sj-pdf-1-smm-10.1177_09622802221080753 - Supplemental material for A Bayesian phase I/II biomarker-based design for identifying subgroup-specific optimal dose for immunotherapy

Supplemental material, sj-pdf-1-smm-10.1177_09622802221080753 for A Bayesian phase I/II biomarker-based design for identifying subgroup-specific optimal dose for immunotherapy by Beibei Guo and Yong Zang in Statistical Methods in Medical Research</p

Supplemental material for A Bayesian adaptive phase II clinical trial design accounting for spatial variation

Supplemental material for A Bayesian adaptive phase II clinical trial design accounting for spatial variation by Beibei Guo and Yong Zang in Statistical Methods in Medical Research</p

Treatment Comparisons in Adaptive Platform Trials Adjusting for Temporal Drift

An adaptive platform trial (APT) is a multi-arm trial in the context of a single disease where treatment arms are allowed to enter or leave the trial based on some decision rule. If a treatment enters the trial later than the control arm, there exist nonconcurrent controls who were not randomized between the two arms under comparison. As APTs typically take long periods of time to conduct, temporal drift may occur, which requires the treatment comparisons to be adjusted for this temporal change. Under the causal inference framework, we propose two approaches for treatment comparisons in APTs that account for temporal drift, both based on propensity score weighting. In particular, to address unmeasured confounders, one approach is doubly robust in the sense that it remains valid so long as either the propensity score model is correctly specified or the time effect model is correctly specified. Simulation study shows that our proposed approaches have desirable operating characteristics with well controlled Type I error rates and high power with or without unmeasured confounders.</p

Ruthenium Complexes with PNN Pincer Ligands Based on (Chiral) Pyrrolidines: Synthesis, Structure, and Dynamic Stereochemistry

We report the synthesis of lutidine-based PNN type metal pincer complexes, using achiral (pyrrolidine) as well as chiral ((R,R)-2,5-dimethylpyrrolidine and (R)-2-methylpyrrolidine) substituents at the N side arm of the pincer ligand. With the six-coordinate saturated Ru pincers (PNN)­Ru­(H)­(CO)­(Cl), which have an aromatic pyridine ligand backbone, as the starting materials, treatment with strong base (KOtBu) generated the corresponding dearomatized pincer complexes (PNN′)­Ru­(H)­(CO). Spectroscopic, crystallographic, and computational studies demonstrate that the C-centered chirality from the chiral pyrrolidine group exerts a small but non-negligible influence on the preferred stereochemistry at Ru (and N in the case of (R)-2-methylpyrrolidine) that is reflected in the equilibrium distribution of diastereomers of these Ru complexes in solution. Our data show that the N- and Ru-based stereogenic centers in this class of compounds are stereochemically labile and the mechanisms for epimerization are discussed. Inversion at the Ru center in the dearomatized complexes is proposed to occur via a rearomatized Ru(0) intermediate in which the Ru-bound hydride is transferred to the ligand. Support for this comes from the spectroscopic characterization of a closely related Ru(0) species that is obtained by reaction with CO. Testing these catalysts in enantioselective oxa-Michael addition or transfer hydrogenation led to racemic products, while a low ee (8%) was observed in the hydrogenation of 4-fluoroacetophenone. The lack of appreciable enantioinduction with these catalysts is ascribed to the kinetic lability of the Ru stereocenter, which results in the formation of equilibrium mixtures in which several diastereomers of the catalyst are present

Antirrhinum reticulatum

The newly designed organic ligand 2-(<i>p</i>-bromophenyl)-1<i>H</i>-imidazole-4,5-dicarboxylic acid (<i>p</i>-BrPhH₃IDC) has been successfully prepared and its coordination features were explored. By the reactions of <i>p</i>-BrPhH₃IDC with main group or transition metals, six metal–organic frameworks (MOFs), namely, [Ca­(<i>p</i>-BrPhHIDC)­(H₂O)₂]_<i>n</i> (<b>1</b>), [Sr­(<i>p</i>-BrPhHIDC)­(H₂O)]_<i>n</i> (<b>2</b>), [Zn­(<i>p</i>-BrPhHIDC)­(H₂O)]_<i>n</i> (<b>3</b>), {[Co­(<i>p</i>-BrPhH₂IDC)₂]­·2H₂O}_<i>n</i> (<b>4</b>), [Cd_1.5(<i>p</i>-BrPhHIDC)­(<i>p</i>-BrPhH₂IDC)­(H₂O)]_<i>n</i> (<b>5</b>), and {[Cd₂(<i>p</i>-BrPhHIDC)₂­(4,4′-bipy)]­·4H₂O}_<i>n</i> (4,4′-bipy = 4,4′-bipyridine) (<b>6</b>) have been synthesized under hydro­(solvo)­thermal conditions. X-ray single-crystal analyses reveal that they have rich structural chemistry ranging from one-dimensional (1D) (<b>3</b>), two-dimensional (2D) (<b>1</b>,<b> 2</b>,<b> 4</b>, and <b>5</b>) to three-dimensional (3D) polymers (<b>6</b>). Furthermore, the existence of intermolecular hydrogen bonds and/or π···π stacking interactions between the aromatic groups supplies the additional stabilization for the solid-state supramolecular structures of polymers <b>3</b>, <b>4</b>, and <b>5</b>. The solid-state photoluminescence properties of the polymers <b>1</b>–<b>6</b> have been investigated as well

