Accumulation and Pulse Electron Paramagnetic Resonance Spectroscopic Investigation of the 4-Oxidobenzyl Radical Generated in the Radical S-Adenosyl-l-methionine Enzyme HydG.

The radical S-adenosyl-l-methionine (SAM) enzyme HydG cleaves tyrosine to generate CO and CN- ligands of the [FeFe] hydrogenase H-cluster, accompanied by the formation of a 4-oxidobenzyl radical (4-OB•), which is the precursor to the HydG p-cresol byproduct. Native HydG only generates a small amount of 4-OB•, limiting detailed electron paramagnetic resonance (EPR) spectral characterization beyond our initial EPR lineshape study employing various tyrosine isotopologues. Here, we show that the concentration of trapped 4-OB• is significantly increased in reactions using HydG variants, in which the "dangler Fe" to which CO and CN- bind is missing or substituted by a redox-inert Zn2+ ion. This allows for the detailed characterization of 4-OB• using high-field EPR and electron nuclear double resonance spectroscopy to extract its g-values and 1H/13C hyperfine couplings. These results are compared to density functional theory-predicted values of several 4-OB• models with different sizes and protonation states, with a best fit to the deprotonated radical anion configuration of 4-OB•. Overall, our results depict a clearer electronic structure of the transient 4-OB• radical and provide new insights into the radical SAM chemistry of HydG.

Divalent Lanthanide Metallocene Complexes with a Linear Coordination Geometry and Pronounced 6s-5d Orbital Mixing.

A small but growing number of molecular compounds have been isolated featuring divalent lanthanides with 4fn5dz21 electron configurations. While the majority of these possess trigonal coordination geometries, we previously reported the first examples of linear divalent metallocenes Ln(CpiPr5)2 (Ln = Tb, Dy; CpiPr5 = pentaisopropylcyclopentadienyl). Here, we report the synthesis and characterization of the remainder of the Ln(CpiPr5)2 (1-Ln) series (including Y and excluding Pm). The compounds can be synthesized through salt metathesis of LnI3 and NaCpiPr5 followed by potassium graphite reduction for Ln = Y, La, Ce, Pr, Nd, Gd, Ho, and Er, by in situ reduction during salt metathesis of LnI3 and NaCpiPr5 for Ln = Tm and Lu, or through salt metathesis from LnI2 and NaCpiPr5 for Ln = Sm, Eu, and Yb. Single crystal X-ray diffraction analyses of 1-Ln confirm a linear coordination geometry with pseudo-D5d symmetry for the entire series. Structural and ultraviolet-visible spectroscopy data support a 4fn+1 electron configuration for Ln2+ = Sm, Eu, Tm, and Yb and a 4fn5dz21 configuration for the other lanthanides ([Kr]4dz21 for Y2+). Characterization of 1-Ln (Ln = Y, La) using electron paramagnetic resonance spectroscopy reveals significant s-d orbital mixing in the highest occupied molecular orbital and hyperfine coupling constants that are the largest reported to date for divalent compounds of yttrium and lanthanum. Evaluation of the room temperature magnetic susceptibilities of 1-Ln and comparison with values previously reported for trigonal Ln2+ compounds suggests that the more pronounced 6s-5d mixing may be associated with weaker 4f-5d spin coupling.

CaMn3IV O4 Cubane Models of the Oxygen-Evolving Complex: Spin Ground States S<9/2 and the Effect of Oxo Protonation.

We report the single crystal XRD and MicroED structure, magnetic susceptibility, and EPR data of a series of CaMn3IV O4 and YMn3IV O4 complexes as structural and spectroscopic models of the cuboidal subunit of the oxygen-evolving complex (OEC). The effect of changes in heterometal identity, cluster geometry, and bridging oxo protonation on the spin-state structure was investigated. In contrast to previous computational models, we show that the spin ground state of CaMn3IV O4 complexes and variants with protonated oxo moieties need not be S=9/2. Desymmetrization of the pseudo-C3 -symmetric Ca(Y)Mn3IV O4 core leads to a lower S=5/2 spin ground state. The magnitude of the magnetic exchange coupling is attenuated upon oxo protonation, and an S=3/2 spin ground state is observed in CaMn3IV O3 (OH). Our studies complement the observation that the interconversion between the low-spin and high-spin forms of the S2 state is pH-dependent, suggesting that the (de)protonation of bridging or terminal oxygen atoms in the OEC may be connected to spin-state changes.

