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1. pH- and chaotropic anion-induced conformational changes of tertiary amine-containing binary heterografted star molecular bottlebrushes in aqueous solution

   https://doi.org/10.1039/D0PY01466D  

   Kent, Ethan W. ; Lewoczko, Evan M. ; Zhao, Bin ( January 2021 , Polymer Chemistry)

   null (Ed.)

   This article reports on the conformational behavior of binary heterografted three-arm star molecular bottlebrushes composed of poly(ethylene oxide) (PEO) and either poly(2-( N , N -dimethylamino)ethyl methacrylate) (PDMAEMA, the brushes denoted as SMB-1) or poly(2-( N , N -diethylamino)ethyl methacrylate) (PDEAEMA, the brushes denoted as SMB-2) side chains in aqueous solutions in response to pH changes and addition of salts containing chaotropic anions (CAs). PEO was introduced into the brushes as a stabilizer when the tertiary amine-containing side chains collapsed. While a small size decrease of SMB-1 was observed with increasing pH from acidic to basic, SMB-2 exhibited a large and abrupt size transition caused by the pH-induced solubility change of PDEAEMA. Atomic force microscopy imaging revealed a star-to-globule shape transition of SMB-2 upon increasing pH across the p K a ; in contrast, SMB-1 stayed in the starlike state at both low and high pH values. Intriguingly, both SMB-1 and -2 displayed star-to-globule shape transitions in acidic solutions upon addition of salts containing sufficiently strong CAs such as ClO 4 − , with SMB-2 showing a greater sensitivity to moderate CAs than SMB-1. Moreover, superchaotropic anions ( e.g. , Fe(CN) 6 3− and S 2 O 8 2− ) were significantly more efficient in inducing shape changing than common CAs. The CA-induced shape transitions resulted from the ion pairing of CAs and protonated tertiary amine groups and the high propensity of CAs to associate with hydrophobic moieties in the brushes, which decreased the solubility of the tertiary amine-containing side chains and caused the brushes to collapse. The findings reported here may enable potential applications of molecular bottlebrushes in, e.g. , encapsulation and release of ionic substances. 

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2. Salt- and pH-induced swelling of a poly(acrylic acid) brush via quartz crystal microbalance w/dissipation (QCM-D)

   https://doi.org/10.1039/c9sm01289c  

   Hollingsworth, Nisha R. ; Wilkanowicz, Sabina I. ; Larson, Ronald G. ( October 2019 , Soft Matter)

   We infer the swelling/de-swelling behavior of weakly ionizable poly(acrylic acid) (PAA) brushes of 2–39 kDa molar mass in the presence of KCl concentrations from 0.1–1000 mM, pH = 3, 7, and 9, and grafting densities σ = 0.12–2.15 chains per nm 2 using a Quartz Crystal Microbalance with Dissipation (QCM-D), confirming and extending the work of Wu et al. to multiple chain lengths. At pH 7 and 9 (above the p K a ∼ 5), the brush initially swells at low KCl ionic strength (<10 mM) in the “osmotic brush” regime, and de-swells at higher salt concentrations, in the “salted brush” regime, and is relatively unaffected at pH 3, below the p K a , as expected. At pH 7, at low and moderate grafting densities, our results in the high-salt “salted brush” regime ( C s > 10 mM salt) agree with the predicted scaling H ∼ Nσ +1/3 C s −1/3 of brush height H , while in the low-salt “osmotic brush” regime ( C s < 10 mM salt), we find H ∼ Nσ +1/3 C s +0.28–0.38 , whose dependence on C s agrees with scaling theory for this regime, but the dependence on σ strongly disagrees with it. The predicted linearity in the degree of polymerization N is confirmed. The new results partially confirm scaling theory and clarify where improved theories and additional data are needed. 

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3. Unveiling the warm and dense ISM in z  > 6 quasar host galaxies via water vapor emission

   https://doi.org/10.1051/0004-6361/202243406  

   Pensabene, A. ; van der Werf, P. ; Decarli, R. ; Bañados, E. ; Meyer, R. A. ; Riechers, D. ; Venemans, B. ; Walter, F. ; Weiß, A. ; Brusa, M. ; et al ( November 2022 , Astronomy & Astrophysics)

