustrated by reaction of 2 with tert-butylphosphaalkyne, which affords distinct 1,3-diphosphacyclobutadiene complexes. The heteroleptic sandwich complex [(Depnacnac)MgCo(P2C2tBu2)]2 (4) is selectively formed in toluene, while the homoleptic bis(1,3-diphosphacyclobutadiene) complex [(Depnacnac)Mg(THF)3][Co(P2C2tBu2)2] (5) is obtained in THF. Complex 4 is a precursor to further unusual phosphaorganometallic compounds. Substitution of the labile COD ligand in 4 by white phosphorus (P4) enabled the synthesis of the phosphorus-rich sandwich compound [(Depnacnac)MgCoP4(P2C2tBu2)]2 (6). The heterobimetallic complex (Cp*NiP2C2tBu2)Co(COD) (7) was isolated after treatment of 4 with Cp*Ni(acac) (Cp* = C5Me5, acac = acetylacetonate)., Ion-pairing strongly influence the reactivity of low-oxidation state transition metalate anions, enabling the synthesis of novel phosphaorganometallic compounds.

Oxidative addition of the P-P single bond of an ortho-carborane-derived 1,2-diphosphetane (1,2-C-2(PMes)(2)B10H10) (Mes = 2,4,6-Me3C6H2) to cobalt(-i) and nickel(0) sources affords the first heteroleptic complexes of a carborane-bridged bis(phosphanido) ligand. The complexes also incorporate labile ligands suitable for further functionalisation. Thus, the cobalt(i) complex [K([18]crown-6)][Co{1,2-(PMes)(2)C2B10H10}(cod)] (cod = 1,5-cyclooctadiene) bearing a labile cyclooctadiene ligand undergoes facile ligand exchange reactions with isonitriles and tert-butyl phosphaalkyne with retention of the bis(phosphanido) ligand. However, in the reaction with one equivalent of P-4, the electron-rich bis(phosphanido) moiety abstracts a single phosphorus atom with formation of a new P-3 chain, while the remaining three P atoms derived from P-4 form an eta(3)-coordinating cyclo-P-3 ligand. In contrast, when the same reaction is performed with two equivalents of the cobalt(i) complex, a dinuclear product is formed which features an unusual P-4 chain in its molecular structure., Chemical Science, 12 (33), ISSN:2041-6520, ISSN:2041-6539

Background Sepsis guidelines recommend daily review to de-escalate or stop antibiotics in appropriate patients. This randomized, controlled trial evaluated an opt-out protocol to decrease unnecessary antibiotics in patients with suspected sepsis. Methods We evaluated non–intensive care adults on broad-spectrum antibiotics despite negative blood cultures at 10 US hospitals from September 2018 through May 2020. A 23-item safety check excluded patients with ongoing signs of systemic infection, concerning or inadequate microbiologic data, or high-risk conditions. Eligible patients were randomized to the opt-out protocol vs usual care. Primary outcome was post-enrollment antibacterial days of therapy (DOT). Clinicians caring for intervention patients were contacted to encourage antibiotic discontinuation using opt-out language. If continued, clinicians discussed the rationale for continuing antibiotics and de-escalation plans. To evaluate those with zero post-enrollment DOT, hurdle models provided 2 measures: odds ratio of antibiotic continuation and ratio of mean DOT among those who continued antibiotics. Results Among 9606 patients screened, 767 (8%) were enrolled. Intervention patients had 32% lower odds of antibiotic continuation (79% vs 84%; odds ratio, 0.68; 95% confidence interval [CI], .47–.98). DOT among those who continued antibiotics were similar (ratio of means, 1.06; 95% CI, .88–1.26). Fewer intervention patients were exposed to extended-spectrum antibiotics (36% vs 44%). Common reasons for continuing antibiotics were treatment of localized infection (76%) and belief that stopping antibiotics was unsafe (31%). Thirty-day safety events were similar. Conclusions An antibiotic opt-out protocol that targeted patients with suspected sepsis resulted in more antibiotic discontinuations, similar DOT when antibiotics were continued, and no evidence of harm. Clinical Trials Registration NCT03517007.

