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The hexagonally close-packed (HCP) sphere phase is predicted to be stable across a narrow region of linear block copolymer phase space, but the small free energy difference separating it from face-centered cubic spheres usually results in phase coexistence. Here, we report the discovery of pure HCP spheres in linear block copolymer melts with A = poly(2,2,2-trifluoroethyl acrylate) ("F") and B = poly(2-dodecyl acrylate) ("2D") or poly(4-dodecyl acrylate) ("4D"). In 4DF diblocks and F4DF triblocks, the HCP phase emerges across a substantial range of A-block volume fractions (circa f A = 0.25-0.30), and in F4DF, it forms reversibly when subjected to various processing conditions which suggests an equilibrium state. The time scale associated with forming pure HCP upon quenching from a disordered liquid is intermediate to the ordering kinetics of the Frank-Kasper σ and A15 phases. However, unlike σ and A15, HCP nucleates directly from a supercooled liquid or soft solid without proceeding through an intermediate quasicrystal. Self-consistent field theory calculations indicate the stability of HCP is intimately tied to small amounts of molar mass dispersity ( Đ ); for example, an HCP-forming F4DF sample with f A = 0.27 has an experimentally measured Đ = 1.04. These insights challenge the conventional wisdom that pure HCP is difficult to access in linear block copolymer melts without the use of blending or other complex processing techniques.

As the scope of additive manufacturing broadens, interest has developed in 3D-printed objects that are derived from recyclable resins with chemical and mechanical tunability. Dynamic covalent bonds have the potential to not only increase the sustainability of 3D-printed objects, but also serve as reactive sites for postprinting derivatization. In this study, we use boronate esters as a key building block for the development of catalyst-free, 3D-printing resins with the ability to undergo room-temperature exchange at the cross-linking sites. The orthogonality of boronate esters is exploited in fast-curing, oxygen-tolerant thiol-ene resins in which the dynamic character of 3D-printed objects can be modulated by the addition of a static, covalent cross-linker with no room-temperature bond exchange. This allows the mechanical properties of printed parts to be varied between those of a traditional thermoset and a vitrimer. Objects printed with a hybrid dynamic/static resin exhibit a balance of structural stability (residual stress = 18%) and rapid exchange (characteristic relaxation time = 7 s), allowing for interfacial welding and postprinting functionalization. Modulation of the cross-linking density postprinting is enabled by selective hydrolysis of the boronate esters to generate networks with swelling capacities tunable from 1.3 to 3.3.

Molecular architecture plays a key role in the self-assembly of block copolymers, but few studies have systematically examined the influence of chain connectivity on tetrahedrally close-packed (TCP) sphere phases. Here, we report a versatile material platform comprising two blocks with substantial conformational asymmetry, A = poly(trifluoroethyl acrylate) and B = poly(dodecyl acrylate), and use it to compare the phase behavior of AB diblocks, ABA triblocks, and (AB) n radial star copolymers with n = 3 or 4. Each architecture forms TCP sphere phases at minority A block compositions ( f A < 0.5), namely, σ and A15, but with differences in the location of order-order phase boundaries that are not anticipated by mean-field self-consistent field theory simulations. These results expand the palette of polymer architectures that readily self-assemble into complex TCP structures and suggest important design considerations when targeting specific phases of interest.

A versatile and scalable strategy is reported for the rapid generation of block copolymer libraries spanning a wide range of compositions starting from a single parent copolymer. This strategy employs automated and operationally simple chromatographic separation that is demonstrated to be applicable to a variety of block copolymer chemistries on multigram scales with excellent mass recovery. The corresponding phase diagrams exhibit increased compositional resolution compared to those traditionally constructed via multiple, individual block copolymer syntheses. Increased uniformity and lower dispersity of the chromatographic libraries lead to differences in the location of order-order transitions and observable morphologies, highlighting the influence of dispersity on the self-assembly of block copolymers. Significantly, this separation technique greatly simplifies the exploration of block copolymer phase space across a range of compositions, monomer pairs, and molecular weights (up to 50000 amu), producing materials with increased control and homogeneity when compared to conventional strategies.

