Multimetallic lithium complexes derived from the acids Ph₂C(X)CO₂H (X = OH, NH₂) : synthesis, structure and ring opening polymerization of lactides and lactones

Reaction of LiOR (R=t-Bu, Ph) with the acids 2,2/-Ph₂C(X)(CO₂H), X=OH (benzH), NH₂ (dpgH) was investigated. For benzH, one equivalent LiOt-Bu in THF afforded [Li(benz)]2⋅2THF (1⋅2THF), which adopts a 1D chain structure. If acetonitrile is used (mild conditions), another polymorph of 1 is isolated; LiOPh also led to 1. Robust work-up afforded [Li₇(benz)₇(MeCN)] 2MeCN THF (2⋅2MeCN⋅THF). Use of LiOt-Bu (2 equivalents) led to {Li₈(Ot-Bu)₂[(benz)](OCPh₂CO₂CPh₂CO2t-Bu)₂(THF)₄} (3), the core of which comprises two open cubes linked by benz ligands. For dpgH, two equivalents of LiOt-Bu in THF afforded [Li6(Ot-Bu)₂(dpg)₂(THF)₂] (4), which contains an Li₂Ov 6-step ladder. Similar reaction of LiOPh afforded [Li₈(PhO)₄(dpg)₄(MeCN)₄] (5). Complexes 1–5 were screened for their potential as catalysts for ring opening polymerization (ROP) of ϵ-caprolactone (ϵ-CL), rac-lactide (rac-LA) and δ-valerolactone (δ-VL). For ROP of ϵ-CL, conversions > 70 % were achievable at 110 °C with good control. For rac-LA and δ-VL, temperatures of at least 110 °C over 12 h were necessary for activity (conversions > 60 %). Systems employing 2 were inactiv

A novel fluorescent "turn-on" chemosensor for nanomolar detection of Fe(III) from aqueous solution and its application in living cells imaging

An electronically active and spectral sensitive fluorescent “turn-on” chemosensor (BTP-1) based on the benzo-thiazolo-pyrimidine unit was designed and synthesized for the highly selective and sensitive detection of Fe³⁺ from aqueous medium. With Fe³⁺, the sensor BTP-1 showed a remarkable fluorescence enhancement at 554 nm (λex=314 nm) due to the inhibition of photo-induced electron transfer. The sensor formed a host-guest complex in 1:1 stoichiometry with the detection limit down to 0.74 nM. Further, the sensor was successfully utilized for the qualitative and quantitative intracellular detection of Fe³⁺ in two liver cell lines i.e., HepG2 cells (human hepatocellular liver carcinoma cell line) and HL-7701 cells (human normal liver cell line) by a confocal imaging technique

The Future Role of Strategic Landpower

Recent Russian aggression in Ukraine has reenergized military strategists and senior leaders to evaluate the role of strategic Landpower. American leadership in the European theater has mobilized allies and partners to reconsider force postures for responding to possible aggression against NATO members. Although Russian revisionist activity remains a threat in Europe, the challenges in the Pacific for strategic Landpower must also be considered. At the same time, the homeland, the Arctic, climate change, and the results of new and emerging technology also challenge the application of strategic Landpower. This publication serves as part of an enduring effort to evaluate strategic Landpower’s role, authorities, and resources for accomplishing the national strategic goals the Joint Force may face in the next conflict. This study considers multinational partners, allies, and senior leaders that can contribute to overcoming these enduring challenges. The insights derived from this study, which can be applied to both the European and Indo-Pacific theaters, should help leaders to consider these challenges, which may last a generation. Deterrence demands credible strategic response options integrated across warfighting functions. This valuable edition will continue the dialogue about addressing these issues as well as other emerging ones.https://press.armywarcollege.edu/monographs/1959/thumbnail.jp