Koronare Vasomotionsstörungen stellen eine relevante Ursache für Angina pectoris bei Patienten ohne hämodynamisch relevante atherosklerotische Plaques dar. Die Genese der Vasomotionsstörungen ist multifaktoriell und nicht final geklärt. Mittels Acetylcholin-Testung lassen sich epikardiale von mikrovaskulären Spasmen differenzieren. Ziel der Arbeit war die Analyse koronarer Morphologiekriterien und deren Einfluss auf mögliche Testergebnisse. Die Kriterien einer geringgradigen Atherosklerose, Muskelbrücken, Aneurysmata und Gefäßschlängelungen wurden untersucht. Die Koronarangiographien von 610 Patienten, die im Robert-Bosch-Krankenhaus Stuttgart einen Acetylcholin-Test erhalten haben wurden auf jene Morphologiekriterien untersucht. Diese Patienten wiesen eine Angina pectoris auf, in Abwesenheit höhergradiger Stenosen. Im Anschluss wurden die Morphologiekriterien mit dem Acetylcholin-Testergebnis verglichen. Es lässt sich eine signifikante Häufung geringgradiger Atherosklerose bei Patienten mit epikardialem Koronarspasmus im Acetylcholin-Test erkennen. Zudem scheint es beim Vorhandensein von koronaren Gefäßschlängelungen weniger epikardiale Spasmusformen im Acetylcholintest zu geben.

The neutral, homoleptic pyridylphosphininenickel(0) complex [Ni(2-Py-4,6-Ph2-PC5H2)2] (1) has been obtained by reaction of the formal Ni(0) source [(IPr)Ni(H2C═CHSiMe3)2] with 2 equiv of 2-(2′-pyridyl)-4,6-diphenylphosphinine (L). Compound 1 can be oxidized both electrochemically and through the use of ferrocenium salts, to afford the corresponding Ni(I) complexes [1]BF4, [1(THF)]PF6, and [12](BArF4)2. The structures of these salts reveal an interesting dependence on the nature of the anion. While [1]BF4 and [1(THF)]PF6 show trigonal-bipyramidal coordination of Ni in the solid state, [12](BArF4)2 exists as a dinuclear Ni(I) complex and possesses a bridging phosphinine moiety in a rare μ2 mode. Reactions of 1 with halobenzenes highlight the noninnocent behavior of the aromatic phosphinine ligand, leading to the formation of oxidized Ni complexes but not to classical oxidative addition products. The reaction of 1 with bromobenzene affords the λ5 phosphinine 2 and the bipyramidal Ni(I) complex [1]Br, whereas a more unconventional oxidation product 3 is formed from the reaction of 1 and iodobenzene.

The reaction of zerovalent nickel compounds with white phosphorus (P4) is a barely explored route to binary nickel phosphide clusters. Here, we show that coordinatively and electronically unsaturated N‐heterocyclic carbene (NHC) nickel(0) complexes afford unusual cluster compounds with P1, P3, P5 and P8 units. Using [Ni(IMes)2] [IMes=1,3‐bis(2,4,6‐trimethylphenyl)imidazolin‐2‐ylidene], electron‐deficient Ni3P4 and Ni3P6 clusters have been isolated, which can be described as superhypercloso and hypercloso clusters according to the Wade–Mingos rules. Use of the bulkier NHC complexes [Ni(IPr)2] or [(IPr)Ni(η6‐toluene)] [IPr=1,3‐bis(2,6‐diisopropylphenyl)imidazolin‐2‐ylidene] affords a closo‐Ni3P8 cluster. Inverse‐sandwich complexes [(NHC)2Ni2P5] (NHC=IMes, IPr) with an aromatic cyclo‐P5− ligand were identified as additional products.

The reaction of zerovalent nickel compounds with white phosphorus (P4) is a barely explored route to binary nickel phosphide clusters. Here, we show that coordinatively and electronically unsaturated N‐heterocyclic carbene (NHC) nickel(0) complexes afford unusual cluster compounds with P1, P3, P5 and P8 units. Using [Ni(IMes)2] [IMes=1,3‐bis(2,4,6‐trimethylphenyl)imidazolin‐2‐ylidene], electron‐deficient Ni3P4 and Ni3P6 clusters have been isolated, which can be described as superhypercloso and hypercloso clusters according to the Wade–Mingos rules. Use of the bulkier NHC complexes [Ni(IPr)2] or [(IPr)Ni(η6‐toluene)] [IPr=1,3‐bis(2,6‐diisopropylphenyl)imidazolin‐2‐ylidene] affords a closo‐Ni3P8 cluster. Inverse‐sandwich complexes [(NHC)2Ni2P5] (NHC=IMes, IPr) with an aromatic cyclo‐P5 − ligand were identified as additional products., Active nickel: Activation of white phosphorus (P4) by N‐heterocyclic carbene nickel(0) complexes affords binary nickel phosphorus cluster compounds. Both the degradation of P4 to P1 and P3 units and the aggregation to P5 and P8 moieties has been observed. The structures of the resulting Ni3P4, Ni3P6, and Ni3P8 clusters can be understood with the Wade–Mingos electron‐counting rules.

