Dimer Formation Research Articles

Water dimer in CCl4 investigated by in-situ infrared spectroscopy and computational analysis

The low solubility of solute molecules in a nonpolar solvent and the weak interactions between solute and solvent molecules can be utilized to study isolated solute molecules. The in-situ inclusion process of H2O and D2O in CCl4 was observed by infrared absorption spectroscopy. These in-situ spectra showed deviations from the monomer spectrum over time attributed to the formation of water dimers. The water dimer spectrum was extracted by subtraction between the time-series spectra. DFT calculations allowed the assignment of the four vibrational modes in the dimer spectrum. The most notable changes from the monomer to the dimer spectra were in the donor molecule, which showed a peak redshift and a large increase in the absorption strengths, especially for the donor OH (OD) bond which participates in the hydrogen bonding to the acceptor water molecule. Using free energy calculations, the equilibrium constants of H2O and D2O dimers dissolved in CCl4 were determined to be 0.013 and 0.015, respectively, and the concentrations were determined to be ∼1 μM. The intensity ratio between the v3 mode of the water monomer and the vBD mode of the dimer calculated through DFT was found to be in close agreement with the ratios from the monomer and dimer spectra. In contrast, when the solvent was chloroform, the increase of the vBD mode of the dimer from the experiment did not agree with that from the calculations, indicating that the specific interaction of the water molecules with chloroform should be considered.

Abstract IA011: Polymerase-based bypass of atypical UV photoproducts

Abstract UV light is a ubiquitous environmental mutagen that is an etiological cause of skin cancers like melanoma. While the genomes of human cutaneous melanomas have high mutation burdens primarily consisting of C to T substitutions in TC and CC dinucleotides (consistent with cyclobutane pyrimidine dimer formation), many of the driver mutations contributing to disease progression involve other types of substitutions at non-dipyrimidine sequences. Our whole genome sequencing of UVB or UVC irradiated yeast has revealed non-canonical UV induced substitution types. These mutations included TA to TT and AC to TT substitutions that commonly occur as activating BRAF mutations in human melanomas. UV treatment and sequencing of deletion mutants of DNA polymerase eta, the protein mutated in human XPV patients, indicated that this polymerase does not impact TA to TT mutagenesis, but contributes to the formation of AC to TT substitutions. Surprisingly, loss of pol eta revealed additional CA to AA substitutions, highlighting another UV-induced mutation class possibly created by a non-canonical photoproduct. All novel mutation classes in pol eta deficient yeast displayed transcriptional asymmetry, consistent with the repair of the cognate lesion by transcription-coupled nucleotide excision repair. However, UV-induced mutations lacked replication asymmetry in both wild type and rad30Δ yeast, suggesting TLS occurs nearly equally on leading and lagging strands. Both TA to TT and AC to TT substitutions were dependent on DNA polymerase zeta, and altered by a mutant of DNA polymerase epsilon, suggesting the involvement of both TLS and replicative polymerases in UV-induced mutagenesis. These results emphasize the importance of non-canonical UV lesions in driving melanomagenesis, provide mechanisms of how these lesions result in mutations, and suggest the variable accuracy of TLS polymerases across from atypical UV photoproducts may alter the trajectory of skin cancer evolution in XPV patients. Citation Format: Steven A. Roberts. Polymerase-based bypass of atypical UV photoproducts [abstract]. In: Proceedings of the AACR Special Conference in Cancer Research: DNA Damage Repair: From Basic Science to Future Clinical Application; 2024 Jan 9-11; Washington, DC. Philadelphia (PA): AACR; Cancer Res 2024;84(1 Suppl):Abstract nr IA011.

Impact of temperature on the role of Criegee intermediates and peroxy radicals in dimer formation from β-pinene ozonolysis