Planetary Science Technology Infusion Study: Findings and Recommendations Status

The Planetary Science Division (PSD) within the National Aeronautics and Space Administrations (NASA) Science Mission Directorate (SMD) at NASA Headquarters sought to understand how to better realize a scientific return on spacecraft system technology investments currently being funded. In order to achieve this objective, a team at NASA Glenn Research Center was tasked with surveying the science and mission communities to collect their insight on technology infusion and additionally sought inputs from industry, universities, and other organizations involved with proposing for future PSD missions. This survey was undertaken by issuing a Request for Information (RFI) activity that requested input from the proposing community on present technology infusion efforts. The Technology Infusion Study was initiated in March 2013 with the release of the RFI request. The evaluation team compiled and assessed this input in order to provide PSD with recommendations on how to effectively infuse new spacecraft systems technologies that it develops into future competed missions enabling increased scientific discoveries, lower mission cost, or both. This team is comprised of personnel from the Radioisotope Power Systems (RPS) Program and the In-Space Propulsion Technology (ISPT) Program staff.The RFI survey covered two aspects of technology infusion: 1) General Insight, including: their assessment of barriers to technology infusion as related to infusion approach; technology readiness; information and documentation products; communication; integration considerations; interaction with technology development areas; cost-capped mission areas; risk considerations; system level impacts and implementation; and mission pull. 2) Specific technologies from the most recent PSD Announcements of Opportunities (AOs): The Advanced Stirling Radioisotope Generator (ASRG), aerocapture and aeroshell hardware technologies, the NASA Evolutionary Xenon Thruster (NEXT) ion propulsion system, and the Advanced Materials Bi-propellant Rocket (AMBR) engine.This report will present the teams Findings from the RFI inputs and the recommendations that arose from these findings. Methodologies on the findings and recommendations development are discussed

Water-Soluble Rhenium Phosphine Complexes Incorporating the Ph2C(X) Motif (X = O–, NH–): Structural and Cytotoxicity Studies

Reaction of [ReOCl3(PPh3)2] or [ReO2I(PPh3)2] with 2,2′-diphenylglycine (dpgH2) in refluxing ethanol afforded the air-stable complex [ReO(dpgH)(dpg)(PPh3)] (1). Treatment of [ReO(OEt)I2(PPh3)2] with 1,2,3-triaza-7-phosphaadamantane (PTA) afforded the complex [ReO(OEt)I2(PTA)2] (2). Reaction of [ReOI2(PTA)3] with dpgH2 led to the isolation of the complex [Re(NCPh2)I2(PTA)3]·0.5EtOH (3·0.5EtOH). A similar reaction but using [ReOX2(PTA)3] (X = Cl, Br) resulted in the analogous halide complexes [Re(NCPh2)Cl2(PTA)3]·2EtOH (4·2EtOH) and [Re(NCPh2)(PTA)3Br2]·1.6EtOH (5·1.6EtOH). Using benzilic acid (2,2′-diphenylglycolic acid, benzH) with 2 afforded the complex [ReO(benz)2(PTA)][PTAH]·EtOH (6·EtOH). The potential for the formation of complexes using radioisotopes with relatively short half-lives suitable for nuclear medicine applications by developing conditions for [Re(NCPh2)(dpg)I(PTA)3] (7)[ReO4]− in a 4 h time scale was investigated. A procedure for the technetium analog of complex [Re(NCPh2)I2(PTA)3] (3) from 99mTc[TcO4]− was then investigated. The molecular structures of 1–7 are reported; complexes 3–7 have been studied using in vitro cell assays (HeLa, HCT116, HT-29, and HEK 293) and were found to have IC50 values in the range of 29–1858 μM

Physiotherapy and occupational therapy vs no therapy in mild to moderate Parkinson disease: a randomized clinical trial

IMPORTANCE It is unclear whether physiotherapy and occupational therapy are clinically effective and cost-effective in Parkinson disease (PD). OBJECTIVE To perform a large pragmatic randomized clinical trial to evaluate the clinical effectiveness of individualized physiotherapy and occupational therapy in PD. DESIGN, SETTING, AND PARTICIPANTS The PD REHAB Trial was a multicenter, open-label, parallel group, controlled efficacy trial. A total of 762 patients with mild to moderate PD were recruited from 38 sites across the United Kingdom. Recruitment took place between October 2009 and June 2012, with 15 months of follow-up. INTERVENTIONS Participants with limitations in activities of daily living (ADL) were randomized to physiotherapy and occupational therapy or no therapy. MAIN OUTCOMES AND MEASURES The primary outcome was the Nottingham Extended Activities of Daily Living (NEADL) Scale score at 3 months after randomization. Secondary outcomes were health-related quality of life (assessed by Parkinson Disease Questionnaire–39 and EuroQol-5D); adverse events; and caregiver quality of life. Outcomes were assessed before trial entry and then 3, 9, and 15 months after randomization. RESULTS Of the 762 patients included in the study (mean [SD] age, 70 [9.1] years), 381 received physiotherapy and occupational therapy and 381 received no therapy. At 3 months, there was no difference between groups in NEADL total score (difference, 0.5 points; 95%CI, −0.7 to 1.7; P = .41) or Parkinson Disease Questionnaire–39 summary index (0.007 points; 95%CI, −1.5 to 1.5; P = .99). The EuroQol-5D quotient was of borderline significance in favor of therapy (−0.03; 95%CI, −0.07 to −0.002; P = .04). The median therapist contact time was 4 visits of 58 minutes over 8 weeks. Repeated-measures analysis showed no difference in NEADL total score, but Parkinson Disease Questionnaire–39 summary index (diverging 1.6 points per annum; 95%CI, 0.47 to 2.62; P = .005) and EuroQol-5D score (0.02; 95%CI, 0.00007 to 0.03; P = .04) showed small differences in favor of therapy. There was no difference in adverse events. CONCLUSIONS AND RELEVANCE Physiotherapy and occupational therapy were not associated with immediate or medium-term clinically meaningful improvements in ADL or quality of life in mild to moderate PD. This evidence does not support the use of low-dose, patient-centered, goal-directed physiotherapy and occupational therapy in patients in the early stages of PD. Future research should explore the development and testing of more structured and intensive physical and occupational therapy programs in patients with all stages of PD