Reported fatal cases of bovine babesiosis (syn.: piroplasmosis, red water fever) in cattle were analyzed to identify spatial and temporal clusters of their incidence in the Austrian province of Styria. Data were collected within a governmental babesiosis compensation program. Diagnosis was performed using a standardized necropsy protocol. Between 1998 and 2016, a total of 1257 cases of fatal babesiosis were registered and compensated. Within the study interval, annual numbers of fatal babesiosis differed significantly among municipalities. Spatiotemporal analysis covering the entire study period revealed one high-risk cluster in the western and central northern region of Styria and a low-risk cluster in the southeastern part of Styria. Annual temporal analysis demonstrated that cases accumulated in June. Annual spatial analysis revealed consistently that cases mainly occurred in the western and central northern regions, whereas they occurred rarely in the southeastern regions. These results should increase awareness and facilitate protective actions against ticks during certain time periods and geographic areas.

PURPOSE The Oncology Care Model (OCM) is an episode-based alternative payment model for cancer care that seeks to reduce Medicare spending while maintaining care quality. We evaluated the impact of OCM on appropriate use of supportive care medications during cancer treatment. METHODS We evaluated chemotherapy episodes assigned to OCM (n = 201) and comparison practices (n = 534) using Medicare claims (2013-2019). We assessed denosumab use for beneficiaries with bone metastases from breast, lung, or prostate cancer; prophylactic WBC growth factor use for beneficiaries receiving chemotherapy for breast, lung, or colorectal cancer; and prophylactic use of neurokinin-1 (NK1) antagonists and long-acting serotonin antagonists for beneficiaries receiving chemotherapy for any cancer type. Analyses used a difference-in-difference approach. RESULTS After its launch in 2016, OCM led to a relative reduction in the use of denosumab for beneficiaries with bone metastases receiving bone-modifying medications (eg, 5.0 percentage point relative reduction in breast cancer episodes [90% CI, –7.1 to –2.8]). There was no OCM impact on use of prophylactic WBC growth factors during chemotherapy with high or low risk for febrile neutropenia. Among beneficiaries receiving chemotherapy with intermediate febrile neutropenia risk, OCM led to a 7.6 percentage point reduction in the use of prophylactic WBC growth factors during breast cancer episodes (90% CI, –12.6 to –2.7); there was no OCM impact in lung or colorectal cancer episodes. Among beneficiaries receiving chemotherapy with high or moderate emetic risk, OCM led to reductions in the prophylactic use of NK1 antagonists and long-acting serotonin antagonists (eg, 6.0 percentage point reduction in the use of NK1 antagonists during high emetic risk chemotherapy [90% CI, –9.0 to –3.1]). CONCLUSION OCM led to the reduced use of some high-cost supportive care medications, suggesting more value-conscious care.

Background This study aimed to compare the results of irradiation with protons versus irradiation with carbon ions in a raster scan technique in patients with skull base chordomas and to identify risk factors that may compromise treatment results. Methods A total of 147 patients (85 men, 62 women) were irradiated with carbon ions (111 patients) or protons (36 patients) with a median dose of 66 Gy (RBE (Relative biological effectiveness); carbon ions) in 4 weeks or 74 Gy (RBE; protons) in 7 weeks at the Heidelberg Ion Beam Therapy Center (HIT) in Heidelberg, Germany. The median follow-up time was 49.3 months. All patients had gross residual disease at the beginning of RT. Compression of the brainstem was present in 38%, contact without compression in 18%, and no contact but less than 3 mm distance in 16%. Local control and overall survival were evaluated using the Kaplan–Meier Method based on scheduled treatment (protons vs. carbon ions) and compared via the log rank test. Subgroup analyses were performed to identify possible prognostic factors. Results During the follow-up, 41 patients (27.9%) developed a local recurrence. The median follow-up time was 49.3 months (95% CI: 40.8–53.8; reverse Kaplan–Meier median follow-up time 56.3 months, 95% CI: 51.9–60.7). No significant differences between protons and carbon ions were observed regarding LC, OS, or overall toxicity. The 1‑year, 3‑year, and 5‑year LC rates were 97%, 80%, and 61% (protons) and 96%, 80%, and 65% (carbon ions), respectively. The corresponding OS rates were 100%, 92%, and 92% (protons) and 99%, 91%, and 83% (carbon ions). No significant prognostic factors for LC or OS could be determined regarding the whole cohort; however, a significantly improved LC could be observed if the tumor was > 3 mm distant from the brainstem in patients presenting in a primary situation. Conclusion Outcomes of proton and carbon ion treatment of skull base chordomas seem similar regarding tumor control, survival, and toxicity. Close proximity to the brainstem might be a negative prognostic factor, at least in patients presenting in a primary situation.