Abstract. Stabilized Criegee intermediates (SCIs) and organic peroxy radicals (RO2) are critical in atmospheric oxidation processes and secondary organic aerosol (SOA) formation. However, the influence of temperature on their corresponding reaction mechanisms in SOA formation is unclear. Through utilizing formic acid as a SCI scavenger and regulating the ratio of hydroperoxyl radials (HO2) to RO2 ([HO2]/[RO2]) from ∼ 0.3 to ∼ 1.9 using different concentrations of CO, the roles of RO2 and SCIs in SOA formation were investigated from 248 to 298 K, particularly for dimer formation in β-pinene ozonolysis. The SOA yield increased by 21 % from 298 to 273 K, while it decreased by 40 % from 273 to 248 K. Both changing [HO2]/[RO2] and scavenging SCIs significantly affect SOA yield and composition. SCI reactions accounted for more than 40 % of dimer and SOA mass formation for all temperatures. Increasing [HO2]/[RO2] inhibited dimer and SOA formation, and this inhibition became larger with decreasing temperature. Compared to low [HO2]/[RO2] (0.30–0.34), the dimer abundance at high [HO2]/[RO2] (1.53–1.88) decreased by about 31 % at 298 K and 70 % at 248 K. [HO2]/[RO2] has a specific impact on SCI-controlled dimers at lower temperatures by especially influencing the C9–SCI reactions with RO2. The dimers formed from C9–SCI reactions with RO2 were estimated to decrease by 61 % at high [HO2]/[RO2] compared to low [HO2]/[RO2] at 248 K. The high reactivity and substantial contribution to SOA of β-pinene-derived SCIs at lower temperatures observed in this study suggest that monoterpene-derived SCI reactions should be accounted for in describing colder regions of the atmosphere.

Multi-scale structures of the mammalian radial spoke and divergence of axonemal complexes in ependymal cilia

Radial spokes (RS) transmit mechanochemical signals between the central pair (CP) and axonemal dynein arms to coordinate ciliary motility. Atomic-resolution structures of metazoan RS and structures of axonemal complexes in ependymal cilia, whose rhythmic beating drives the circulation of cerebrospinal fluid, however, remain obscure. Here, we present near-atomic resolution cryo-EM structures of mouse RS head-neck complex in both monomer and dimer forms and reveal the intrinsic flexibility of the dimer. We also map the genetic mutations related to primary ciliary dyskinesia and asthenospermia on the head-neck complex. Moreover, we present the cryo-ET and sub-tomogram averaging map of mouse ependymal cilia and build the models for RS1-3, IDAs, and N-DRC. Contrary to the conserved RS structure, our cryo-ET map reveals the lack of IDA-b/c/e and the absence of Tektin filaments within the A-tubule of doublet microtubules in ependymal cilia compared with mammalian respiratory cilia and sperm flagella, further exemplifying the structural diversity of mammalian motile cilia. Our findings shed light on the stepwise mammalian RS assembly mechanism, the coordinated rigid and elastic RS-CP interaction modes beneficial for the regulation of asymmetric ciliary beating, and also facilitate understanding on the etiology of ciliary dyskinesia-related ciliopathies and on the ependymal cilia in the development of hydrocephalus.

Role of GARP family transcription factors in the regulatory network for nitrogen and phosphorus acquisition

The GARP (Golden2, ARR-B, Psr1) family proteins with a conserved DNA-binding domain, called the B-motif, are plant-specific transcription factors involved in the regulation of various physiological processes. The GARP family proteins are divided into members that function as monomeric transcription factors, and members that function as transcription factors in the dimeric form, owing to the presence of a coiled-coil dimerization domain. Recent studies revealed that the dimer-forming GARP family members, which are further divided into the PHR1 and NIGT1 subfamilies, play critical roles in the regulation of phosphorus (P) and nitrogen (N) acquisition. In this review, we present a general overview of the GARP family proteins and discuss how several members of the PHR1 and NIGT1 subfamilies are involved in the coordinated acquisition of P and N in response to changes in environmental nutrient conditions, while mainly focusing on the recent findings that enhance our knowledge of the roles of PHR1 and NIGT1 in phosphate starvation signaling and nitrate signaling.

In vitro photoprotective potential of aryl-sandwiched (thio)semicarbazones against UVA mediated cellular and DNA damage