Pulse EPR Spectroscopic Characterization of the S3 State of the Oxygen-Evolving Complex of Photosystem II Isolated from Synechocystis.

The S3 state is the last semi-stable state in the water splitting reaction that is catalyzed by the Mn4O5Ca cluster that makes up the oxygen-evolving complex (OEC) of photosystem II (PSII). Recent high-field/frequency (95 GHz) electron paramagnetic resonance (EPR) studies of PSII isolated from the thermophilic cyanobacterium Thermosynechococcus elongatus have found broadened signals induced by chemical modification of the S3 state. These signals are ascribed to an S3 form that contains a five-coordinate MnIV center bridged to a cuboidal MnIV3O4Ca unit. High-resolution X-ray free-electron laser studies of the S3 state have observed the OEC with all-octahedrally coordinated MnIV in what is described as an open cuboid-like cluster. No five-coordinate MnIV centers have been reported in these S3 state structures. Here, we report high-field/frequency (130 GHz) pulse EPR of the S3 state in Synechocystis sp. PCC 6803 PSII as isolated in the presence of glycerol. The S3 state of PSII from Synechocystis exhibits multiple broadened forms (≈69% of the total signal) similar to those seen in the chemically modified S3 centers from T. elongatus. Field-dependent ELDOR-detected nuclear magnetic resonance resolves two classes of 55Mn nuclear spin transitions: one class with small hyperfine couplings (|A| ≈ 1-7 MHz) and another with larger hyperfine couplings (|A| ≈ 100 MHz). These results are consistent with an all-MnIV4 open cubane structure of the S3 state and suggest that the broadened S3 signals arise from a perturbation of Mn4A and/or Mn3B, possibly induced by the presence of glycerol in the as-isolated Synechocystis PSII.

S = 3 Ground State for a Tetranuclear MnIV4O4 Complex Mimicking the S3 State of the Oxygen-Evolving Complex.

The S3 state is currently the last observable intermediate prior to O-O bond formation at the oxygen-evolving complex (OEC) of Photosystem II, and its electronic structure has been assigned to a homovalent MnIV4 core with an S = 3 ground state. While structural interpretations based on the EPR spectroscopic features of the S3 state provide valuable mechanistic insight, corresponding synthetic and spectroscopic studies on tetranuclear complexes mirroring the Mn oxidation states of the S3 state remain rare. Herein, we report the synthesis and characterization by XAS and multifrequency EPR spectroscopy of a MnIV4O4 cuboidal complex as a spectroscopic model of the S3 state. Results show that this MnIV4O4 complex has an S = 3 ground state with isotropic 55Mn hyperfine coupling constants of -75, -88, -91, and 66 MHz. These parameters are consistent with an αααß spin topology approaching the trimer-monomer magnetic coupling model of pseudo-octahedral MnIV centers. Importantly, the spin ground state changes from S = 1/2 to S = 3 as the OEC is oxidized from the S2 state to the S3 state. This same spin state change is observed following oxidation of the previously reported MnIIIMnIV3O4 cuboidal complex to the MnIV4O4 complex described here. This sets a synthetic precedent for the observed low-spin to high-spin conversion in the OEC.

Cueing healthier alternatives for take-away: a field experiment on the effects of (disclosing) three nudges on food choices.

