Metal-organic frameworks (MOFs) have received attention for a myriad of potential applications including catalysis, gas storage, and gas separation. Coordinatively unsaturated metal ions often enable key functional behavior of these materials. Most commonly, MOFs have been metalated from the condensed phase (i.e., from solution). Here we introduce a new synthetic strategy capable of metallating MOFs from the gas phase: atomic layer deposition (ALD). Key to enabling metalation by ALD In MOFs (AIM) was the synthesis of NU-1000, a new, thermally stable, Zr-based MOF with spatially oriented -OH groups and large 1D mesopores and apertures.

Through in situ quartz crystal microbalance (QCM) monitoring, we resolve the growth of a self-assembled monolayer (SAM) and subsequent metal oxide deposition with high resolution. We introduce the fitting of mass deposited during each atomic layer deposition (ALD) cycle to an analytical island-growth model that enables quantification of growth inhibition, nucleation density, and the uninhibited ALD growth rate. A long-chain alkanethiol was self-assembled as a monolayer on gold-coated quartz crystals in order to investigate its effectiveness as a barrier to ALD. Compared to solution-loading, vapor-loading is observed to produce a SAM with equal or greater inhibition ability in minutes vs days. The metal oxide growth temperature and the choice of precursor also significantly affect the nucleation density, which ranges from 0.001 to 1 sites/nm(2). Finally, we observe a minimum 100 cycle inhibition of an oxide ALD process, ZnO, under moderately optimized conditions.

Using recently reported robust porphyrinic metal-organic framework (RPM) materials, we have examined the systematic exchange of pillaring linkers/struts as a means of accessing new versions of these materials.Dipyridyl-porphyrin Zn(II) (Zn-dipy) struts were successfully replaced by M 2 -dipy (M 2 ¼ 2H(+), Al(III), Sn(IV)), forming crystalline solid solutions of Zn(Zn 1Àx M x )-RPM in variable ratios. In addition, post-synthetic metallation was demonstrated using Zn2H-RPM, again with retention of crystallinity. We examined catalytic activity for an epoxide ring-opening reaction with a series of ZnM 2 -RPMs. The catalytic activity depends strongly on the identity of the metal ion present in the dipyridyl-porphyrin unit.Scheme 1 Synthesis of M 1 M 2 -RPM materials from M 1 -tetraacid, M 2 -dipy and Zn(NO 3 ) 2 $6H 2 O. Crystallography derived stick representations of the unit cells of RPM (yellow ¼ Zn, red ¼ O, green ¼ F, blue ¼ N, gray ¼ C). Hydrogen atoms and disordered solvent molecules have been omitted for clarity.

The structure-activity relationship (SAR) for the N-benzyl group in the clinical antiepileptic agent (R)-lacosamide ((R)-N-benzyl 2-acetamido-3-methoxypropionamide, (R)-3) has been explored. Forty-three compounds were prepared and then evaluated at the National Institute of Neurological Disorders and Stroke Anticonvulsant Screening Program for seizure protection in the maximal electroshock (MES) and subcutaneous Metrazol models. Comparing activities for two series of substituted aryl regioisomers (2′, 3′, 4′) showed that 4′-modified derivatives had the highest activity. Significantly, structural latitude existed at the 4′-site. The SAR indicated that non-bulky 4′-substituted (R)-3 derivatives exhibited superb activity, independent of their electronic properties. Activities in the MES test of several compounds were either comparable with or exceeded that of (R)-3, and surpassed the activities observed for the traditional antiepileptic agents phenytoin, phenobarbital, and valproate.Epilepsy, a major neurological disorder that affects all populations, 1 describes the types of recurrent seizures produced by paroxysmal, excessive, synchronous neuronal discharges in the brain. 2,3 In the United States alone, over 2 million people suffer from epilepsy and its sequelae; 340,000 are children. 4 For many of these individuals, the disabilities and associated neuropsychological and behavioral factors adversely affect their quality of life. The lifestyle restrictions plus the large expense for treatment, lost productivity, and rehabilitation result in a huge cost to society. 4 The treatment mainstay for patients with epileptic disorders has been the long-term and consistent administration of anticonvulsant drugs. 5,6 Unfortunately, current medications are ineffective for approximately one-third of these patients. 7 Many continue to have seizures, while others experience disturbing side effects (e.g., drowsiness, dizziness, nausea, liver damage). 8 Thus, there is a need for more efficacious drugs that function by different pharmacological pathways.CORRESPONDING AUTHOR: Division of Medicinal Chemistry and Natural Products, UNC Eshelman School of Pharmacy, University of North Carolina, Chapel Hill, North Carolina 27599-7568 and Department of Chemistry, University of North Carolina, Chapel Hill, North Carolina 27599-3290, hkohn@email.unc.edu, Telephone: 919-843-8112, Fax number: 919-966-0204. Supporting Information Available: Synthetic procedures for the intermediates leading to the preparation of (R)-4, 7-31, 33-39, 60, and 61, and (S)-11, 21, 23, 26, 28, 29, 34, and 38, elemental analyses, 1 H and 13 C NMR spectra of compounds evaluated in this study. This material is available free of charge via the internet at http://pubs.acs.org. NIH Public AccessAuthor Manuscript J Med Chem. Author manuscript; available in PMC 2011 February 11. NIH-PA Author ManuscriptNIH-PA Author Manuscript NIH-PA Author ManuscriptIn 1985, we discovered a novel class of anticonvulsant agents, termed functionalized amino acids (FAA, a 1). ...

Hematite (α-Fe2O3) is one of just a few candidate electrode materials that possess all of the following photocatalyst-essential properties for scalable application to water oxidation: excellent stability, earth-abundance, suitability positive valence-band-edge energy, and significant visible light absorptivity. Despite these merits, hematite's modest oxygen evolution reaction kinetics and its poor efficiency in delivering photogenerated holes, especially holes generated by green photons, to the electrode/solution interface, render it ineffective as a practical water-splitting catalyst. Here we show that hole delivery and catalytic utilization can be substantially improved through Ti alloying, provided that the alloyed material is present in ultrathin-thin-film form. Notably, the effects are most pronounced for charges photogenerated by photons with energy comparable to the band gap for excitation of Fe(3d)→Fe(3d) transitions (i.e., green photons). Additionally, at the optimum Ti substitution level the lifetimes of surface-localized holes, competent for water oxidation, are extended. Together these changes explain an overall improvement in photoelectrochemical performance, especially enhanced internal quantum efficiencies, observed upon Ti(IV) incorporation.