The most prevalent solar ultraviolet radiation is ultraviolet-A (UVA) radiation. It is the inducer of reactive oxygen species (ROS), a potent mediator of inflammation and photocarcinogenesis. Regular application of sunscreens containing UVA filters is an effective preventive measure in mitigating the risk associated with the formation of dermal carcinoma. Therefore, the development of new photoprotective agents is of great need. The current work examined the in vitro photoprotection of the aryl-linked (thio)semicarbazone derivatives against UVA-mediated DNA damage, inflammation, reactive nitrogen species (RNS), and ROS. Except for the inflammatory cytokine assay, which was carried out on the human monocytic leukemia (THP-1) cell line, all tests were conducted on the human dermal fibroblast (BJ) cell line. In comparison to benzophenone (reference compound), the compound (2Z, 2′Z)-2,2′-(1,3-Phenylenebis (methanylylidene)) bis (hydrazine-1-carbothioamide) (DD-21) demonstrated considerable protection against UVA-induced damage. Compared to the UVA-irradiated control, DD-21 significantly decreased the levels of nitric oxide (NO) and ROS (p < 0.001). In the presence of DD-21, the release of UVA-induced pro-inflammatory cytokines, tumor necrosis factor-α (TNF-α) and interleukin-1β (IL-1β), was also significantly reduced (p < 0.05). Moreover, it was observed that DD-21 protected the cells from UVA-mediated DNA strand breaks and also inhibited the formation of cyclobutane pyrimidine dimers (CPDs) upon comparison to the UVA-exposed control cells (p < 0.001). In conclusion, the findings of this study revealed that DD-21 exhibits remarkable photoprotective properties, thus demonstrating its potential as a candidate UVA filter.

A–D–A'–D–A type nonfused ring electron acceptors for efficient organic solar cells via synergistic molecular packing and orientation control

AbstractNonfused ring electron acceptors (NFREAs) are promising candidates for future commercialization of organic solar cells (OSCs) due to their simple synthesis. Still, the power conversion efficiencies (PCEs) of NFREA‐based OSCs have large room for improvement. In this work, by merging end group halogenation and side chain engineering, we developed four A–D–A'–D–A type NFREAs, which we refer to as EH‐4F, C4‐4F, EH‐4Cl, and C4‐4Cl. Single crystal X‐ray diffraction revealed that multiple intermolecular S···F interactions between cyclopentadithiophene and 5,6‐difluoro‐3‐(dicyanomethylene)indanone could cause an unfavorable dimer formation, leading to ineffective π–π stackings in EH‐4F and C4‐4F, whereas no such dimer was found in EH‐4Cl and C4‐4Cl after replacing with 5,6‐dichloro‐3‐(dicyanomethylene)indanone. Moreover, although the shorter n‐butyl side chain resulted in a closer molecular packing in C4‐4Cl, EH‐4Cl (2‐ethylhexyl substitution) with proper crystallinity exhibited enhanced face‐on orientation in thin film, which is favorable for vertical charge transport and further reducing charge recombination. As a result, a PCE of 13.0% is obtained for EH‐4Cl‐based OSC with a fill factor of 0.70. This work highlights the importance of molecular packing and orientation control toward future high‐performance A–D–A'–D–A type NFREAs.

Islatravir Dimer: Crystal Form Dependence of a Radiation-Induced Degradation Product.

A rare example of crystal form-dependent, gamma radiation-induced degradation is presented. Islatravir is known to exist in several polymorphic forms, but only one of these forms shows the generation of a specific dimer degradation product under gamma irradiation. Extended gamma irradiation studies demonstrated that only one of the known crystalline forms shows an appreciable rate of dimer formation. Additionally, this dimer is not observed to form under other forced stress conditions. We present the structural elucidation of this dimer impurity and rationalize its form-dependent generation based on the analysis of the underlying crystal structure.

Attraction between Like Charged Ions in Ionic Liquids: Unveiling the Enigma of Tetracyanoborate Anions.

Intermolecular interactions in ionic liquids are mainly governed by Coulombic forces. Attraction between cations has been previously observed and was attributed to dispersion interactions between nonpolar moieties, hydrogen bonding, or π stacking. In this study, we present the intriguing behavior of tetracyanoborate anions in ionic liquids that, unlike their dicyanamide and tricyanomethanide counterparts, form dimers in both solid and liquid phases. A joint simulation and experimental study uncovers the origin of such anion-anion attraction: stabilization by induction and dispersion forces between several cyano groups, which is strong enough to overcome electrostatic repulsion. These findings open up new opportunities in the rational design of ionic liquids, where interactions between ions of the same charge can be controlled and fine-tuned by the presence of cyano groups.