The stability of tetrahedrally close-packed (TCP) phases in block copolymer melts is predicted by theory to depend on molecular architecture, yet no experimental studies to date have probed its effect. Motivated by this open question, here we report an efficient synthesis of asymmetric AB n miktoarm star polymers using functionalized sugars as cores for orthogonal grafting-from block copolymerizations. A combination of ring-opening and atom transfer radical polymerization produced model low dispersity materials comprising a single A = poly(lactide) (L) and multiple B = poly(dodecyl acrylate) (D) arms that amplify "conformational asymmetry" through two concerted effects: the mikto architecture and disparate block statistical segment lengths. Analyzing the self-assembly of LD 2 and LD 3 samples resulted in the discovery of two TCP phases, σ and A15, that remained stable to significantly higher A-block volume fractions as the number of B arms increased. These results experimentally establish the importance of conformational asymmetry and molecular architecture as powerful design tools for the self-assembly of block copolymers into nonclassical phases.

Herein, we report the development of a scalable and synthetically robust building block based on norbornadiene (NBD) that can be broadly incorporated into a variety of macromolecular architectures using traditional living polymerization techniques. By taking advantage of a selective and rapid deprotection with tetrazine, highly reactive "masked" cyclopentadiene (Cp) functionalities can be introduced into synthetic polymers as chain-end groups in a quantitative and efficient manner. The orthogonality of this platform further enables a cascade "click" process where the "unmasked" Cp can rapidly react with dienophiles, such as maleimides, through a conventional Diels-Alder reaction. Coupling proceeds with quantitative conversions allowing high molecular weight star and dendritic block copolymers to be prepared in a single step under ambient conditions.

The self-assembly of block polymers into well-ordered nanostructures underpins their utility across fundamental and applied polymer science, yet only a handful of equilibrium morphologies are known with the simplest AB-type materials. Here, we report the discovery of the A15 sphere phase in single-component diblock copolymer melts comprising poly(dodecyl acrylate)- block -poly(lactide). A systematic exploration of phase space revealed that A15 forms across a substantial range of minority lactide block volume fractions ( f L = 0.25 - 0.33) situated between the σ-sphere phase and hexagonally close-packed cylinders. Self-consistent field theory rationalizes the thermodynamic stability of A15 as a consequence of extreme conformational asymmetry. The experimentally observed A15-disorder phase transition is not captured using mean-field approximations but instead arises due to composition fluctuations as evidenced by fully fluctuating field-theoretic simulations. This combination of experiments and field-theoretic simulations provides rational design rules that can be used to generate unique, polymer-based mesophases through self-assembly., Competing Interests: The authors declare no conflict of interest.

The relationship between plasma carotenoids, plasma cholesterol, cigarette smoking, vitamin supplement use, and intakes of alcohol, vitamin A, and carotene were investigated in 1981 for 187 Multiple Risk Factor Intervention Trial men in Pittsburgh. The total plasma carotenoid value was positively correlated with the dietary carotene and vitamin A indices (estimated by a food frequency questionnaire), vitamin A supplement usage, and plasma cholesterol, and inversely related to cigarette smoking, alcohol intake, and serum aspartate transaminase. The mean plasma carotenoid level was higher in nonsmokers (means = 186 micrograms/dl, 95% confidence interval (CI) 178-195) as compared with cigarette smokers (means = 164 micrograms/dl, 95% CI 151-178) and in vitamin A supplement users (means = 206 micrograms/dl, 95% CI 188-224) as compared with nonusers (means = 172 micrograms/dl, 95% CI 164-179). Variables associated with the total plasma carotenoids in multiple regression analyses included dietary vitamin A and carotene, calorie intake, weekly alcohol intake, cigarette smoking, vitamin supplement usage, and plasma cholesterol, and accounted for 27% of the variance. The total plasma carotenoid value was also highly correlated with plasma beta-carotene (r = 0.67) and lycopene (r = 0.68). The mean beta-carotene (30 micrograms/dl), however, accounted for only 16% of the total plasma carotenoids.

