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1.
Ecol Appl ; 32(7): e2673, 2022 10.
Article in English | MEDLINE | ID: mdl-35584048

ABSTRACT

Marine heatwaves threaten the persistence of kelp forests globally. However, the observed responses of kelp forests to these events have been highly variable on local scales. Here, we synthesize distribution data from an environmentally diverse region to examine spatial patterns of canopy kelp persistence through an unprecedented marine heatwave. We show that, although often overlooked, temperature variation occurring at fine spatial scales (i.e., a few kilometers or less) can be a critical driver of kelp forest persistence during these events. Specifically, though kelp forests nearly all persisted toward the cool outer coast, inshore areas were >3°C warmer at the surface and experienced extensive kelp loss. Although temperatures remained cool at depths below the thermocline, kelp persistence in these thermal refugia was strongly constrained by biotic interactions, specifically urchin populations that increased during the heatwave and drove transitions to urchin barrens in deeper rocky habitat. Urchins were, however, largely absent from mixed sand and cobble benthos, leading to an unexpected association between bottom substrate and kelp forest persistence at inshore sites with warm surface waters. Our findings demonstrate both that warm microclimates increase the risk of habitat loss during marine heatwaves and that biotic interactions modified by these events will modulate the capacity of cool microclimates to serve as thermal refugia.


Subject(s)
Kelp , Climate Change , Ecosystem , Forests , Kelp/physiology , Microclimate , Sand
2.
Chemistry ; 28(24): e202104562, 2022 Apr 27.
Article in English | MEDLINE | ID: mdl-35289447

ABSTRACT

The outer coordination sphere of metalloenzyme often plays an important role in its high catalytic activity, however, this principle is rarely considered in the design of man-made molecular catalysts. Herein, four Ru-bda (bda=2,2'-bipyridine-6,6'-dicarboxylate) based molecular water oxidation catalysts with well-defined outer spheres are designed and synthesized. Experimental and theoretical studies showed that the hydrophobic environment around the Ru center could lead to thermodynamic stabilization of the high-valent intermediates and kinetic acceleration of the proton transfer process during catalytic water oxidation. By this outer sphere stabilization, a 6-fold rate increase for water oxidation catalysis has been achieved.


Subject(s)
Protons , Water , Catalysis , Humans , Kinetics , Oxidation-Reduction , Water/chemistry
3.
Org Biomol Chem ; 19(30): 6633-6637, 2021 08 05.
Article in English | MEDLINE | ID: mdl-34286795

ABSTRACT

Two dipyridyl ligands were synthesized, where the pyridyl donor fragments were separated by an isophthalamide (1) or a dipicolinamide moiety (2). Both ligands formed [Pd2(Ligand)4][BF4]4 complexes in CD2Cl2 containing 5% dmso-d6. It was found that while [Pd2(1)4][BF4]4 readily binds to n-octyl glycosides and to nitrate anions, [Pd2(2)4][BF4]4 did not. The difference in binding properties could be rationalized based on the reduced flexibility and size of the [Pd2(2)4]2+ cage and/or stronger interior binding of a BF4- counter anion.

4.
Chem Commun (Camb) ; 57(58): 7184-7187, 2021 Jul 20.
Article in English | MEDLINE | ID: mdl-34190254

ABSTRACT

The hollow [PdL][BArF]2 complex 1 of a tetra-pyridyl (py) ligand (L) has a [Pd(py)4]2+ coordination environment. Addition of coordinating anions resulted in the formation of a neutral species with Pd(py)2(anion)2 coordination environment (12A). These species bind further to the coordinating anions in the order Cl- > N3- > Br- > I- > AcO- with Ka1 : 1 ≤ 414 M-1. With relatively non-coordinating anions 1 remains intact and displays 1 : 2 binding behaviour dominated by the 1 : 1 stoichiometry in the order NO3- (∼105 M-1) ¼ ClO4- and BF4- (∼103 M-1). As evidenced by crystal structure data, DFT calculations and {1H-19F}-HOESY NMR with BF4-, the anions are bound by charge assisted [C-H]+···anion interactions.