Construction and Properties of Six Metal–Organic Frameworks Based on the Newly Designed 2‑(<i>p</i>‑Bromophenyl)-Imidazole Dicarboxylate Ligand

The newly designed organic ligand 2-(p-bromophenyl)-1H-imidazole-4,5-dicarboxylic acid (p-BrPhH3IDC) has been successfully prepared and its coordination features were explored. By the reactions of p-BrPhH3IDC with main group or transition metals, six metal–organic frameworks (MOFs), namely, [Ca­(p-BrPhHIDC)­(H2O)2]n (1), [Sr­(p-BrPhHIDC)­(H2O)]n (2), [Zn­(p-BrPhHIDC)­(H2O)]n (3), {[Co­(p-BrPhH2IDC)2]­·2H2O}n (4), [Cd1.5(p-BrPhHIDC)­(p-BrPhH2IDC)­(H2O)]n (5), and {[Cd2(p-BrPhHIDC)2­(4,4′-bipy)]­·4H2O}n (4,4′-bipy = 4,4′-bipyridine) (6) have been synthesized under hydro­(solvo)­thermal conditions. X-ray single-crystal analyses reveal that they have rich structural chemistry ranging from one-dimensional (1D) (3), two-dimensional (2D) (1, 2, 4, and 5) to three-dimensional (3D) polymers (6). Furthermore, the existence of intermolecular hydrogen bonds and/or π···π stacking interactions between the aromatic groups supplies the additional stabilization for the solid-state supramolecular structures of polymers 3, 4, and 5. The solid-state photoluminescence properties of the polymers 1–6 have been investigated as well

Ruthenium Complexes with PNN Pincer Ligands Based on (Chiral) Pyrrolidines: Synthesis, Structure, and Dynamic Stereochemistry

We report the synthesis of lutidine-based PNN type metal pincer complexes, using achiral (pyrrolidine) as well as chiral ((R,R)-2,5-dimethylpyrrolidine and (R)-2-methylpyrrolidine) substituents at the N side arm of the pincer ligand. With the six-coordinate saturated Ru pincers (PNN)­Ru­(H)­(CO)­(Cl), which have an aromatic pyridine ligand backbone, as the starting materials, treatment with strong base (KOtBu) generated the corresponding dearomatized pincer complexes (PNN′)­Ru­(H)­(CO). Spectroscopic, crystallographic, and computational studies demonstrate that the C-centered chirality from the chiral pyrrolidine group exerts a small but non-negligible influence on the preferred stereochemistry at Ru (and N in the case of (R)-2-methylpyrrolidine) that is reflected in the equilibrium distribution of diastereomers of these Ru complexes in solution. Our data show that the N- and Ru-based stereogenic centers in this class of compounds are stereochemically labile and the mechanisms for epimerization are discussed. Inversion at the Ru center in the dearomatized complexes is proposed to occur via a rearomatized Ru(0) intermediate in which the Ru-bound hydride is transferred to the ligand. Support for this comes from the spectroscopic characterization of a closely related Ru(0) species that is obtained by reaction with CO. Testing these catalysts in enantioselective oxa-Michael addition or transfer hydrogenation led to racemic products, while a low ee (8%) was observed in the hydrogenation of 4-fluoroacetophenone. The lack of appreciable enantioinduction with these catalysts is ascribed to the kinetic lability of the Ru stereocenter, which results in the formation of equilibrium mixtures in which several diastereomers of the catalyst are present

Organocatalytic Ring-Opening Copolymerization of Trimethylene Carbonate and Dithiolane Trimethylene Carbonate: Impact of Organocatalysts on Copolymerization Kinetics and Copolymer Microstructures

The ring opening copolymerization of trimethylene carbonate (TMC) and dithiolane trimethylene carbonate (DTC) using acidic and basic organocatalysts, i.e., diphenyl phosphate (DPP) and triazabicyclo[4.4.0]­dec-5-ene (TBD), was systemically investigated. Interestingly, DPP and TBD gave rise to completely different polymerization kinetics and copolymer sequences. The copolymerization of TMC and DTC using methoxy poly­(ethylene glycol) (mPEG–OH) as an initiator and DPP as a catalyst proceeded in a first-order manner and to near completion in 72 h for both monomers, yielding well-controlled copolymers with random sequences, predictable molar mass, and low dispersity (<i>M</i>_w/<i>M</i>_n = 1.09–1.19). By contrast, TBD brought about much faster copolymerization of TMC and DTC under similar conditions (high monomer conversion achieved in 2–4 h), to furnish copolymers with controlled molar mass and moderate dispersity (<i>M</i>_w/<i>M</i>_n = 1.27–1.80). Moreover, polymerization kinetics revealed that DTC was preferentially polymerized followed by first-order polymerization of TMC, leading to blocky copolymers. These results signify that type of organocatalysts has a critical influence on polymerization kinetics of cyclic carbonates, copolymer sequence, and molar mass control

