Chiral [MnIIMnIII3M'] (M' = NaI, CaII, MnII) and [MnIIMnIII6NaI2] clusters built from an enantiomerically pure Schiff base: synthetic, chiroptical and magnetic properties

From the reaction of manganese halides with the chiral Schiff bases obtained by condensation of o-vanillin and (R)- or (S)-phenylglycinol, 11 complexes based on pentanuclear cages with trigonal bipyramidal [MnIIMnIII3M'] (M'=NaI, CaII, MnII) or enneanuclear [MnIIMnIII6NaI2] cores were synthesized. Structural, supramolecular chirality, and optical properties were explored. The magnetic properties of related systems were reviewed, and the magnetic response of the new systems was rationalized to the bond parameters

Trinuclear Complexes Derived from R/S Schiff Bases - Chiral Single-Molecule Magnets

The employment of enantiomerically pure Schiff bases in manganese chemistry is revealed to be an excellent method to obtain chiral single-molecule magnets and has allowed the characterization of several pairs of enantiomers, for which the magnetic properties were investigated. The reported systems consist of Mn-III-Mn-II-Mn-III linear trimers or Mn-3(III) cations in a triangular arrangement including the first example of a mu(3)-Cl bridge in an isolated manganese triangle

Syntheses, structures, chiroptical and magnetic properties of chiral clusters built from Schiff bases: a novel [MnIIMnIII6NaI2] core

Chiral clusters with MnIIMnIII3NaI and the new MnIIMnIII6NaI2 cores have been synthesised employing enantiomerically pure Schiff bases and halide ligands. The new compounds have been characterized by electronic circular dichroism (ECD) and magnetic susceptibility

Nuclear safety policy working group recommendations on nuclear propulsion safety for the space exploration initiative

An interagency Nuclear Safety Working Group (NSPWG) was chartered to recommend nuclear safety policy, requirements, and guidelines for the Space Exploration Initiative (SEI) nuclear propulsion program. These recommendations, which are contained in this report, should facilitate the implementation of mission planning and conceptual design studies. The NSPWG has recommended a top-level policy to provide the guiding principles for the development and implementation of the SEI nuclear propulsion safety program. In addition, the NSPWG has reviewed safety issues for nuclear propulsion and recommended top-level safety requirements and guidelines to address these issues. These recommendations should be useful for the development of the program's top-level requirements for safety functions (referred to as Safety Functional Requirements). The safety requirements and guidelines address the following topics: reactor start-up, inadvertent criticality, radiological release and exposure, disposal, entry, safeguards, risk/reliability, operational safety, ground testing, and other considerations

From Mesocates to Helicates: Structural, Magnetic and Chiro-Optical Studies on Nickel(II) Supramolecular Assemblies Derived from Tetradentate Schiff Bases

The systematic reactions of a family of tetradentate pyridyl/imine and quinolyl/imine racemic or enantiopure Schiff bases with Ni(NO3)(2) or Ni(ClO4)(2) in the presence of sodium azide yielded, as a function of the starting racemic, chiral or achiral base, a set of chiral, meso or achiral complexes. In all cases, the compounds consist of two Ni-II cations linked by a double azido bridge in its end-on coordination mode. All the dimers exhibit a mesocate supramolecular structure and one of them, the unprecedented mix of helicate and mesocate in 2:1 ratio. The transition from mesocate to helicate conformation has been reached by tuning the flexibility of the central spacers of the Schiff bases and the size of the substituents. Electronic circular dichroism (ECD) studies have been performed for two pairs of enantiomers and interpreted by means of DFT calculations. Susceptibility measurements show a ferromagnetic coupling between the Ni-II cations mediated by the end-on azido bridges

Diversity and Strain Specificity of Plant Cell Wall Degrading Enzymes Revealed by the Draft Genome of Ruminococcus flavefaciens FD-1

Ruminococcus flavefaciens is a predominant cellulolytic rumen bacterium, which forms a multi-enzyme cellulosome complex that could play an integral role in the ability of this bacterium to degrade plant cell wall polysaccharides. Identifying the major enzyme types involved in plant cell wall degradation is essential for gaining a better understanding of the cellulolytic capabilities of this organism as well as highlighting potential enzymes for application in improvement of livestock nutrition and for conversion of cellulosic biomass to liquid fuels