   Water vapor (H₂O) is one of the brightest molecular emitters after carbon monoxide (CO) in galaxies with high infrared (IR) luminosity, allowing us to investigate the warm and dense phase of the interstellar medium (ISM) where star formation occurs. However, due to the complexity of its radiative spectrum, H₂O is not frequently exploited as an ISM tracer in distant galaxies. Therefore, H₂O studies of the warm and dense gas at high-zremain largely unexplored. In this work, we present observations conducted with the Northern Extended Millimeter Array (NOEMA) toward threez > 6 IR-bright quasarsJ2310+1855,J1148+5251, andJ0439+1634targeted in their multiple para- and ortho-H₂O transitions (3₁₂ − 3₀₃, 1₁₁ − 0₀₀, 2₂₀ − 2₁₁, and 4₂₂ − 4₁₃), as well as their far-IR (FIR) dust continuum. By combining our data with previous measurements from the literature, we estimated the dust masses and temperatures, continuum optical depths, IR luminosities, and star formation rates (SFR) from the FIR continuum. We modeled the H₂O lines using the MOLPOP-CEP radiative transfer code, finding that water vapor lines in our quasar host galaxies are primarily excited in the warm, dense (with a gas kinetic temperature and density ofT_kin = 50 K,n_H2 ∼ 10^4.5 − 10⁵ cm⁻³) molecular medium with a water vapor column density ofN_H2O ∼ 2 × 10¹⁷ − 3 × 10¹⁸ cm⁻³. High-JH₂O lines are mainly radiatively pumped by the intense optically-thin far-IR radiation field associated with a warm dust component at temperatures ofT_dust ∼ 80 − 190 K that account for < 5 − 10% of the total dust mass. In the case of J2310+1855, our analysis points to a relatively high value of the continuum optical depth at 100 μm (τ₁₀₀ ∼ 1). Our results are in agreement with expectations based on the H₂O spectral line energy distribution of local and high-zultra-luminous IR galaxies and active galactic nuclei (AGN). The analysis of the Boltzmann diagrams highlights the interplay between collisions and IR pumping in populating the high H₂O energy levels and it allows us to directly compare the excitation conditions in the targeted quasar host galaxies. In addition, the observations enable us to sample the high-luminosity part of the H₂O–total-IR (TIR) luminosity relations (L_H2O − L_TIR). Overall, our results point to supralinear trends that suggest H₂O–TIR relations are likely driven by IR pumping, rather than the mere co-spatiality between the FIR continuum- and line-emitting regions. The observedL_H2O/L_TIRratios in ourz > 6 quasars do not show any strong deviations with respect to those measured in star-forming galaxies and AGN at lower redshifts. This supports the notion that H₂O can be likely used to trace the star formation activity buried deep within the dense molecular clouds.

    

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4. Clickable polymer scaffolds enable Ce recovery with peptide ligands

   https://doi.org/10.1039/d2sm01664h  

   Hostert, Jacob D. ; Sepesy, Maura R. ; Duval, Christine E. ; Renner, Julie N. ( April 2023 , Soft Matter)

   Rare earth elements (REEs) are a vital part of many technologies with particular importance to the renewable energy sector and there is a pressing need for environmentally friendly and sustainable processes to recover and recycle them from waste streams. Functionalized polymer scaffolds are a promising means to recover REEs due to the ability to engineer both transport properties of the porous material and specificity for target ions. In this work, REE adsorbing polymer scaffolds were synthesized by first introducing poly(glycidyl methacrylate) (GMA) brushes onto porous polyvinylidene fluoride (PVDF) surface through activator generated electron transfer atom transfer radical polymerization (AGET ATRP). Azide moieties were then introduced through a ring opening reaction of GMA. Subsequently, REE-binding peptides were conjugated to the polymer surface through copper catalyzed azide alkyne cycloaddition (CuAAC) click chemistry. The presence of GMA, azide, and peptide was confirmed through Fourier transform infrared spectroscopy. Polymer scaffolds functionalized with the REE-binding peptide bound cerium, while polymer scaffolds functionalized with a scrambled control peptide bound significantly less cerium. Importantly, this study shows that the REE binding peptide retains its functionality when bound to a polymer surface. The conjugation strategy employed in this work can be used to introduce peptides onto other polymeric surfaces and tailor surface specificity for a wide variety of ions and small molecules. 

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5. Amphiphilic Heterografted Molecular Bottlebrushes with Tertiary Amine‐Containing Side Chains as Efficient and Robust pH‐Responsive Emulsifiers

   https://doi.org/10.1002/anie.202315424  

   Kelly, Michael T. ; Chen, Zhan ; Russell, Thomas P. ; Zhao, Bin ( November 2023 , Angewandte Chemie International Edition)

   By combining the unique characteristics of molecular bottlebrushes (MBBs) and the properties of stimuli‐responsive polymers, we show that MBBs with randomly grafted poly(n‐butyl acrylate) and pH‐responsive poly(2‐(N,N‐diethylamino)ethyl methacrylate) (PDEAEMA) side chains are efficient and robust pH‐responsive emulsifiers. Water‐in‐toluene emulsions were formed at pH 4.0 and disrupted by increasing the pH to 10.0. The emulsion generation and disruption was reversible over the ten cycles investigated, and the bottlebrushes remained intact. The exceptional emulsion stability stemmed from the high interfacial binding energy of MBBs, imparted by their large molecular size and Janus architecture at the interface, as evidenced by the interfacial jamming and wrinkling of the assemblies upon reducing the interfacial area. At pH 10.0, PDEAEMA became water‐insoluble, and the MBBs desorbed from the interface, causing de‐emulsification. Consequently, we have shown that the judicious design of MBBs can generate properties of particle emulsifiers from their large size, while the responsiveness of the MBBs enables more potential applications.

    

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