An alpha,omega-functionalized polymenthide was synthesized by the ring-opening polymerization of menthide in the presence of diethylene glycol with diethyl zinc as the catalyst. Termination with water afforded the dihydroxy polymenthide. The reaction of this telechelic polymer with triethylaluminum formed the corresponding aluminum alkoxide macroinitiator that was used for the controlled polymerization of lactide to yield biorenewable polylactide-b-polymenthide-b-polylactide triblock copolymers. The molecular weight and chemical composition were easily adjusted by the monomer-to-initiator ratios. Microphase separation in these triblock copolymers was confirmed by small-angle X-ray scattering and differential scanning calorimetry. A representative triblock was prepared with a hexagonally packed cylindrical morphology as determined by small-angle X-ray scattering, and tensile testing was employed to assess the mechanical behavior. On the basis of the ultimate elongations and elastic recovery, these triblock copolymers behaved as thermoplastic elastomers.

A. Calculation of the effective solution potential, E eff (A/AThe concentration corrections for the A/A -redox species performed herein have followed conditions previously outlined. 5 Figure S1 highlights the effect of this concentration correction for an ntype semiconductor-liquid junction photoelectrochemical cell. Point A denotes an experimentallyobtained V oc value at solution redox potential E(A/A -) at which the concentrations of oxidized species

A series of polylactide-polymenthide-polylactide triblock copolymers containing either amorphous poly(D,L-lactide) or semicrystalline, enantiopure poly(L-lactide) or poly(D-lactide) end segments were synthesized. Small-angle X-ray scattering and differential scanning calorimetry data were consistent with microphase separation of these materials. The Young's moduli and ultimate tensile strengths of the semicrystalline triblock copolymers were 2- and 3-fold greater, respectively, than their amorphous analogs. Symmetric (50:50) and asymmetric (95:5) blends of the triblock copolymers containing two different enantomeric forms of the polylactide segments formed stereocomplex crystallites, as revealed by wide-angle X-ray scattering and differential scanning calorimetry. Compared to the enantiopure analogs, these blends exhibited similar ultimate elongations and tensile strengths, but significantly increased Young's moduli. Collectively, these results demonstrate that the properties of these new biorenewable thermoplastic elastomers can be systematically modulated by changing the stereochemistry of the polylactide end blocks.

The band-edge positions of H-, Cl-, Br-, methyl-, and ethyl-terminated Si(111) surfaces were investigated through a combination of density functional theory (DFT) and many-body perturbation theory, as well as by photoelectron spectroscopy and electrical device measurements. The calculated trends in surface potential shifts as a function of the adsorbate type and coverage are consistent with the calculated strength and direction of the dipole moment of the adsorbate radicals in conjunction with simple electronegativity-based expectations. The quasi-particle energies, such as the ionization potential (IP), that were calculated by use of many-body perturbation theory were in good agreement with experiment. The IP values that were calculated by DFT exhibited substantial errors, but nevertheless, the IP differences, i.e., IPR–Si(111)–IPH–Si(111), computed using DFT were in good agreement with spectroscopic and electrical measurements.

Figure S1. Throughput of GATR setup was 11.8% at 2500 cm -1 .2 Figure S2. a) Representative transmission spectra of surfaces made with χ CH 2 CHCH 2 MgCl = 0.02, 0.10, 0.50, and 1.00 referenced to CH 3 -Si(111) used to quantify mixed monolayer composition. The C=C stretch of the allyl-group at 1628 cm -1 , the CH 3 -umbrella mode at (111))/(peak intensity of CH 2 CHCH 2 -Si(111)), was determined using the 1628 cm -1 (C=C) peak area, where 0.8 is the fractional Si-C coverage of CH 2 CHCH 2 -Si (111) surfaces as determined by XPS. The error bars indicate ± 1 standard deviation. Figure S2.c shows that CH 3 -and CH 2 CHCH 2 -groups were both present on the surface, and that the MM-Si(111) monolayer compositions were not linearly dependent on the compositon of the reaction solution.4 Figure S3. Typical XPS spectrum of CH 3 -Si (111) showing survey spectrum and high reslution Si2p and C1s (2.5x scans of Si) regions. Peaks were fit using a Shirley background. C region was fit to C-O, adventitious C, and C-Si. Si region was fit to bulk