5.
Angew Chem Int Ed Engl ; 60(29): 16178-16183, 2021 07 12.
Article in English | MEDLINE | ID: mdl-33964110

ABSTRACT

Galectins are a galactoside specific subclass of carbohydrate binding proteins (lectins) involved in various cellular activities, certain cancers, infections, inflammations, and many other biological processes. The molecular basis for the selectivity of galectins is well-documented and revolves around appropriate interaction complementarity: an aromatic residue for C-H⋅⋅⋅π interactions and polar residues for (charge assisted) hydrogen bonds with the axial hydroxyl group of a galactoside. However, no synthetic mimics are currently available. We now report on the design and synthesis of the first galectin mimic (6), and show that it has a higher than 65-fold preference for n-octyl-ß-galactoside (8) over n-octyl-ß-glucoside (7) in CD2 Cl2 containing 5 % [D6 ]DMSO (with Ka ≥4500 M-1 for 6:8). Molecular modeling informed by nOe studies reveal a high degree of interaction complementarity between 6 and galactoside 8, which is very similar to the interaction complementarity found in natural galectins.

6.
Angew Chem Int Ed Engl ; 60(26): 14504-14511, 2021 Jun 21.
Article in English | MEDLINE | ID: mdl-33861495

ABSTRACT

O-O bond formation with Ru(bda)L2 -type catalysts is well-known to proceed through a bimolecular reaction pathway, limiting the potential application of these catalysts at low concentrations. Herein, we achieved high efficiencies with mononuclear catalysts, with TOFs of 460±32 s-1 at high catalyst loading and 31±3 s-1 at only 1 µM catalyst concentration, by simple structural considerations on the axial ligands. Kinetic and DFT studies show that introduction of an off-set in the interaction between the two catalytic units reduces the kinetic barrier of the second-order O-O bond formation, maintaining high catalytic activity even at low catalyst concentrations. The results herein furthermore suggest that π-π interactions may only play a minor role in the observed catalytic activity, and that asymmetry can also rationalize high activity observed for Ru(bda)(isoq)2 type catalysts and offer inspiration to overcome the limitations of 2nd order catalysis.

7.
J Chem Educ ; 98(2): 540-545, 2021 Feb 09.
Article in English | MEDLINE | ID: mdl-33583952

ABSTRACT

Mixing the liquids hexafluorobenzene (1) and 1,3,5-trimethylbenzene (mesitylene, 2) results in a crystalline solid with a melting point of 34 °C. The solid consists of alternating π-π stacked pillars of both aromatics. This simple experiment can be used to visually demonstrate the existence and the effect of noncovalent intermolecular π-π stacking interactions. Both benzene derivatives are relatively benign and widely available, and the experiment can be performed within minutes for less than $15 when done on a 22 mL scale (total volume). The demonstration is very robust, as 1:2 mixtures in volume ratios between 2/3 and 3/2 all give a visually similar result (molar ratios of 1.8-0.8). Substituting 2 with the liquid aromatics o-xylene, p-xylene, and aniline also resulted in the formation of a crystalline solid, while using many other liquid aromatics did not.

8.
Inorg Chem ; 60(2): 1202-1207, 2021 Jan 18.
Article in English | MEDLINE | ID: mdl-33382240

ABSTRACT

Water provides an ideal source for the production of protons and electrons required for generation of renewable fuels. Among the most-prominent electrocatalysts capable of water oxidation at low overpotentials are Ru(bda)L2-type catalysts. Although many studies were dedicated to the investigation of the influence of structural variations, the true implication of the bda backbone on catalysis remains mostly unclarified. In this work, we further investigated if electronic effects are contributing to catalysis by Ru(bda)(pic)2 or if the intrinsic catalytic activity mainly originates from the structural features of the ligand. Through introduction of pyrazines in the bda backbone, forming Ru(N1-bda)(pic)2 and Ru(N2-bda)(pic)2, electronic differences were maximized while minimizing changes in the geometry and other intermolecular interactions. Through a combination of electrochemical analysis, chemical oxygen evolution, and density functional theory calculations, we reveal that the catalytic activity is unaffected by the electronic features of the backbone and that the unique bimolecular reactivity of the Ru(bda)L2 family of catalysts thus purely depends on the spatial geometry of the ligand.