UV-C LED-induced cyclobutane pyrimidine dimer formation, lesion repair and mutagenesis in the biofilm-forming diatom, Navicula incerta

The use of ultraviolet-C (UV-C) irradiation in marine biofouling control is a relatively new and potentially disruptive technology. This study examined effects of UV-C exposure on the biofilm-forming diatom, Navicula incerta. UV-C-induced mutations were identified via Illumina HiSeq. A de novo genome was assembled from control sequences and reads from UV-C-exposed treatments were mapped to this genome, with a quantitative estimate of mutagenesis then derived from the frequency of single nucleotide polymorphisms. UV-C exposure increased cyclobutane pyrimidine dimer (CPD) abundance with a direct correlation between lesion formation and fluency. Cellular repair mechanisms gradually reduced CPDs over time, with the highest UV-C fluence treatments having the fastest repair rates. Mutation abundances were, however, negatively correlated with CPD abundance suggesting that UV-C exposure may influence lesion repair. The threshold fluence for CPD formation exceeding CPD repair was >1.27 J cm−2. Fluences >2.54 J cm−2 were predicted to inhibit repair mechanisms. While UV-C holds considerable promise for marine antifouling, diatoms are just one, albeit an important, component of marine biofouling communities. Determining fluence thresholds for other representative taxa, highlighting the most resistant, would allow UV-C treatments to be specifically tuned to target biofouling organisms, whilst limiting environmental effects and the power requirement.

Computational study of the dimerization of glyphosate: mechanism and effect of solvent.

A computational study on the structure and stability of different series of glyphosate (Glyph) dimers comprising nonionized (N) and zwitterionic structures (Z) for neutral monomers, followed by an analysis of energetics of Glyph dimerization process have been performed by means of quantum chemical calculations in different media. Optimized geometries for energy minima, as well as relative potential and free energies of the possible various conformers of each series of Glyph dimer were computed as a function of the medium at B3LYP-D3/6-311++G(2d,2p) level. The solvation model based on density (SMD) is employed for all solution phase computations. Non-ionized dimers (DN), anion-cation (AC) and either zwitterion-zwitterion (DZP and DZC) or non-ionized-phosphonate zwitterion (NZP) ionized neutral forms of Glyph dimer are predicted to exist in the gas phase and in solution in large contrast to Glyph monomers. The DZC dimer form exhibiting a centrosymmetric arrangement of two carboxylate zwitterion units was found to be the most stable dimer structure in all media. In aqueous solution, the DZP and AC dimer type structures are significantly stabilized by hydration. The tautomerisms between DZC, DZP and AC dimer type structures have been investigated in the gas phase and in solution. The DZC type structures are more prone to experience proton transfer in water than in the gas phase and in cyclohexane. The mechanism for the tautomerization process in neutral ionized Glyph dimers proceeds via two direct proton transfer paths: DZP ⇋ AC ⇋ DZC. Results show that solvents play a key role in modulating the energetics of the dimerization process of Glyph. Solvation in cyclohexane, favors the dimerization process however, hydration opposed it. In aqueous solution, the mechanism of the dimerization of Glyph from its phosphonate zwitterionic monomer form (ZP) could be described by a set of equilibria including direct proton transfer paths as follows: 2ZP ⇋ DZP ⇋ AC ⇋ DZC. According to our results, in aqueous solution, DZC Glyph dimers and their corresponding DZP and AC tautomers should be present in higher concentration than phosphonate zwitterionic Glyph monomers for high Glyph concentration, a fact that seems controversial in the literature.

Formation of atmospheric molecular clusters containing nitric acid with ammonia, methylamine, and dimethylamine.

This study investigates the formation of atmospheric molecular clusters containing ammonia (NH3, A), methylamine (CH3NH2, MA), or dimethylamine (CH3NHCH3, DMA) with nitric acid (HNO3, NA) using quantum mechanics. The Atmospheric Cluster Dynamic Code (ACDC) was employed to simulate the total evaporation rate, formation rate, and growth pathways of three types of clusters under dry and hydrated conditions. This study evaluates the enhancing potential of A/MA/DMA for NA-based new particle formation (NPF) at parts per trillion (ppt) levels. The results indicate that A/MA/DMA can enhance NA-based NPF at high nitric acid concentrations and low temperatures in the atmosphere. The enhancing potential of MA is weaker than that of DMA but stronger than that of A. Cluster growth predominantly follows the lowest free energy pathways on the acid-base grid, with the formation of initial acid-base dimers (NA)(A), (NA)(MA), and (NA)(DMA) being crucial. Hydration influences the evaporation rate and formation rate of clusters, especially for initial clusters. When the humidity is at 100%, the formation rate for NA-A, NA-MA, and NA-DMA clusters can increase by approximately 109, 107, and 104-fold compared to the corresponding unhydrated clusters, respectively. These results highlight the significance of nitric acid nucleation in NPF events in low-temperature, high-humidity atmospheres, particularly in regions like China with significant automobile exhaust pollution.