Construction and Properties of Six Metal–Organic Frameworks Based on the Newly Designed 2‑(<i>p</i>‑Bromophenyl)-Imidazole Dicarboxylate Ligand

The newly designed organic ligand 2-(<i>p</i>-bromophenyl)-1<i>H</i>-imidazole-4,5-dicarboxylic acid (<i>p</i>-BrPhH₃IDC) has been successfully prepared and its coordination features were explored. By the reactions of <i>p</i>-BrPhH₃IDC with main group or transition metals, six metal–organic frameworks (MOFs), namely, [Ca­(<i>p</i>-BrPhHIDC)­(H₂O)₂]_<i>n</i> (<b>1</b>), [Sr­(<i>p</i>-BrPhHIDC)­(H₂O)]_<i>n</i> (<b>2</b>), [Zn­(<i>p</i>-BrPhHIDC)­(H₂O)]_<i>n</i> (<b>3</b>), {[Co­(<i>p</i>-BrPhH₂IDC)₂]­·2H₂O}_<i>n</i> (<b>4</b>), [Cd_1.5(<i>p</i>-BrPhHIDC)­(<i>p</i>-BrPhH₂IDC)­(H₂O)]_<i>n</i> (<b>5</b>), and {[Cd₂(<i>p</i>-BrPhHIDC)₂­(4,4′-bipy)]­·4H₂O}_<i>n</i> (4,4′-bipy = 4,4′-bipyridine) (<b>6</b>) have been synthesized under hydro­(solvo)­thermal conditions. X-ray single-crystal analyses reveal that they have rich structural chemistry ranging from one-dimensional (1D) (<b>3</b>), two-dimensional (2D) (<b>1</b>,<b> 2</b>,<b> 4</b>, and <b>5</b>) to three-dimensional (3D) polymers (<b>6</b>). Furthermore, the existence of intermolecular hydrogen bonds and/or π···π stacking interactions between the aromatic groups supplies the additional stabilization for the solid-state supramolecular structures of polymers <b>3</b>, <b>4</b>, and <b>5</b>. The solid-state photoluminescence properties of the polymers <b>1</b>–<b>6</b> have been investigated as well

Construction and Properties of Six Metal–Organic Frameworks Based on the Newly Designed 2‑(<i>p</i>‑Bromophenyl)-Imidazole Dicarboxylate Ligand

The newly designed organic ligand 2-(<i>p</i>-bromophenyl)-1<i>H</i>-imidazole-4,5-dicarboxylic acid (<i>p</i>-BrPhH₃IDC) has been successfully prepared and its coordination features were explored. By the reactions of <i>p</i>-BrPhH₃IDC with main group or transition metals, six metal–organic frameworks (MOFs), namely, [Ca­(<i>p</i>-BrPhHIDC)­(H₂O)₂]_<i>n</i> (<b>1</b>), [Sr­(<i>p</i>-BrPhHIDC)­(H₂O)]_<i>n</i> (<b>2</b>), [Zn­(<i>p</i>-BrPhHIDC)­(H₂O)]_<i>n</i> (<b>3</b>), {[Co­(<i>p</i>-BrPhH₂IDC)₂]­·2H₂O}_<i>n</i> (<b>4</b>), [Cd_1.5(<i>p</i>-BrPhHIDC)­(<i>p</i>-BrPhH₂IDC)­(H₂O)]_<i>n</i> (<b>5</b>), and {[Cd₂(<i>p</i>-BrPhHIDC)₂­(4,4′-bipy)]­·4H₂O}_<i>n</i> (4,4′-bipy = 4,4′-bipyridine) (<b>6</b>) have been synthesized under hydro­(solvo)­thermal conditions. X-ray single-crystal analyses reveal that they have rich structural chemistry ranging from one-dimensional (1D) (<b>3</b>), two-dimensional (2D) (<b>1</b>,<b> 2</b>,<b> 4</b>, and <b>5</b>) to three-dimensional (3D) polymers (<b>6</b>). Furthermore, the existence of intermolecular hydrogen bonds and/or π···π stacking interactions between the aromatic groups supplies the additional stabilization for the solid-state supramolecular structures of polymers <b>3</b>, <b>4</b>, and <b>5</b>. The solid-state photoluminescence properties of the polymers <b>1</b>–<b>6</b> have been investigated as well