Interpretable Sequence Classification via Discrete Optimization

Sequence classification is the task of predicting a class label given a sequence of observations. In many applications such as healthcare monitoring or intrusion detection, early classification is crucial to prompt intervention. In this work, we learn sequence classifiers that favour early classification from an evolving observation trace. While many state-of-the-art sequence classifiers are neural networks, and in particular LSTMs, our classifiers take the form of finite state automata and are learned via discrete optimization. Our automata-based classifiers are interpretable---supporting explanation, counterfactual reasoning, and human-in-the-loop modification---and have strong empirical performance. Experiments over a suite of goal recognition and behaviour classification datasets show our learned automata-based classifiers to have comparable test performance to LSTM-based classifiers, with the added advantage of being interpretable

Sulfided heterogeneous, bimetallic Ru/Mo catalysts derived from mixtures of Ru 3 (CO) 12 (or RuCl 3 ) and a molybdenum heteropolyanion: The reactions of ethanol with tetrahydroquinoline

Efforts have been made to develop Ru/Mo bimetallic catalyst systems for hydrodenitrogenation (HDN) of tetrahydroquinoline (THQ). In the course of these studies, it was discovered that in ethanol, under hydrogen and in the presence of carbon disulfide (CS 2 ), precatalyst solutions containing ruthenium [as Ru 3 (CO) 12 or RuCl 3 ] and molybdenum [as the H 3 PMo 12 O 40 heteropolyanion (HPA)] decompose to form bimetallic, sulfided particles. Particle diameters run from 0.1 to 5Μm depending on the rate of stirring. Catalyst particles with sizes ranging from 0.1 to 1Μm can be prepared reproducibly. BET-measured surface areas for these size particles ranged from 2 to 20m 2 g −1 . These sulfided particles were found to catalyze, at temperatures of 200–250°C and hydrogen pressures of 200–1000 psig (1.4–6.9 MPa) hydrogen, the N -ethylation of THQ to form N -ethyltetrahydroquinoline ( N -Et-THQ), rather than the formation of propylcyclohexane or propylbenzene, reaction products expected for HDN of THQ. Monometallic heterogeneous catalysts prepared from the individual precatalyst complexes, under identical conditions, show minimal activity for N -ethylation by comparison with the bimetallic catalyst. In the absence of hydrogen, the reaction proceeds so that THQ is converted to quinoline, N -Et-THQ, N -C 4 H 9 -THQ and N -C 6 H 13 -THQ. The latter products appear to arise via acetaldehyde, formed as an intermediate by dehydrogenation of ethanol. Acetaldehyde either condenses with THQ to form N -Et-THQ, or self-condenses (aldol condensation) prior to reaction with THQ, thereby giving higher-homolog alkylation products.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/38297/1/590060505_ftp.pd

Ruthenacycles and Iridacycles as Catalysts for Asymmetric Transfer Hydrogenation and Racemisation

Ruthenacycles, which are easily prepared in a single step by reaction between enantiopure aromatic amines and [Ru(arene)Cl2]2 in the presence of NaOH and KPF6, are very good asymmetric transfer hydrogenation catalysts. A range of aromatic ketones were reduced using isopropanol in good yields with ee’s up to 98%. Iridacycles, which are prepared in similar fashion from [IrCp*Cl2]2 are excellent catalysts for the racemisation of secondary alcohols and chlorohydrins at room temperature. This allowed the development of a new dynamic kinetic resolution of chlorohydrins to the enantiopure epoxides in up to 90% yield and 98% enantiomeric excess (ee) using a mutant of the enzyme Haloalcohol dehalogenase C and an iridacycle as racemisation catalyst.

Addition of Amines to a Carbonyl Ligand: Syntheses, Characterization, and Reactivities of Iridium(III) Porphyrin Carbamoyl Complexes

