Contents 1. General Experimental Methods 2. Experimental Procedures 2.1 Monomer Syntheses 2.2 Polymerization Procedures 2.3 Optimization of "Click-Chemistry" for Ethynyl-Terminated Poly(3-hexylthiophene) 2.4 Model Compound for End "Clicking" Reactions 2.5 Synthesis of Naphthalenediimides 2.6 Application of "Click-Chemistry" Conditions to Post-Polymerization Side-Chain Functionalization 3. NMR Spectra 4. Supplementary GPC Data 5. Supplementary UV-vis Data S2 General Experimental MethodsAll chemicals were purchased from commercial sources (Acros, Aldrich, Alfa Aesar, TCI, and Strem) and used without further purification, unless otherwise noted. THF was distilled from sodium-benzophenone ketyl. NBS was recrystallized from water. t-BuMgCl (nominally 1.0 M in THF) and ethynyl-MgBr (nominally 0.50 M in THF) were titrated against salicylaldehyde phenylhydrazone according to the method of Love (J. Org. Chem. 1999, 64(10), 3755). Common solvents were purchased from EMD (through VWR). Routine monitoring of reactions was carried out on glass-supported EMD silica gel 60 F 254 TLC plates. Flash chromatography was performed using silica gel from Sorbent Technologies (Standard Grade, 60 Å, 32-63 μm). All 1 H and 13 C{ 1 H} NMR spectra were recorded on a Bruker Avance400 spectrometer. 19 F NMR spectra were recorded on a Bruker DPX300 spectrometer. Chemical shifts and coupling constants (J) are reported in parts per million (δ) and Hertz, respectively. Deuterated solvents were obtained from Cambridge Isotope Laboratories, Inc. Chloroform-D (CDCl 3 ) contained 0.05% v/v tetramethylsilane (TMS) and this peak was set to 0.00 ppm on all proton spectra. In the case of 1,1,2,2-tetrachloroethane-D 2 (TCE), which did not contain TMS, the residual solvent peak was set to 6.00 ppm. Gel permeation chromatography (GPC) was done in the NSF-sponsored MaterialsResearch Science and Engineering Center on Polymers (MRSEC) at the University of Massachusetts Amherst. GPC analyses were performed on a Polymer Laboratories GPC50 integrated system with tetrahydrofuran (1.0 mL/min, 35 ºC) elution, 3 x Mixed C (300 x 7.5 mm) columns, and RI detection. Molecular weights were obtained based on polystyrene standards, with toluene as the flow rate marker, and may be overestimated by a factor of 1.5-2.0.UV-vis absorption spectra were measured with a Shimadzu UV 2600PC spectrometer in the laboratory of Prof. Paul M. Lahti (University of Massachusetts Amherst, Department of Chemistry). Stock solutions of polymers (c = 1 mg/10 mL) were prepared in spectrophotometric grade chloroform (Fisher, Optima) and diluted 10x (c = 1 mg/100 mL) in order to attain absorbances < 1.0. Films for UV-vis experiments were prepared by drop-casting solutions of polymer (c = 1 mg/mL) onto glass cover slips (Fisher Cat. No. 12-548-B) and allowing the solvent to freely evaporate.

Introduction Despite being reported since 1943 as well as being the subject of a large body of literature since that time, no consensus has been reached regarding the etiology of opioid induced hyperalgesia (OIH). It is often described as a paradoxical increased pain response to noxious stimuli due to increased sensitization or an acute tolerance to opioids. Case We report the case of a 60 year old patient on chronic Intrathecal combined fentanyl and Bupivacaine who had worsening pain with increasing doses and improved after weaning off intrathecal opioids. Conclusion OIH has been described in various settings including patients on methadone maintenance therapy, perioperative opioid administration, cancer patients on opioids, and healthy volunteers who are acutely exposed to opioids, including high dose intrathecal opioids such as Morphine and Sufentanil. To our knowledge, no cases of opioid induced hyperalgesia was previously reported in the case of intrathecal Fentanyl.

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Objective: Lower extremities nerves damage is a known complication of prostatectomies. Lumbar sympathetic block is a well-established treatment for sympathetically-mediated lower extremity pain. We report a case of bilateral lower extremity pain in a femoral distribution that developed after a robotic assisted prostatectomy and resolved after a lumbar sympathetic block.Case Report: A 69-year-old male patient presented with bilateral thigh pain one month after an uneventful robotic-assisted laparoscopic prostatectomy in the femoral nerve distribution. CT scan was unremarkable save for expected postsurgical changes. The patient failed conservative treatment. Considering a possible sympathetically-mediated pain, we performed a right lumbar sympathetic block that improved his pain. Conclusions:A lumbar sympathetic block can be used a salvage therapy when conservative management fails. Materials and MethodsPatient informed consent was obtained for submission of the case report. Case PresentationA 69-year-old male patient with a history of well controlled noninsulin-dependent diabetes presented to the pain clinic with unbearable bilateral thigh pain. One month prior to presentation he underwent an uncomplicated robotic-assisted laparoscopic nerve sparing radical prostatectomy with lymph node dissection. Three days after an uneventful postoperative course, he developed a worsening sharp, shooting pain involving the L1, L2, L3, L4 dermatomes, worse on the right side, exacerbated by weather changes, associated with allodynia and hyperalgesia over the affected areas. There was no associated motor weakness, swelling, fever, or muscle spasm. CT scan of the abdomen and pelvis with and without contrast were unremarkable save for expected postsurgical changes.The patient failed conservative treatment including Amitriptyline, Gabapentin, Zonisamide, Duloxetine, and Oxycodone. Due to lack of response to neuropathic medications and a possibly sympathetically-mediated pain, we attempted a right lumbar sympathetic block the mid L3 vertebral body. On follow-up, the patient reported 80% pain reduction, with pain reported as 2/10 which decreased from 8-9/10 pre-injection and an increase in function.