The modification of cyclopentadienyl ligands with carefully selected substituents is a widely used strategy for tuning their steric and electronic properties. We describe the synthesis of an extremely bulky penta-terphenyl cyclopentadienyl ligand (Cp

[LC RP((PhP)2C2H4)][OTf] (4 a,b[OTf]) and [LC iPrP(PPh2)2][OTf] (5 b[OTf]) were prepared from the reaction of imidazoliumyl‐substituted dipyrazolylphosphane triflate salts [LC RP(pyr)2][OTf] (3 a,b[OTf]; a: R=Me, b=iPr; LC R=1,3‐dialkyl‐4,5‐dimethylimidazol‐2‐yl; pyr=3,5‐dimethylpyrazol‐1‐yl) with the secondary phosphanes PhP(H)C2H4P(H)Ph) and Ph2PH. A stepwise double P−N/P−P bond metathesis to catena‐tetraphosphane‐2,3‐diium triflate salt [(Ph2P)2(LC MeP)2][OTf]2 (7 a[OTf]2) is observed when reacting 3 a[OTf] with diphosphane P2Ph4. The coordination ability of 5 b[OTf] was probed with selected coinage metal salts [Cu(CH3CN)4]OTf, AgOTf and AuCl(tht) (tht=tetrahydrothiophene). For AuCl(tht), the helical complex [{(Ph2PPLC iPr)Au}4][OTf]4 (9[OTf]4) was unexpectedly formed as a result of a chloride‐induced P−P bond cleavage. The weakly coordinating triflate anion enables the formation of the expected copper(I) and silver(I) complexes [(5 b)M(CH3CN)3][OTf]2 (M=Cu, Ag) (10[OTf]2, 11[OTf]2)., Cationic 1,2,3‐triphospholanium salts [LC RP((PhP)2C2H4)][OTf] and dicationic catena‐tetraphosphane‐2,3‐diidum salt [(Ph2P)2(LC MeP)2][OTf]2 were obtained from reactions of Lewis basic phosphanes with dipyrazolylphosphanes [LC RP(pyr)2][OTf] (pyr=3,5‐dimethylpyrazol‐1‐yl). Reaction of triphosphane salt [LC RP(PPh2)2][OTf] with AuCl(tht) led to the cationic gold complex [{(Ph2PPLC iPr)Au}4][OTf]4, which forms a helical structure in the solid state.

Combining laser spectroscopy in a Versatile Arc Discharge and Laser Ion Source, with Penning-trap mass spectrometry at the CERN-ISOLDE facility, this work reports on mean-square charge radii of neutron-rich mercury isotopes across the $N = 126$ shell closure, the electromagnetic moments of $^{207}$Hg and more precise mass values of $^{206-208}$Hg. The odd-even staggering (OES) of the mean square charge radii and the kink at $N = 126$ are analyzed within the framework of covariant density functional theory (CDFT), with comparisons between different functionals to investigate the dependence of the results on the underlying single-particle structure. The observed features are defined predominantly in the particle-hole channel in CDFT, since both are present in the calculations without pairing. However, the magnitude of the kink is still affected by the occupation of the $1i_{11/2}$ and $2g_{9/2}$ orbitals with a dependence on the relative energies as well as pairing., 20 pages, 12 figures, Phys. Rev. C in press

Reactions of di‐tert‐butyldiphosphatetrahedrane (1) with cycloocta‐1,5‐diene‐ or anthracene‐stabilised metalate anions of iron and cobalt consistently afford complexes of the rarely encountered 1,2‐diphosphacyclobutadiene ligand, which have previously been very challenging synthetic targets. The subsequent reactivity of 1,2‐diphosphacyclobutadiene cobaltates toward various electrophiles has also been investigated and is compared to reactions of related 1,3‐diphosphacyclobutadiene complexes. The results highlight the distinct reactivity of such isomeric species, showing that the 1,2‐isomers can act as precursors for previously unknown triphospholium ligands. The electronic structures of the new complexes were investigated by several methods, including NMR, EPR and Mößbauer spectroscopies as well as quantum chemical calculations., Reactions of iron and cobalt metalates with di‐tert‐butyldiphosphatetrahedrane readily afford 1,2‐diphosphacyclobutadiene complexes. The corresponding 1,3‐isomers were accessed by dimerisation of tert‐butylphosphaalkyne on the metal centre. The reactivity of 1,2‐ and 1,3‐diphosphacyclobutadiene cobaltates toward electrophiles was studied and the electronic structures of the new metalates were investigated by spectroscopy and quantum chemical calculations.