BACKGROUND: The current field experiment demonstrates the effectiveness of nudging to promote healthy food choices. METHODS: Three types of nudges were implemented at a take-away food vendor: 1) an accessibility nudge that placed fruits at the front counter; 2) a salience nudge that presented healthy bread rolls to be more visually attractive; and 3) a social proof nudge that conveyed yoghurt as a popular choice. We additionally assessed whether nudging effects would remain robust when a disclosure message was included. The field experiment was conducted over a seven-week period. The measured outcome was the sales of the targeted healthy food products. RESULTS: The accessibility nudge significantly increased the sales of the fresh fruits. The impact of the salience nudge was limited presumably due to existing preferences or habits that typically facilitate bread purchases. As the sales of the yoghurt shakes remained consistently low over the seven-week period the impact of the social proof nudge remained unexamined. Critically, disclosing the purpose of the nudges did not interfere with effects. CONCLUSIONS: Current findings suggest nudging as an effective strategy for healthy food promotion, and offer implications for topical debate regarding the ethics of nudges.

Tetranuclear [MnIIIMn3IVO4] Complexes as Spectroscopic Models of the S2 State of the Oxygen Evolving Complex in Photosystem II.

Despite extensive biochemical, spectroscopic, and computational studies, the mechanism of biological water oxidation by the oxygen evolving complex (OEC) of Photosystem II remains a subject of significant debate. Mechanistic proposals are guided by the characterization of reaction intermediates such as the S2 state, which features two characteristic EPR signals at g = 2 and g = 4.1. Two nearly isoenergetic structural isomers have been proposed as the source of these distinct signals, but relevant structure-electronic structure studies remain rare. Herein, we report the synthesis, crystal structure, electrochemistry, XAS, magnetic susceptibility, variable temperature CW-EPR, and pulse EPR data for a series of [MnIIIMn3IVO4] cuboidal complexes as spectroscopic models of the S2 state of the OEC. Resembling the oxidation state and EPR spectra of the S2 state of the OEC, these model complexes show two EPR signals, a broad low field signal and a multiline signal, that are remarkably similar to the biological system. The effect of systematic changes in the nature of the bridging ligands on spectroscopy were studied. Results show that the electronic structure of tetranuclear Mn complexes is highly sensitive to even small geometric changes and the nature of the bridging ligands. Our model studies suggest that the spectroscopic properties of the OEC may also react very sensitively to small changes in structure; the effect of protonation state and other reorganization processes need to be carefully assessed.

Nudging healthy food choices: a field experiment at the train station.

BACKGROUND: Recognizing the mindless nature of many food decisions, it has been suggested that attempts to increase healthy eating should not focus on convincing people what is 'right' but rather aim to adjust the environment such that people are automatically directed toward healthy choices. This study investigated a nudge aiming to promote healthy food choices in train station snack shops. METHODS: The nudge involved a repositioning of food products: healthy foods were placed at the cash register desk, while keeping unhealthy products available elsewhere in the shop. Three snack shops were included: a control condition; a nudge condition repositioning healthy products and a nudge + disclosure condition employing the same nudge together with an explanatory sign. Next to examining its effectiveness during 1 week, the study assessed customers' acceptance of the nudge. RESULTS: Controlling for a baseline week, more healthy (but not fewer unhealthy) products were sold in both nudge conditions, with no difference between the nudge and the nudge + disclosure condition. A majority of customers reported positive attitudes toward the nudge. CONCLUSIONS: Repositioning healthy foods is a simple, effective and well-accepted nudge to increase healthy purchases. Moreover, disclosing its purpose does not impact on effectiveness.

Preventing the pack size effect: exploring the effectiveness of pictorial and non-pictorial serving size recommendations.

