The working curve informs resin properties and print parameters for stereolithography, digital light processing, and other photopolymer additive manufacturing (PAM) technologies. First demonstrated in 1992, the working curve measurement of cure depth vs radiant exposure of light is now a foundational measurement in the field of PAM. Despite its widespread use in industry and academia, there is no formal method or procedure for performing the working curve measurement, raising questions about the utility of reported working curve parameters.
View Article and Find Full Text PDFVat photopolymerization additive manufacturing (Vat AM) technologies have found niche industrial use being able to produce personalized parts in moderate quantity. However, Vat AM lacks in its ability to produce parts of satisfactory thermal and mechanical properties for structural applications. The purpose of this investigation was to develop high-performance resins with glass transition temperatures (Tg) above 200 °C for Vat AM, evaluate the properties of the produced thermosets and establish a structure-property relationship of the thermosets produced.
View Article and Find Full Text PDFSelective excited-state intramolecular proton-transfer (ESIPT) photocycloaddition of 3-hydroxyflavones with trans, trans-1,4-diphenyl-1,3-butadiene is described. Using this methodology, total syntheses of the natural products (±)-foveoglin A and (±)-perviridisin B were accomplished. Enantioselective ESIPT photocycloaddition using TADDOLs as chiral hydrogen-bonding additives provided access to (+)-foveoglin A.
View Article and Find Full Text PDFPhotochemical transformations are a powerful tool in organic synthesis to access structurally complex and diverse synthetic building blocks. However, this great potential remains untapped in the mainstream synthetic community due to the challenges associated with stereocontrol originating from excited state(s). The finite lifetime of an excited state and nearly barrierless subsequent processes present significant challenges in manipulating the stereochemical outcome of a photochemical reaction.
View Article and Find Full Text PDFAtropisomeric enone-imides and enone-amides featuring N-CAryl bond rotation were evaluated for intramolecular [2 + 2] photocycloaddition. Straight addition product was observed over cross-addition product with good control over reactivity. The atropselectivity was found to be dependent on the substituent on the aryl ring.
View Article and Find Full Text PDFDirect irradiation of atropisomeric α-substituted acrylanilides in the presence of alkali metal ions gave high ee values in the 3,4-dihydro-2-quinolin-2-one photoproduct, while in the absence of alkali metal ions, racemic photoproduct was observed. The heavy atom effect leading to enhanced triplet yields alters the reactive pathway leading to the observed enantioselectivity in the photoproduct.
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