Locklearhowe9667

Organic donor-acceptor (D-A) co-crystals have attracted much interest due to their important optical and electronic properties. Co-crystals having ⋯DADA⋯ π-stacked morphologies are especially interesting because photoexcitation produces a charge-transfer (CT) exciton, D˙+-A˙-, between adjacent D-A molecules. Although several studies have reported on the steady-state optical properties of this type of CT exciton, very few have measured the dynamics of its formation and decay in a single D-A co-crystal. We have co-crystallized a peri-xanthenoxanthene (PXX) donor with a N,N-bis(3-pentyl)-2,5,8,11-tetraphenylperylene-3,49,10-bis(dicarboximide) (Ph4PDI) acceptor to give an orthorhombic PXX-Ph4PDI ⋯DADA⋯ π-stacked co-crystal with a CT transition dipole moment that is perpendicular to the transition moments for S n ← S0 excitation of PXX and Ph4PDI. Using polarized, broadband, femtosecond pump-probe microscopy, we have determined that selective photoexcitation of Ph4PDI in the single co-crystal results in CT exciton formation within the 300 fs instrument response time. At early times (0.3 ≤ t ≤ 500 ps), the CT excitons decay with a t -1/2 dependence, which is attributed to CT biexciton annihilation within the one-dimensional ⋯DADA⋯ π-stacks producing high-energy, long-lived (>8 ns) electron-hole pairs in the crystal. These energetic charge carriers may prove useful in applications ranging from photovoltaics and opto-electronics to photocatalysis.Ultrafast transient absorption spectroscopy reveals new excited-state dynamics following excitation of trans-azobenzene (t-Az) and several alkyl-substituted t-Az derivatives encapsulated in a water-soluble supramolecular host-guest complex. Encapsulation increases the excited-state lifetimes and alters the yields of the trans → cis photoisomerization reaction compared with solution. Kinetic modeling of the transient spectra for unsubstituted t-Az following nπ* and ππ* excitation reveals steric trapping of excited-state species, as well as an adiabatic excited-state trans → cis isomerization pathway for confined molecules that is not observed in solution. Analysis of the transient spectra following ππ* excitation for a series of 4-alkyl and 4,4'-dialkyl substituted t-Az molecules suggests that additional crowding due to lengthening of the alkyl tails results in deeper trapping of the excited-state species, including distorted trans and cis structures. The variation of the dynamics due to crowding in the confined environment provides new evidence to explain the violation of Kasha's rule for nπ* and ππ* excitation of azobenzenes based on competition between in-plane inversion and out-of-plane rotation channels.The cell membrane is composed of a network of glycoconjugates including glycoproteins and glycolipids that presents a dense matrix of carbohydrates playing critical roles in many biological processes. Lectin-based technology has been widely used to characterize glycoconjugates in tissues and cell lines. However, their specificity toward their putative glycan ligand and sensitivity in situ have been technologically difficult to study. Additionally, because they recognize primarily glycans, the underlying glycoprotein targets are generally not known. In this study, we employed lectin proximity oxidative labeling (Lectin PROXL) to identify cell surface glycoproteins that contain glycans that are recognized by lectins. Commonly used lectins were modified with a probe to produce hydroxide radicals in the proximity of the labeled lectins. The underlying polypeptides of the glycoproteins recognized by the lectins are oxidized and identified by the standard proteomic workflow. As a result, approximately 70% of identified glycoproteins were oxidized in situ by all the lectin probes, while only 5% of the total proteins were oxidized. The correlation between the glycosites and oxidation sites demonstrated the effectiveness of the lectin probes. The specificity and sensitivity of each lectin were determined using site-specific glycan information obtained through glycomic and glycoproteomic analyses. Notably, the sialic acid-binding lectins and the fucose-binding lectins had higher specificity and sensitivity compared to other lectins, while those that were specific to high mannose glycans have poor sensitivity and specificity. This method offers an unprecedented view of the interactions of lectins with specific glycoproteins as well as protein networks that are mediated by specific glycan types on cell membranes.Longeracemine, a member of the Daphniphyllum family of alkaloids contains a novel carbon framework featuring a highly functionalized 2-azabicyclo[2.2.1]heptane core as part of an overall 5/6/5/5/6/5 skeleton. A synthetic intermediate containing the core of longeracemine has been efficiently prepared by employing a stereoselective SmI2-mediated cascade reaction to advance a 7-azabicyclo[2.2.1]heptadiene to a 2-azabicyclo[2.2.1]heptene that is functionally poised for conversion to the natural product.Abundant n → π* interactions between adjacent backbone carbonyl groups, identified by statistical analysis of protein structures, are predicted to play an important role in dictating the structure of proteins. However, experimentally testing the prediction in proteins has been challenging due to the weak nature of this interaction. By amplifying the strength of the n → π* interaction via amino acid substitution and thioamide incorporation at a solvent exposed β-turn within the GB1 proteins and Pin 1 WW domain, we demonstrate that an n → π* interaction increases the structural stability of proteins by restricting the ϕ torsion angle. read more Our results also suggest that amino acid side-chain identity and its rotameric conformation play an important and decisive role in dictating the strength of an n → π* interaction.Framework materials at the molecular level, such as metal-organic frameworks (MOF), were recently found to exhibit exotic and counterintuitive micromechanical properties. Stimulated by host-guest interactions, these so-called soft porous crystals can display counterintuitive adsorption phenomena such as negative gas adsorption (NGA). NGA materials are bistable frameworks where the occurrence of a metastable overloaded state leads to pressure amplification upon a sudden framework contraction. How can we control activation barriers and energetics via functionalization of the molecular building blocks that dictate the frameworks' mechanical response? In this work we tune the elastic and inelastic properties of building blocks at the molecular level and analyze the mechanical response of the resulting frameworks. From a set of 11 frameworks, we demonstrate that widening of the backbone increases stiffness, while elongation of the building blocks results in a decrease in critical yield stress of buckling. We further functionalize the backbone by incorporation of sp3 hybridized carbon atoms to soften the molecular building blocks, or stiffen them with sp2 and sp carbons.