Treatment of (carbonyl)chloro(meso-tetra-p-tolylporphyrinato)iridium(III), (TTP)Ir(CO)Cl (1), with excess primary amines at 23 °C in the presence of Na2CO3 produces the trans-amine-coordinated iridium carbamoyl complexes (TTP)Ir(NH2R)[C(O)NHR] (R = Bn (2a), n-Bu (2b), i-Pr (2c), t-Bu (2d)) with isolated yields up to 94%. The trans-amine ligand is labile and can be replaced with quinuclidine (1-azabicyclo[2.2.2]octane, ABCO), 1-methylimidazole (1-MeIm), triethyl phosphite (P(OEt)3), and dimethylphenylphosphine (PMe2Ph) at 23 °C to afford the hexacoordinated carbamoyl complexes (TTP)Ir(L)[C(O)NHR] (for R = Bn: L = ABCO (3a), 1-MeIm (4a), P(OEt)3 (5a), PMe2Ph (6a)). On the basis of ligand displacement reactions and equilibrium studies, ligand binding strengths to the iridium metal center were found to decrease in the order PMe2Ph \u3e P(OEt)3 \u3e 1-MeIm \u3e ABCO \u3e BnNH2 ≫ Et3N, PCy3. The carbamoyl complexes (TTP)Ir(L)[C(O)NHR] (L = RNH2 (2a,b), 1-MeIm (4a)) undergo protonolysis with HBF4 to give the cationic carbonyl complexes [(TTP)Ir(NH2R)(CO)]BF4 (7a,b) and [(TTP)Ir(1-MeIm)(CO)]BF4 (8), respectively. In contrast, the carbamoyl complexes (TTP)Ir(L)[C(O)NHR] (L = P(OEt)3 (5a), PMe2Ph (6a,c)) reacted with HBF4 to afford the complexes [(TTP)Ir(PMe2Ph)]BF4 (9) and [(TTP)IrP(OEt)3]BF4 (10), respectively. The carbamoyl complexes (TTP)Ir(L)[C(O)NHR] (L = RNH2 (2a–d), 1-MeIm (4a), P(OEt)3 (5b), PMe2Ph (6c)) reacted with methyl iodide to give the iodo complexes (TTP)Ir(L)I (L = RNH2 (11a–d), 1-MeIm (12), P(OEt)3(13), PMe2Ph (14)). Reactions of the complexes [(TTP)Ir(PMe2Ph)]BF4 (9) and [(TTP)IrP(OEt)3]BF4 (10) with [Bu4N]I, benzylamine (BnNH2), and PMe2Ph afforded (TTP)Ir(PMe2Ph)I (14), (TTP)Ir[P(OEt)3]I (13), [(TTP)Ir(PMe2Ph)(NH2Bn)]BF4 (16), and trans-[(TTP)Ir(PMe2Ph)2]BF4 (17), respectively. Metrical details for the molecular structures of 4a and17 are reported

Activation and Deactivation of a Robust Immobilized Cp*Ir-Transfer Hydrogenation Catalyst: A Multielement in Situ X-ray Absorption Spectroscopy Study

A highly robust immobilized [Cp*IrCl2]2 precatalyst on Wang resin for transfer hydrogenation, which can be recycled up to 30 times, was studied using a novel combination of X-ray absorption spectroscopy (XAS) at Ir L3-edge, Cl K-edge, and K K-edge. These culminate in in situ XAS experiments that link structural changes of the Ir complex with its catalytic activity and its deactivation. Mercury poisoning and “hot filtration” experiments ruled out leached Ir as the active catalyst. Spectroscopic evidence indicates the exchange of one chloride ligand with an alkoxide to generate the active precatalyst. The exchange of the second chloride ligand, however, leads to a potassium alkoxide–iridate species as the deactivated form of this immobilized catalyst. These findings could be widely applicable to the many homogeneous transfer hydrogenation catalysts with Cp*IrCl substructure

Tumour treating fields in a combinational therapeutic approach

© Branter et al. The standard of care for patients with newly diagnosed Glioblastoma multiforme (GBM) has remained unchanged since 2005, with patients undergoing maximal surgical resection, followed by radiotherapy plus concomitant and maintenance Temozolomide. More recently, Tumour treating fields (TTFields) therapy has become FDA approved for adult recurrent and adult newly-diagnosed GBM following the EF-11 and EF-14 trials, respectively. TTFields is a non-invasive anticancer treatment which utilizes medium frequency alternating electric fields to target actively dividing cancerous cells. TTFields selectively targets cells within mitosis through interacting with key mitotic proteins to cause mitotic arrest and cell death. TTFields therapy presents itself as a candidate for the combinational therapy route due to the lack of overlapping toxicities associated with electric fields. Here we review current literature pertaining to TTFields in combination with alkylating agents, radiation, anti-angiogenics, mitotic inhibitors, immunotherapies, and also with novel agents. This review highlights the observed synergistic and additive effects of combining TTFields with various other therapies, as well highlighting the strategies relating to combinations with electric fields