Crosslingual Generalization through Multitask Finetuning

Multitask prompted finetuning (MTF) has been shown to help large language models generalize to new tasks in a zero-shot setting, but so far explorations of MTF have focused on English data and models. We apply MTF to the pretrained multilingual BLOOM and mT5 model families to produce finetuned variants called BLOOMZ and mT0. We find finetuning large multilingual language models on English tasks with English prompts allows for task generalization to non-English languages that appear only in the pretraining corpus. Finetuning on multilingual tasks with English prompts further improves performance on English and non-English tasks leading to various state-of-the-art zero-shot results. We also investigate finetuning on multilingual tasks with prompts that have been machine-translated from English to match the language of each dataset. We find training on these machine-translated prompts leads to better performance on human-written prompts in the respective languages. Surprisingly, we find models are capable of zero-shot generalization to tasks in languages they have never intentionally seen. We conjecture that the models are learning higher-level capabilities that are both task- and language-agnostic. In addition, we introduce xP3, a composite of supervised datasets in 46 languages with English and machine-translated prompts. Our code, datasets and models are freely available at https://github.com/bigscience-workshop/xmtf.Comment: 9 main pages (119 with appendix), 16 figures and 11 table

Cosmological parameters from SDSS and WMAP

We measure cosmological parameters using the three-dimensional power spectrum P(k) from over 200,000 galaxies in the Sloan Digital Sky Survey (SDSS) in combination with WMAP and other data. Our results are consistent with a ``vanilla'' flat adiabatic Lambda-CDM model without tilt (n=1), running tilt, tensor modes or massive neutrinos. Adding SDSS information more than halves the WMAP-only error bars on some parameters, tightening 1 sigma constraints on the Hubble parameter from h~0.74+0.18-0.07 to h~0.70+0.04-0.03, on the matter density from Omega_m~0.25+/-0.10 to Omega_m~0.30+/-0.04 (1 sigma) and on neutrino masses from <11 eV to <0.6 eV (95%). SDSS helps even more when dropping prior assumptions about curvature, neutrinos, tensor modes and the equation of state. Our results are in substantial agreement with the joint analysis of WMAP and the 2dF Galaxy Redshift Survey, which is an impressive consistency check with independent redshift survey data and analysis techniques. In this paper, we place particular emphasis on clarifying the physical origin of the constraints, i.e., what we do and do not know when using different data sets and prior assumptions. For instance, dropping the assumption that space is perfectly flat, the WMAP-only constraint on the measured age of the Universe tightens from t0~16.3+2.3-1.8 Gyr to t0~14.1+1.0-0.9 Gyr by adding SDSS and SN Ia data. Including tensors, running tilt, neutrino mass and equation of state in the list of free parameters, many constraints are still quite weak, but future cosmological measurements from SDSS and other sources should allow these to be substantially tightened.Comment: Minor revisions to match accepted PRD version. SDSS data and ppt figures available at http://www.hep.upenn.edu/~max/sdsspars.htm

Deficit of circulating stem – progenitor cells in opiate addiction: a pilot study

A substantial literature describes the capacity of all addictive drugs to slow cell growth and potentiate apoptosis. Flow cytometry was used as a means to compare two lineages of circulating progenitor cells in addicted patients. Buprenorphine treated opiate addicts were compared with medical patients. Peripheral venous blood CD34+ CD45+ double positive cells were counted as haemopoietic stem cells (HSC's), and CD34+ KDR+ (VEGFR2+) cells were taken as endothelial progenitor cells (EPC's). 10 opiate dependent patients with substance use disorder (SUD) and 11 non-addicted (N-SUD) were studied. The ages were (mean + S.D.) 36.2 + 8.6 and 56.4 + 18.6 respectively (P <0.01). HSC's were not different in the SUD (2.38 + 1.09 Vs. 3.40 + 4.56 cells/mcl). EPC's were however significantly lower in the SUD (0.09 + 0.14 Vs. 0.26 + 0.20 cells/mcl; No. > 0.15, OR = 0.09, 95% C.I. 0.01–0.97), a finding of some interest given the substantially older age of the N-SUD group. These laboratory data are thus consistent with clinical data suggesting accelerated ageing in addicted humans and implicate the important stem cell pool in both addiction toxicology and ageing. They carry important policy implications for understanding the fundamental toxicology of addiction, and suggest that the toxicity both of addiction itself and of indefinite agonist maintenance therapies may have been seriously underestimated