Oleic acid emulsions stabilized with albumin were infused into fasted rats. Blood samples taken before and during infusion were analyzed for free fatty acids (FFA), ketone bodies, glucose, and insulin. Turnover rates of FFA and ketone bodies were also determined using constant infusion of radioactive tracers. During oleic acid infusions at a rate of 2 mumoles/min/100 g body weight, FFA concentrations increased for a short time and then decreased to preinfusion levels. The decreases in concentrations were due to decreases in the endogenous rates of appearance of FFA into the blood. When oleic acid was infused at a rate of 3.5 mumoles/min/100 g body weight, FFA concentrations increased and remained elevated throughout the infusion. Ketone body concentrations more than doubled during infusions at 2 and 3.5 mumoles/min/100 g body weight and showed no signs of decreasing even when FFA concentrations decreased. Insulin concentrations doubled during infusion and glucose concentrations decreased. Insulin injected during infusion had little effect on concentrations of FFA or ketone bodies. It was concluded that infusions of oleic acid inhibit adipose tissue lipolysis and increase blood ketone concentrations in intact fasted rats. The injection of insulin does not inhibit ketogenesis when blood FFA levels are maintained by infusion.

We have previously reported the existence of an association between endogenous male sex hormone and lipoprotein levels in elderly men confined to a nursing home. In a further attempt to elucidate the significance of the association mentioned, we studied the relationship existing in that population between serum testosterone and fasting insulin levels, and between fasting insulin level and lipoprotein pattern. The data were analysed by means of stepwise multiple regression analyses. Serum testosterone and fasting insulin were found to be strongly correlated; this is consistent with the notion that androgen secretion affects directly circulating insulin level. But no independent relationship was demonstrable between fasting insulin and the three lipid-lipoprotein categories studied, namely total serum cholesterol, triglyceride and HDL-cholesterol, suggesting that in this particular population, the effect of male sex hormones upon lipoproteins is not mediated through insulin. Together, these various observations support the belief that androgen secretion affects significantly CAD risk factor levels in elderly men.

Acetoacetate or DL-3-hydroxybutyrate were infused into fasted rats at rates comparable to the endogenous rate of ketone body release. Blood samples taken before and during infusion were analyzed for concentrations of ketone bodies, free fatty acids, and immunoreactive insulin. During infusion of acetoacetate or DL-3-hydroxybutyrate, blood concentrations of total ketone bodies doubled. While the HBA/AcAc ratios remained constant in rats infused with DL-3-hydroxybutyrate, the ratios decreased significantly during infusion of acetoacetate, reflecting increases in acetoacetate concentrations without proportionate increases in concentrations of D-3-hydroxybutyrate. Blood concentrations of free fatty acids decreased more rapidly in the rats infused with DL-3-hydroxybutyrate than in the rats infused with acetoacetate. The decrease in free fatty acid concentrations was related to increases in blood D-3-hydroxybutyrate in both the DL-3-hydroxybutyrate-infused rats and in the acetoacetate-infused rats. Plasma immunoreactive insulin concentrations were significantly higher in the DL-3-hydroxybutyrate-infused rats than in the acetoacetate-infused rats. Acetoacetate and DL-3-hydroxybutyrate were infused into depancreatized, functionally hepatectomized fasted rats at rates comparable to those used in the intact fasted rats. Only small decreases in free fatty acid concentrations were observed during infusion. From these experiments it was concluded that increases in blood concentrations of D-3-hydroxybutyrate were more effective than acetoacetate in causing decreases in free fatty acid concentrations in the fasting rat. The pancreas is required for this effect.

In an effort to better understand the relationship existing between lipoprotein pattern and longevity, we studied the lipid and lipoprotein distribution of 94 men over age 80 who lived in a nursing home, and assessed the role of selective mortality, body mass and sex hormone secretion in determining these distributions. High density lipoprotein subfraction and serum testosterone measurements were obtained on subsamples. The main findings were: (a) Presence of a lipoprotein pattern characterized by low LDL (total serum cholesterol: 179.6 +/- 36.0 mg/dl; LDL cholesterol: 106.3 +/- 31.2 mg/dl) and high HDL2 cholesterol (18.5 +/- 10.2 mg/dl) levels. (b) Occurrence of a positive association between LDL and HDL3 (r = 0.51, P less than 0.01), resulting in an overall high HDL2/HDL3 ratio. Mortality over a 6-month period was directly related to LDL level and possibly inversely related to HDL2 level, suggesting that selective mortality played a major role in determining the pattern observed. Body mass and serum testosterone concentration, which tended to be low, were independently correlated with lipoprotein level; a particularly strong correlation (positive) existed between free testosterone and triglyceride (r = 0.68, P less than 0.01). The latter results suggest that changes related to senescence also influenced lipid and lipoprotein levels.