Detailed 31P{1H} NMR spectroscopic investigations provide deeper insight into the complex, multi‐step mechanisms involved in the recently reported photocatalytic arylation of white phosphorus (P4). Specifically, these studies have identified a number of previously unrecognized side products, which arise from an unexpected non‐innocent behavior of the commonly employed terminal reductant Et3N. The different rate of formation of these products explains discrepancies in the performance of the two most effective catalysts, [Ir(dtbbpy)(ppy)2][PF6] (dtbbpy=4,4′‐di‐tert‐butyl‐2,2′‐bipyridine) and 3DPAFIPN. Inspired by the observation of PH3 as a minor intermediate, we have developed the first catalytic procedure for the arylation of this key industrial compound. Similar to P4 arylation, this method affords valuable triarylphosphines or tetraarylphosphonium salts depending on the steric profile of the aryl substituents., 31P{1H} NMR spectroscopic studies provide significant, new insights into the mechanism of the recently reported photocatalytic arylation of white phosphorus (P4). Through the first‐time observation of a series of reaction intermediates, these studies have also inspired the development of the first examples of direct, catalytic arylation of PH3, which is a key synthetic intermediate for industrial phosphorus chemistry.

The multidrug resistance protein 4 (MRP4) is highly expressed in platelets and several lines of evidence point to an impact on platelet function. MRP4 represents a transporter for cyclic nucleotides as well as for certain lipid mediators. The aim of the present study was to comprehensively characterize the effect of a short-time specific pharmacological inhibition of MRP4 on signaling pathways in platelets. Transport assays in isolated membrane vesicles showed a concentrationdependent inhibition of MRP4-mediated transport of cyclic nucleotides, thromboxane (Tx)B2 and fluorescein (FITC)- labeled sphingosine-1-phosphate (S1P) by the selective MRP4 inhibitor Ceefourin-1. In ex vivo aggregometry studies in human platelets, Ceefourin-1 significantly inhibited platelet aggregation by about 30-50% when ADP or collagen was used as activating agents, respectively. Ceefourin-1 significantly lowered the ADP-induced activation of integrin aIIbb3, indicated by binding of FITC-fibrinogen (about 50% reduction at 50 mM Ceefourin-1), and reduced calcium influx. Furthermore, pre-incubation with Ceefourin-1 significantly increased PGE1- and cinaciguat-induced vasodilatorstimulated phosphoprotein (VASP) phosphorylation, indicating increased cytosolic cAMP as well as cGMP concentrations, respectively. The release of TxB2 from activated human platelets was also attenuated. Finally, selective MRP4 inhibition significantly reduced both the total area covered by thrombi and the average thrombus size by about 40% in a flow chamber model. In conclusion, selective MRP4 inhibition causes reduced platelet adhesion and thrombus formation under flow conditions. This finding is mechanistically supported by inhibition of integrin aIIbb3 activation, elevated VASP phosphorylation and reduced calcium influx, based on inhibited cyclic nucleotide and thromboxane transport as well as possible further mechanisms.

This paper presents the architecture and techniques used to realize the first direct-digitization open-loop gyroscope frontend, which achieves an input range of +/-8000°/s (4x larger than state of art [1]–[4]) with a noise floor of 0.0047°/s/√Hz, deployed in an inertial measurement unit (IMU) drawing 650μA from a 1.8V supply in gyroscope-only mode.

Phosphorus compounds are ubiquitous in the chemical sciences, finding applications throughout industry and academia. Of particular interest to synthetic chemists are organophosphorus compounds, which contain P—C bonds. However, state-of-the-art processes for the synthesis of these important materials rely on an inefficient, stepwise methodology involving initial oxidation of white phosphorus (P4) with hazardous chlorine gas and the subsequent displacement of chloride ions. Catalytic P4 organofunctionalisation reactions have remained elusive, as they require multiple P—P bond breaking and P—C bond formation events to break down the P4 core, all of which must occur in a controlled manner. Herein, we describe an efficient transition metal-catalyzed process capable of forming P—C bonds from P4. Using blue light photocatalysis, this method directly affords valuable triarylphosphines and tetraarylphosphonium salts in a single reaction step.