Monotelechelic Poly(oxa)norbornenes by Ring-Opening Metathesis Polymerization Using Direct End-Capping and Cross-Metathesis

Two different methodologies for the synthesis of monotelechelic poly(oxa)norbornenes prepared by living ring-opening metathesis polymerization (ROMP) are presented. The first method, termed direct end-capping, is carried out by adding an internal cis-olefin terminating agent (TA) to the reaction mixture immediately after the completion of the living ROMP reaction. The second method relies on cross-metathesis (CM) between a methylene-terminated poly(oxa)norbornene and a cis-olefin TA mediated by the ruthenium olefin metathesis catalyst (H_(2)IMes)(Cl)_(2)Ru(CH-o-OiPrC_(6)H_4) (H_(2)IMes = 1,3-dimesitylimidazolidine-2-ylidene). TAs containing various functional groups, including alcohols, acetates, bromides, α-bromoesters, thioacetates, N-hydroxysuccinimidyl esters, and Boc-amines, as well as fluorescein and biotin groups, were synthesized and tested. The direct end-capping method typically resulted in >90% end-functionalization efficiency, while the CM method was nearly as effective for TAs without polar functional groups or significant steric bulk. End-functionalization efficiency values were determined by ^(1)H NMR spectroscopy

50th Anniversary Perspective: Living Polymerization—Emphasizing the Molecule in Macromolecules

The ideal of living polymerization has defined research in polymer chemistry over the past 50 years. In this Perspective, we present the case that this concept has enabled the treatment of polymers as organic molecules, rather than impure mixtures of species, and allowed the translation of methods developed by synthetic organic chemists into ever more accessible living and/or controlled polymerization methods. The concurrent development of rapid analytical methods for screening new polymerization methods for living characteristics, chiefly size exclusion chromatography, has greatly aided in the expansion of living polymerization methods

Z-Selective Homodimerization of Terminal Olefins with a Ruthenium Metathesis Catalyst

The cross-metathesis of terminal olefins using a novel ruthenium catalyst results in excellent selectivity for the Z-olefin homodimer. The reaction was found to tolerate a large number of functional groups, solvents, and temperatures while maintaining excellent Z-selectivity, even at high reaction conversions

Addressing the challenges of modeling the scattering from bottlebrush polymers in solution

Small‐angle scattering measurements of complex macromolecules in solution are used to establish relationships between chemical structure and conformational properties. Interpretation of the scattering data requires an inverse approach where a model is chosen and the simulated scattering intensity from that model is iterated to match the experimental scattering intensity. This raises challenges in the case where the model is an imperfect approximation of the underlying structure, or where there are significant correlations between model parameters. We examine three bottlebrush polymers (consisting of polynorbornene backbone and polystyrene side chains) in a good solvent using a model commonly applied to this class of polymers: the flexible cylinder model. Applying a series of constrained Monte‐Carlo Markov Chain analyses demonstrates the severity of the correlations between key parameters and the presence of multiple close minima in the goodness of fit space. We demonstrate that a shape‐agnostic model can fit the scattering with significantly reduced parameter correlations and less potential for complex, multimodal parameter spaces. We provide recommendations to improve the analysis of complex macromolecules in solution, highlighting the value of Bayesian methods. This approach provides richer information for understanding parameter sensitivity compared to methods which produce a single, best fit

Linear Rheological Response of a Series of Densely Branched Brush Polymers

We have examined the linear rheological responses of a series of welldefined, dense, regularly branched brush polymers. These narrow molecular weight distribution brush polymers had polynorobornene backbones with degrees of polymerization (DP) of 200, 400, and 800 and polylactide side chains with molecular weight of 1.4 kDa, 4.4 kDa, and 8.7 kDa. The master curves for these brush polymers were obtained by time temperature superposition (TTS) of the dynamic moduli over the range from the glassy region to the terminal flow region. Similar to other long chain branched polymers, these densely branched brush polymers show a sequence of relaxation. Subsequent to the glassy relaxation, two different relaxation processes can be observed for samples with the high molecular weight (4.4 and 8.7 kDa) side chains, corresponding to the relaxation of the side chains and the brush polymer backbone. Influenced by the large volume fraction of high molecular weight side chains, these brush polymers are unentangled. The lowest plateau observed in the dynamic response is not the rubbery entanglement plateau but is instead associated with the steady state recoverable compliance. Side chain properties affect the rheological responses of these densely branched brush polymers and determine their glassy behaviors

Moral Grandstanding in Public Discourse: Status-Seeking Motives as a Potential Explanatory Mechanism in Predicting Conflict