Feasibility of the inhibitor development for cancer: A systematic approach for drug design.

The traditional Chinese medicine (TCM) bupleurum-ginger-licorice formula presents significant anti-cancer effects, but its active ingredients and inhibitory mechanism remain unclear. In this work, the core effective ingredient quercetin and its signal transducer and activator of transcription 3 (Stat3) receptor both were identified by network pharmacology. Quercetin is a low-toxicity, non-carcinogenic flavonoid with antioxidant, anti-inflammatory and anticancer activities, which is widely distributed in edible plants. Stat3 can bind to specific DNA response elements and serves as a transcription factor to promote the translation of some invasion/migration-related target genes, considered as a potential anticancer target. Here, molecular docking and molecular dynamics (MD) simulation both were used to explore molecular recognition of quercetin with Stat3. The results show that quercetin impairs DNA transcription efficiency by hindering Stat3 dimerization, partially destroying DNA conformation. Specifically, when the ligand occupies the SH2 cavity of the enzyme, spatial rejection is not conductive to phosphokinase binding. It indirectly prevents the phosphorylation of Y705 and the formation of Stat3 dimer. When the inhibitor binds to the DT1005 position, it obviously shortens the distance between DNA and DBD, enhances their binding capacity, and thereby reduces the degree of freedom required for transcription. This work not only provides the binding modes between Stat3 and quercetin, but also contributes to the optimization and design of such anti-cancer inhibitors.

Influence of H+, OH- and salts on hydrophobic self-assembly.

In spite of the ubiquity of acid/base ions and salts in biological systems, their influence on hydrophobic self-assembly remains an open question. Here we use a combined experimental and theoretical strategy to quantify the influence of H+ and OH-, as well as salts containing Li+, Na+, Cl- and Br-, on the hydrophobic self-assembly of micelles composed of neutral oily 1,2-hexanediol surfactants. The distributions of aggregate sizes, both below and above the critical micelle concentration (CMC), are determined using Raman multivariate curve resolution (Raman-MCR) spectroscopy to quantify the multi-aggregation chemical potential surface (MCPS) that drives self-assembly. The results reveal that ions have little influence on the formation of hydrophobic contact dimers but can significantly drive high-order self assembly. Moreover, the hydration-shells of oily solutes are found to expel the above salt ions and OH-, but to attract H+, with wide-ranging implications.

Nickel-catalyzed γ-alkylation of cyclopropyl ketones with unactivated primary alkyl chlorides: balancing reactivity and selectivity via halide exchange.

A novel method was developed for synthesizing γ-alkyl ketones via nickel-catalyzed cross-electrophile coupling of cyclopropyl ketones and non-activated primary alkyl chlorides. High reactivity and selectivity can be achieved with sodium iodide as a crucial cocatalyst that generates a low concentration of alkyl iodide via halide exchange, thus avoiding the formation of alkyl dimers. This reaction possessed excellent regioselectivity and high step economy circumventing in situ or pregenerated organometallics.

Mechanistic and biophysical characterization of polymyxin resistance response regulator PmrA in Acinetobacter baumannii.

Acinetobacter baumannii PmrAB is a crucial two-component regulatory system (TCS) that plays a vital role in conferring resistance to polymyxin. PmrA, a response regulator belonging to the OmpR/PhoB family, is composed of a C-terminal DNA-binding effector domain and an N-terminal receiver domain. The receiver domain can be phosphorylated by PmrB, a transmembrane sensor histidine kinase that interacts with PmrA. Once phosphorylated, PmrA undergoes a conformational change, resulting in the formation of a symmetric dimer in the receiver domain. This conformational change facilitates the recognition of promoter DNA by the DNA-binding domain of PmrA, leading to the activation of adaptive responses. X-ray crystallography was carried out to solve the structure of PmrA receiver domain. Electrophoretic mobility shift assay and Isothermal titration calorimetry were recruited to validate the interaction between the recombinant PmrA protein and target DNA. Field-emission scanning electron microscopy (FE-SEM) was employed to characterize the surface morphology of A. baumannii in both the PmrA knockout and mutation strains. The receiver domain of PmrA follows the canonical α5β5 response regulator assembly, which undergoes dimerization upon phosphorylation and activation. Beryllium trifluoride is utilized as an aspartate phosphorylation mimic in this process. Mutations involved in phosphorylation and dimerization significantly affected the expression of downstream pmrC and naxD genes. This impact resulted in an enhanced cell surface smoothness with fewer modifications, ultimately contributing to a decrease in colistin (polymyxin E) and polymyxin B resistance. Additionally, a conservative direct-repeat DNA PmrA binding sequence TTTAAGNNNNNTTTAAG was identified at the promoter region of the pmrC and naxD gene. These findings provide structural insights into the PmrA receiver domain and reveal the mechanism of polymyxin resistance, suggesting that PmrA could be a potential drug target to reverse polymyxin resistance in Acinetobacter baumannii.