9.
ChemSusChem ; 13(22): 5901-5909, 2020 Nov 20.
Article in English | MEDLINE | ID: mdl-32896049

ABSTRACT

Tuning the local environment of nanomaterial-based catalysts has emerged as an effective approach to optimize their oxygen evolution reaction (OER) performance, yet the controlled electronic modulation around surface active sites remains a great challenge. Herein, directed electronic modulation of NiO nanoparticles was achieved by simple surface molecular modification with small organic molecules. By adjusting the electronic properties of modifying molecules, the local electronic structure was rationally tailored and a close electronic structure-activity relationship was discovered: the increasing electron-withdrawing modification readily decreased the electron density around surface Ni sites, accelerating the reaction kinetics and improving OER activity, and vice versa. Detailed investigation by operando Raman spectroelectrochemistry revealed that the electron-withdrawing modification facilitates the charge-transfer kinetics, stimulates the catalyst reconstruction, and promotes abundant high-valent γ-NiOOH reactive species generation. The NiO-C6 F5 catalyst, with the optimized electronic environment, exhibited superior performance towards water oxidation. This work provides a well-designed and effective approach for heterogeneous catalyst fabrication under the molecular level.

10.
J Fish Biol ; 96(4): 1060-1064, 2020 Apr.
Article in English | MEDLINE | ID: mdl-32060916

ABSTRACT

Stable nitrogen (δ15 N) and carbon (δ13 C) isotope ratios from muscle, liver and yolk were analysed from the mother and embryos of an ovoviviparous shark, Hexanchus griseus. Embryonic liver and muscle had similar δ15 N and δ13 C ratios or were depleted in heavy isotopes, compared to the same maternal somatic and reproductive yolk tissues, but no relationship existed between δ15 N or δ13 C and embryo length, as expected, because a switch to placental nourishment is lacking in this species. This study expands the understanding of maternal nourishment and embryonic stable isotope differences in ovoviviparous sharks.


Subject(s)
Carbon Isotopes/analysis , Nitrogen Isotopes/analysis , Sharks/physiology , Animals , Embryo, Nonmammalian/chemistry , Female , Liver/chemistry , Muscles/chemistry , Ovoviviparity
11.
Chemistry ; 25(63): 14408-14413, 2019 Nov 13.
Article in English | MEDLINE | ID: mdl-31390489

ABSTRACT

The ability to use unprotected carbohydrates in olefin metathesis reactions in aqueous media is demonstrated. By using water-soluble, amine-functionalized Hoveyda-Grubbs catalysts under mildly acidic aqueous conditions, the self-metathesis of unprotected alkene-functionalized α-d-manno- and α-d-galactopyranosides could be achieved through minimization of nonproductive chelation and isomerization. Cross-metathesis with allyl alcohol could also be achieved with reasonable selectivity. The presence of small quantities (2.5 vol %) of acetic acid increased the formation of the self-metathesis product while significantly reducing the alkene isomerization process. The catalytic activity was furthermore retained in the presence of large amounts (0.01 mm) of protein, underlining the potential of this carbon-carbon bond-forming reaction under biological conditions. These results demonstrate the potential of directly using unprotected carbohydrate structures in olefin metathesis reactions under mild conditions compatible with biological systems, and thereby enabling their use in, for example, drug discovery and protein derivatization.

12.
Biosens Bioelectron ; 139: 111328, 2019 Aug 15.
Article in English | MEDLINE | ID: mdl-31136921

ABSTRACT

Quartz crystal microbalance (QCM) methodology has been adopted to unravel important factors contributing to the "cluster glycoside effect" observed in carbohydrate-lectin interactions. Well-defined, glycosylated nanostructures of precise sizes, geometries and functionalization patterns were designed and synthesized, and applied to analysis of the interaction kinetics and thermodynamics with immobilized lectins. The nanostructures were based on Borromean rings, dodecaamine cages, and fullerenes, each of which carrying a defined number of carbohydrate ligands at precise locations. The synthesis of the Borromeates and dodecaamine cages was easily adjustable due to the modular assembly of the structures, resulting in variations in presentation mode. The binding properties of the glycosylated nanoplatforms were evaluated using flow-through QCM technology, as well as hemagglutination inhibition assays, and compared with dodecaglycosylated fullerenes and a monovalent reference. With the QCM setup, the association and dissociation rate constants and the associated equilibrium constants of the interactions could be estimated, and the results used to delineate the multivalency effects of the lectin-nanostructure interactions.


