The thermomechanical properties exhibited
by synthetic macromolecules can be directly linked to their tacticity,
or the relative stereochemistry of repeat units. The development of
stereoselective coordination–insertion polymerization, for
example, led to the discovery of isotactic polypropylene, now one
of the most widely produced commodity plastics in the world. Widespread
interest in controlling polymer tacticity has led to a variety of
stereoselective polymerization methodologies; however, this area of
polymer science has lagged behind when compared to the ability to
control molecular weight, dispersity, and composition. Despite decades
of advancements, many stereoregular vinyl polymers remain unknown,
particularly those comprised of polar functionality or derived from
renewable resources. This Viewpoint provides an overview of recent
developments in stereocontrolled polymerization, with an emphasis
on propagation mechanism, and highlights successes, limitations, and
future challenges for continued innovation.
The potential for genetic biofortification of U.S.-grown lentils ( Lens culinaris L.) with bioavailable folate has not been widely studied. The objectives of this study were (1) to determine the folate concentration of 10 commercial lentil cultivars grown in Minot and McLean counties, North Dakota, USA, in 2010 and 2011, (2) to determine the genotype (G) × environmental (E) interactions for folate concentration in lentil cultivars, and (3) to compare the folate concentration of other pulses [field peas ( Pisum sativum L.) and chickpea ( Cicer arietinum L.)] grown in the United States. Folate concentration in lentil cultivars ranged from 216 to 290 μg/100 g with a mean of 255 μg/100 g. In addition, lentil showed higher folate concentration compared to chickpea (42-125 μg/100 g), yellow field pea (41-55 μg/100 g), and green field pea (50-202 μg/100 g). A 100 g serving of lentils could provide a significant amount of the recommended daily allowance of dietary folates (54-73%) for adults. A significant year × location interaction on lentil folate concentration was observed; this indicates that possible location sourcing may be required for future lentil folate research.
The first total synthesis of (±)-gelsenicine is reported. The synthetic route is highly efficient (13 steps), featuring (1) a pivotal metal-catalyzed isomerization/rearrangement process that forges the central core of the molecule and (2) two facile C–N bond-forming steps that establish the flanking heterocycles.
Isotactic poly(vinyl ether)s (PVEs) have recently been identified as a new class of semicrystalline thermoplastics with a valuable combination of mechanical and interfacial properties. Currently, methods to synthesize isotactic PVEs are limited to strong Lewis acids that require a high catalyst loading and limit the accessible scope of monomer substrates for polymerization. Here, we demonstrate the first Brønsted acid catalyzed stereoselective polymerization of vinyl ethers. A single-component imidodiphosphorimidate catalyst exhibits a sufficiently low pK a to initiate vinyl ether polymerization and acts as a chiral conjugate base to direct the stereochemistry of monomer addition to the oxocarbenium ion reactive chain end. This Brønsted acid catalyzed stereoselective polymerization enabled an expanded substrate scope compared to previous methods, the use of chain transfer agents to lower catalyst loading, and the capability to recycle the catalyst for multiple polymerizations.
A convenient Cadiot-Chodkiewicz protocol that facilitates the use of low
molecular weight alkyne coupling partners is described. The method entails an in
situ elimination from a dibromoolefin precursor and immediately subjecting to
copper-catalyzed conditions, circumventing the hazards of volatile brominated
alkynes. The scope of this method is described, and the internal 1,3-diyne
products are preliminarily evaluated in ruthenium-catalyzed azide alkyne
cycloadditions.
Inositol phosphates are the main form of phosphorous (P) storage in legume seeds. Mutants low in inositol hexaphosphate (IP6), also known as phytic acid (PA), have been developed to increase iron (Fe) bioavailability and reduce P waste to the environment. The objectives of this study were to determine 1) inositol-P form changes during germination, and 2) the effect of P fertilizer application on seed PA, total P, and Fe concentration of three field pea (Pisum sativum L.) cultivars and two low-PA lines grown under greenhouse conditions. Low-PA field pea lines clearly had lower PA (1.3-1.4 mg•g −1) than cultivars (3.1-3.7 mg•g −1). Phytic acid concentration in both cultivars and low-PA lines decreased during germination, but tended to increase seven days after germination. Levels of inositol-3-phosphate-phosphate (IP3-P; 0.6 mg•g-1) and inorganic P (1.8-2.0 mg•g −1) were higher in low-PA lines than in the field pea cultivars. Reduction of PA in low-PA line seeds may reduce seed Fe and total P concentrations, as levels in the low-PA lines (37-42 mg•kg −1 Fe; 4003-4473 mg•kg −1 total P) were typically less than in field pea cultivars (37-55 mg•kg −1 Fe; 3208-4985 mg•kg −1 total P) at different P fertilizer rates. Overall, IP3 is the major form of P present in low-PA field pea lines during germination; however IP6 is the major form of P present in field pea cultivars. Therefore, low-PA field pea lines could be a potential solution to increase Fe bioavailability, feed P utilization, and reduce P waste to the environment.
Two strategies are described en route
to an enantioselective total
synthesis of gelsenicine. One approach centers on a chirality transfer
cycloisomerization that ultimately fell short. Separately, an asymmetric
catalysis route utilizing bisphosphine-gold-catalyzed cycloisomerization
was pursued. A catalytic system was identified that provided a synthetic
intermediate in our Gelsemium alkaloid syntheses
in high enantiopurity and with absolute configuration determined by
electronic circular dichroism, thus representing an enantioselective
formal total synthesis of (+)-gelsenicine.
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