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Exposure of easily reduced aromatic bis(enones) 1a-1e to the methyl Gilman reagent Me(2)CuLi.LiI at 0 degrees C in tetrahydrofuran solvent provides the products of tandem conjugate addition-Michael cyclization, 2a-2e, along with the products of [2 + 2] cycloaddition, 3a-3e. Complete partitioning of the Gilman alkylation and [2 + 2] cycloaddition pathways may be achieved by adjusting the loading of the Gilman reagent, the rate of addition of the Gilman reagent, and the concentration of the reaction mixture. The Gilman alkylation manifold is favored by the rapid addition of excess Gilman reagent at higher substrate concentrations, while the [2 + 2] cycloaddition manifold is favored by slow addition of the same Gilman reagent at lower concentrations and loadings. Notably, [2 + 2] cycloaddition to form 3a-3e is catalytic in Gilman reagent. Kinetic data reveal that the ratio of 2a and 3a changes such that the cycloaddition pathway becomes dominant upon increased consumption of Gilman reagent. These data suggest a concentration-dependent speciation of the Gilman reagent and differential reactivity of the aggregates present at higher and lower concentrations. While the species present at higher concentration induce Gilman alkylation en route to products 2a-2e, the species present at lower concentration provide products of catalytic [2 + 2] cycloaddition, 3a-3e. Moreover, upon electrochemical reduction of the bis(enones) 1a-1e, or chemically induced single-electron transfer from arene anion radicals, the very same [2 + 2] cycloadducts 3a-3e are formed. The collective data suggest that [2 + 2] cycloadducts 3a-3e arising under Gilman conditions may be products of anion radical chain cyclobutanation that derive via electron transfer (ET) from the Me(2)CuLi.LiI aggregate(s) present at low concentration. These observations provide a link between the Gilman alkylation reaction and related ET chemistry and suggest these reaction paths are mechanistically distinct. This analysis is made possible by the recent observation that easily reduced bis(enones) are subject to intramolecular [2 + 2] cycloaddition upon cathodic reduction or chemically induced ET from arene anion radicals, and is herewith showcased as a novel method of testing for the intermediacy of enone anion radicals.

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We demonstrate a method using photoactivation localization microscopy (PALM) in a soft-material system, with a rhodamine-lactam dye that is activated by both ultraviolet light and protonation, to reveal the nanoscale photoacid distribution in a model photoresist. Chemically amplified resists are the principal lithographic materials used in the semiconductor industry. The photoacid distribution generated upon exposure and its subsequent evolution during post-exposure bake is a major limiting factor in determining the resolution and lithographic quality of the final developed resist image. Our PALM data sets resolve the acid distribution in a latent image with subdiffraction limit accuracy. Our overall accuracy is currently limited by residual mechanical drift.

Functional imaging using fluorescent indicators has revolutionized biology but additional sensor scaffolds are needed to access properties such as bright, far-red emission. We introduce a new platform for 'chemigenetic' fluorescent indicators, utilizing the self-labeling HaloTag protein conjugated to environmentally sensitive synthetic fluorophores. This approach affords bright, far-red calcium and voltage sensors with highly tunable photophysical and chemical properties, which can reliably detect single action potentials in neurons. Fluorescent sensors enable noninvasive measurement of cellular function. Although this field began with small-molecule fluorescent dyes, functional imaging in biology rapidly switched to protein-based sensors after the discovery of green fluorescent protein (GFP). Protein-based indicators allow cell-specific expression and take advantage of evolved molecular recognition motifs found in nature. In particular, genetically encoded calcium and voltage indicators (GECIs and GEVIs) have become powerful tools for monitoring neuronal activity in living systems. 1, 2Commonly used GECIs and GEVIs, such as GCaMP 3, 4 and ASAP 5 , rely on the use of a circularly permuted (cp) GFP fused to sensor protein domains like calmodulin (CaM) or a voltage sensitive

ABSTRACT193 immersion lithography has reached its maximal achievable resolution. There are mainly two lithographic strategies that will enable continued increase in resolution. Those are being pursued in parallel. The first is extreme ultraviolet (EUV) lithography and the second is double patterning (exposure) lithography. EUV lithography is counted on to be available in 2013 time frame for 22 nm node [1] . Unfortunately, this technology has suffered several delays due to fundamental problems with source power, mask infrastructure, metrology and overall reliability [2] . The implementation of EUV lithography in the next five years is unlikely due to economic factors. Double patterning lithography (DPL) is a technology that has been implemented by the industry and has already shown the proof of concept for the 22nm node [3] .This technique while expensive is the only current path forward for scaling with no fundamental showstoppers for the 32nm and 22nm nodes. Double exposure lithography (DEL) is being proposed as a cost mitigating approach to advanced lithography. Compared to DPL, DEL offers advantages in overlay and process time, thus reducing the cost-of-ownership (CoO) [4][5] . However, DEL requires new materials that have a non-linear photoresponse. So far, several approaches were proposed for double exposure lithography, from which Optical Threshold Layer (OTL) was found to give the best lithography performance according to the results of the simulation [4][5] . This paper details the principle of the OTL approach. A photochromic polymer was designed and synthesized. The feasibility of the material for application of DEL was explored by a series of evaluations.

Intermediate state two-photon (ISTP) photoacid generator (PAG) and optical threshold layer (OTL) approaches to double exposure lithography have been explored. We have synthesized "transparent" PAG and sensitizer compounds for use in ISTP systems and have demonstrated the possibility of utilizing such energy transfer systems to generate acid. We have also synthesized side chain liquid crystalline polymers and small molecule azobenzene compounds for use in OTL applications and have begun photoswitching studies.

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