Subject(s)
Biosensing Techniques , Lectins/chemistry , Quartz Crystal Microbalance Techniques , Surface Plasmon Resonance , Carbohydrates/chemistry , Concanavalin A/chemistry , Glycosylation , Ligands , Nanostructures/chemistry , Protein Binding
13.
Angew Chem Int Ed Engl ; 58(27): 9155-9159, 2019 07 01.
Article in English | MEDLINE | ID: mdl-31025774

ABSTRACT

The use of water as an oxygen and hydrogen source for the paired oxygenation and hydrogenation of organic substrates to produce valuable chemicals is of utmost importance as a means of establishing green chemical syntheses. Inspired by the active Ni3+ intermediates involved in electrocatalytic water oxidation by nickel-based materials, we prepared NiBx as a catalyst and used water as the oxygen source for the oxygenation of various organic compounds. NiBx was further employed as both an anode and a cathode in a paired electrosynthesis cell for the respective oxygenation and hydrogenation of organic compounds, with water as both the oxygen and hydrogen source. Conversion efficiency and selectivity of ≥99 % were observed during the oxygenation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid and the simultaneous hydrogenation of p-nitrophenol to p-aminophenol. This paired electrosynthesis cell has also been coupled to a solar cell as a stand-alone reactor in response to sunlight.

14.
Chemistry ; 24(1): 101-104, 2018 Jan 02.
Article in English | MEDLINE | ID: mdl-29149517

ABSTRACT

Catalyst discovery from systems of potential precursors is a challenging endeavor. Herein, a new strategy applying dynamic chemistry to the identification of catalyst precursors from C-H activation of imines is proposed and evaluated. Using hydroacylation of imines as a model reaction, the selection of an organometallic reactive intermediate from a dynamic imine system, involving many potential directing group/metal entities, is demonstrated. The identity of the amplified reaction intermediate with the best directing group could be resolved in situ by ESI-MS, and coupling of the procedure to an iterative deconvolution protocol generated a system with high screening efficiency.

15.
Chemistry ; 22(4): 1266-9, 2016 Jan 22.
Article in English | MEDLINE | ID: mdl-26646583

ABSTRACT

An enantioselective synthesis of an intermediate in the Tanino total synthesis of solanoeclepin A has been developed. The key step was an intramolecular [2+2] photocycloaddition, which led to the tricyclo[5.2.1.0(1, 6)] decane core in six steps. The first photosubstrate, prepared through an indium-mediated Barbier-type reaction, gave an excellent [2+2] cycloaddition, but it could not be obtained in sufficient enantiopurity. The second photosubstrate, prepared through an asymmetric allene diborylation in high enantiomeric excess, gave the [2+2] cycloaddition product in high yield on irradiation at 365 nm on 20 g scale in a flow system. Other important steps were the replacement of a boronate group at the quaternary carbon by a vinyl group and diastereoselective cyclopropanation of an allylic alcohol.


Subject(s)
Alkadienes/chemistry , Bridged-Ring Compounds/chemical synthesis , Hexanes/chemical synthesis , Polycyclic Compounds/chemical synthesis , Bridged-Ring Compounds/chemistry , Cycloaddition Reaction , Hexanes/chemistry , Polycyclic Compounds/chemistry , Stereoisomerism
16.
J Am Chem Soc ; 134(1): 201-4, 2012 Jan 11.
Article in English | MEDLINE | ID: mdl-22185581

ABSTRACT

Geminal frustrated Lewis pairs (FLPs) are expected to exhibit increased reactivity when the donor and acceptor sites are perfectly aligned. This is shown for reactions of the nonfluorinated FLP tBu(2)PCH(2)BPh(2) with H(2), CO(2), and isocyanates and supported computationally.


Subject(s)
Electrons , Benzene/chemistry , Models, Molecular , Molecular Conformation
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