The efficient triplet states formation of Se-modified PDI dimers and tetramers in solvents.

The triplet excited states of molecules play an important role in photophysical processes, which has attracted great research interest. Perylene diimide (PDI) is a widely studied material closely associated with the generation of triplet states, and it is highly anticipated to become an electron acceptor material for improving photovoltaic conversion efficiency. In this work, we prepared dimers and tetramers composed of selenium-modified PDI-C5 (N,N'-bis(6-undecyl) perylene-3,4,9,10-bis(dicarboximide)) units. We investigated the photophysical processes of these dimers and tetramers in chloroform and toluene using UV-visible absorption spectroscopy, fluorescence spectroscopy, and femtosecond transient absorption spectroscopy. Both the dimers and tetramers undergo efficient triplet state formation processes in the solvents. Solvents with higher polarity facilitate charge transfer thereby promote the triplet states formation. The differences in the configurations of the dimer and tetramer molecules lead to variations in triplet states generation. The twisted angles in the tetramer restricted the intramolecular electronic coupling, posing certain hindrances to exciton coupling and lowering the intramolecular CT characteristics. The emission of excimer in tetramers also competes with the triplet states formation. The research demonstrates the influence of various factors on the generation of triplet states of PDI oligomers.

Engineered π⋯π interactions favour supramolecular dimers X@[FeL3]2 (X = Cl, Br, I): solid state and solution structure.

Ditopic bis-pyrazolylpyridine ligands usually react with divalent metal ions (M2+) to produce dinuclear triple-stranded helicates [M2L3]4+ or, via π⋯π interactions, dimers of monoatomic complexes ([ML3]2)4+. The introduction of an additional benzene ring at each end of ligand L increases the number of aromatic contacts within the supramolecular aggregate by 40%, driving the self-recognition process in an irreversible manner. Consequently, the mixing of new bis-pyrazolylquinoline L2 with FeX2 salts leads to crystallization of the tripartite high-spin assemblies (X@[Fe(L2)3]2)3+ (X = Cl, Br or I). The aggregates exhibit exceptional stability, as confirmed by a combination of paramagnetic 1H NMR techniques, demonstrating their persistence in solution. Our investigations further reveal that the guests Br- and I- are retained inside the associate in solution but Cl- is immediately released, resulting in the formation of the empty supramolecular dimer ([Fe(L2)3]2)4+.

A library of vinyl phosphonate anions dimerize with cyanostars, form supramolecular polymers and undergo statistical sorting.

Supramolecular dimers are elementary units allowing the build-up of multi-molecule architectures. New among these are cyanostar-stabilized dimers of phosphate and phosphonate anions. While the anion dimerization at the heart of these assemblies is reliable, the covalent synthesis leading to this class of designer anions serves as a bottleneck in the pathway to supramolecular assemblies. Herein, we demonstrate the reliable synthesis of 14 diverse anionic monomers by Heck coupling between vinyl phosphonic acid and aryl bromide compounds. When this synthesis is combined with reliable anion dimerization, we show formation of supramolecular dimers and polymers by co-assembly with cyanostar macrocycles. The removal of the covalent bottleneck opened up a seamless synthetic route to iterate through three monomers affording the solubility needed to characterize the mechanism of supramolecular polymerization. We also test the idea that the small size of these vinyl phosphonates provide identical dimer stabilities across the library by showing how mixtures of anions undergo statistical (social) self-sorting. We exploit this property by preparing soluble copolymers from the mixing of different monomers. This multi-anion assembly shows the utility of a library for programming properties.

A mechanistic study reveals the roles of the ligand and substrate in the Pd-catalyzed C–H bond hydroxylation of a carboxylic acid with molecular oxygen

DFT studies reveal critical factors influencing the reactivity of Pd-catalyzed C–H bond hydroxylation with O2: (1) substrate axial coordination; (2) proton shuttling by the ligand; and (3) dimeric palladium species formation.