Public discourse is often caustic and conflict-filled. This trend seems to be particularly evident when the content of such discourse is around moral issues (broadly defined) and when the discourse occurs on social media. Several explanatory mechanisms for such conflict have been explored in recent psychological and social-science literatures. The present work sought to examine a potentially novel explanatory mechanism defined in philosophical literature: Moral Grandstanding. According to philosophical accounts, Moral Grandstanding is the use of moral talk to seek social status. For the present work, we conducted six studies, using two undergraduate samples (Study 1, N = 361; Study 2, N = 356); a sample matched to U.S. norms for age, gender, race, income, Census region (Study 3, N = 1,063); a YouGov sample matched to U.S. demographic norms (Study 4, N = 2,000); and a brief, one-month longitudinal study of Mechanical Turk workers in the U.S. (Study 5, Baseline N = 499, follow-up n = 296), and a large, one-week YouGov sample matched to U.S. demographic norms (Baseline N = 2,519, follow-up n = 1,776). Across studies, we found initial support for the validity of Moral Grandstanding as a construct. Specifically, moral grandstanding motivation was associated with status-seeking personality traits, as well as greater political and moral conflict in daily life

Predicting Gambling Situations: The Roles of Impulsivity, Substance Use, and Post-Traumatic Stress

Gambling disorder and symptoms of post-traumatic stress are highly comorbid. Numerous studies suggest that the presence of one (either disordered gambling or post-traumatic stress) substantially increases the odds of later developing the other. However, little is known about the etiological links between these two domains or the nuances of the comorbidity. Past research has suggested that symptoms of post-traumatic stress might be related to unique motivations for and beliefs about gambling. The present work sought to examine whether or not symptoms of post-traumatic stress might also be related to specific situational vulnerabilities to gambling behaviors. Using a large cross-sectional sample of Internet-using adults in the United States who were primarily recreational gamblers (N = 743; 46% men,  = 36.0, SD = 11.1), as well as an inpatient sample of US Armed Forces veterans seeking treatment for gambling disorder (N = 332, 80% men,  = 53.5, SD = 11.5), the present work tested whether or not symptoms of post-traumatic stress were uniquely related to a variety of gambling situations. Results in both samples revealed that even when controlling for potentially confounding variables (eg, substance use and trait impulsivity), symptoms of post-traumatic stress were uniquely related to gambling in response to negative affect, gambling in response to social pressure, and gambling due to a need for excitement. These findings are consistent with recent work suggesting that individuals with post-traumatic stress symptoms are more likely to engage in gambling behaviors for unique reasons that differ from gamblers without such symptoms

Free Space Optical Link Utilizing a Modulated Retro-Reflector Intended for Planetary Duplex Communication Links Between an Orbiter and Surface Unit

Presented are simulation and experimental results that provide duplex optical-free space communication links with minimal power and pointing requirements by using a modulated retro-reflector (MRR) for planetary communications. The design is the MRR resides on the surface of a planet or moon, where energy is scarce, while the source of the communication laser resides on an orbiter to achieve satellite-to-ground communications. Also, a simulated scenario using the Mars Reconnaissance Orbiter (MRO) is provided for real world potential results. The information sent through this communication path can range from raw scientific data to multimedia files such as videos and pictures. Bidirectional communications is established with the MRR by using a nested pulse position modulation (PPM) structure. This modulation scheme is then evaluated for its validity in a proof-of-concept experiment. Initial results indicate a promising return-link performance of at least 300 kbps in the nested arrangement

Sports Wagering in the United States: What We Do and Don\u27t Know

Abstract In the wake of the Murphy vs. NCAA decision by the Supreme Court of the United States, over 30 states now permit sports betting and a majority of Americans now have access to this activity. Even so, much remains unknown about the effects of widespread access to sports betting in the U.S. The present work reports interim results of multi-year data collection efforts in the U.S. In April of 2022, a U.S. nationally representative sample of 2,806 Americans and an additional sample of 1,553 sports wagering people were recruited by YouGov opinion polling, with follow up data collected in October of 2022, and planned data collections for January of 2023 and April of 2023, prior to the IGI conference, with more planned throughout 2023 and 2024. Initial results suggest that sports wagering remains a relatively niche gambling activity, but one that is associated with risk for and symptoms of gambling disorder. Additionally, sports betting is associated with a range of other addictive behaviors such as substance use and compulsive sexual behavior. Collectively, these results suggest that sports betting, though not especially common in the American populace, should be thought of as a risk-taking behavior that warrants further empirical study. Implications Statement Sports betting in the U.S. is now more accessible than ever, though many questions remain about the effects of this accessibility. The present study suggests that sports wagering is a unique risk-taking behavior associated with a range of other impulsive and addictive behaviors

50th Anniversary Perspective: Living Polymerization—Emphasizing the Molecule in Macromolecules

The ideal of living polymerization has defined research in polymer chemistry over the past 50 years. In this Perspective, we present the case that this concept has enabled the treatment of polymers as organic molecules, rather than impure mixtures of species, and allowed the translation of methods developed by synthetic organic chemists into ever more accessible living and/or controlled polymerization methods. The concurrent development of rapid analytical methods for screening new polymerization methods for living characteristics, chiefly size exclusion chromatography, has greatly aided in the expansion of living polymerization methods