Climate engineering reconsidered

Stratospheric injection of sulphate aerosols has been advocated as an emergency geoengineering measure to tackle dangerous climate change, or as a stop-gap until atmospheric carbon dioxide levels are reduced. But it may not prove to be the game-changer that some imagine

The PTF Orion Project: a Possible Planet Transiting a T-Tauri Star

We report observations of a possible young transiting planet orbiting a previously known weak-lined T-Tauri star in the 7-10 Myr old Orion-OB1a/25-Ori region. The candidate was found as part of the Palomar Transient Factory (PTF) Orion project. It has a photometric transit period of 0.448413 +- 0.000040 days, and appears in both 2009 and 2010 PTF data. Follow-up low-precision radial velocity (RV) observations and adaptive optics imaging suggest that the star is not an eclipsing binary, and that it is unlikely that a background source is blended with the target and mimicking the observed transit. RV observations with the Hobby-Eberly and Keck telescopes yield an RV that has the same period as the photometric event, but is offset in phase from the transit center by approximately -0.22 periods. The amplitude (half range) of the RV variations is 2.4 km/s and is comparable with the expected RV amplitude that stellar spots could induce. The RV curve is likely dominated by stellar spot modulation and provides an upper limit to the projected companion mass of M_p sin i_orb < 4.8 +- 1.2 M_Jup; when combined with the orbital inclination, i orb, of the candidate planet from modeling of the transit light curve, we find an upper limit on the mass of the planetary candidate of M_p < 5.5 +- 1.4 M_Jup. This limit implies that the planet is orbiting close to, if not inside, its Roche limiting orbital radius, so that it may be undergoing active mass loss and evaporation.Comment: Corrected typos, minor clarifications; minor updates/corrections to affiliations and bibliography. 35 pages, 10 figures, 3 tables. Accepted to Ap

Rationale and Design of the SENECA (StEm cell iNjECtion in cAncer survivors) Trial

Objectives SENECA (StEm cell iNjECtion in cAncer survivors) is a phase I, randomized, double-blind, placebo-controlled study to evaluate the safety and feasibility of delivering allogeneic mesenchymal stromal cells (allo-MSCs) transendocardially in subjects with anthracycline-induced cardiomyopathy (AIC). Background AIC is an incurable and often fatal syndrome, with a prognosis worse than that of ischemic or nonischemic cardiomyopathy. Recently, cell therapy with MSCs has emerged as a promising new approach to repair damaged myocardium. Methods The study population is 36 cancer survivors with a diagnosis of AIC, left ventricular (LV) ejection fraction ≤40%, and symptoms of heart failure (NYHA class II-III) on optimally-tolerated medical therapy. Subjects must be clinically free of cancer for at least two years with a ≤ 30% estimated five-year risk of recurrence. The first six subjects participated in an open-label, lead-in phase and received 100 million allo-MSCs; the remaining 30 will be randomized 1:1 to receive allo-MSCs or vehicle via 20 transendocardial injections. Efficacy measures (obtained at baseline, 6 months, and 12 months) include MRI evaluation of LV function, LV volumes, fibrosis, and scar burden; assessment of exercise tolerance (six-minute walk test) and quality of life (Minnesota Living with Heart Failure Questionnaire); clinical outcomes (MACE and cumulative days alive and out of hospital); and biomarkers of heart failure (NT-proBNP). Conclusions This is the first clinical trial using direct cardiac injection of cells for the treatment of AIC. If administration of allo-MSCs is found feasible and safe, SENECA will pave the way for larger phase II/III studies with therapeutic efficacy as the primary outcome