People eat more from large than from small packs, which is known as the pack size effect. We hypothesized that providing a serving size recommendation would reduce the influence of the pack size on consumption and would thus diminish the pack size effect. Moreover, we hypothesized that a pictorial serving size recommendation, displaying food amounts visually, would be more effective than a non-pictorial recommendation that communicates the recommended amount in grams only. We tested these hypotheses in two online experiments (N = 317 and N = 324) and in one lab experiment (N = 89). In the online experiments, participants were shown a small or a large pack of unhealthy snacks, with or without a serving size recommendation. The main outcome measure was expected consumption. Replicating the pack size effect in an online setting, we found that participants expected to consume more food from large than from small packs. Furthermore, the pack size effect was considerably stronger for men than for women. Importantly, when including portion size preferences as a covariate, the pictorial serving size recommendation significantly reduced expected consumption, especially when placed on a large pack, as hypothesized. The non-pictorial serving size recommendation had no effect. In the lab experiment, students received a large bag of M&M's which did or did not contain the pictorial serving size recommendation. We again included general portion size preferences as a covariate. The serving size recommendation significantly lowered the amount of M&M's that participants served themselves, but only when participants reported to have noticed the serving size recommendation. We conclude that providing a pictorial serving size recommendation can be an effective intervention strategy to reduce the pack size effect, if it attracts sufficient attention.

A brief mindfulness intervention reduces unhealthy eating when hungry, but not the portion size effect.

OBJECTIVE: The present research examined the effects of a mindfulness-based intervention to foster healthy eating. Specifically, we tested whether a brief mindfulness manipulation can prevent the portion size effect, and reduce overeating on unhealthy snacks when hungry. METHODS: 110 undergraduate participants (MAge=20.9±2.3; MBMI=22.3±2.5) were served a small or a large portion of chocolate chip cookies after listening to an audio book or performing a mindfulness exercise (i.e., body scan). Current level of hunger was assessed unobtrusively on a visual analog scale before the eating situation. MAIN OUTCOME MEASURE: Calorie intake from chocolate chip cookies. RESULTS: When presented with a large compared to a small portion, participants consumed more cookies (+83kcal). This was not affected by the mindfulness intervention or by hunger. However, while control participants ate more unhealthy food when hungry than when not hungry (+67kcal), participants in the mindfulness condition did not (+1kcal). CONCLUSIONS: Findings confirm the prevalence and robustness of the portion size effect and suggest that it may be independent from awareness of internal cues. Prevention strategies may benefit more from targeting awareness of the external environment. However, mindfulness-based interventions may be effective to reduce effects of hunger on unhealthy food consumption.

The portion size effect on food intake. An anchoring and adjustment process?

People consistently over-eat when served a large compared with a small (appropriate) portion of food. However, the mechanism underlying this so-called portion size effect is not well understood. We argue that the process of anchoring and adjustment naturally describes this effect, such that the size of a presented portion works as an anchor that strongly influences consumption. The classical anchoring and adjustment paradigm was applied to six hypothetical eating situations. Participants were asked to imagine being served either a small or a large portion of food (i.e., low and high anchor) and to indicate whether they would consume more or less than this amount. Then, they indicated how much they would eat. These estimates were compared with a no-anchor condition where participants did not imagine a specific portion size but only indicated how much they would eat. In addition, half of participants in the anchoring conditions received a discounting instruction stating that the portion size they had been asked to imagine was randomly selected and thus not informative for their consumption estimate. As expected, participants who imagined to be served larger portions estimated to consume significantly more food than participants in the no-anchor condition, and participants who imagined to be served smaller portions estimated to consume significantly less food than participants in the no-anchor condition. The discounting manipulation did not reduce this effect of the anchors. We suggest that the process of anchoring and adjustment may provide a useful framework to understand the portion size effect and we discuss implications of this perspective.

Container size influences snack food intake independently of portion size.

While larger containers have been found to increase food intake, it is unclear whether this effect is driven by container size, portion size, or their combination, as these variables are usually confounded. The study was advertised as examining the effects of snack food consumption on information processing and participants were served M&M's for free consumption in individual cubicles while watching a TV show. Participants were served (1) a medium portion of M&M's in a small (n=30) or (2) in a large container (n=29), or (3) a large portion in a large container (n=29). The larger container increased intake by 129% (199 kcal) despite holding portion size constant, while controlling for different confounding variables. This research suggests that larger containers stimulate food intake over and above their impact on portion size.

Ultrahard magnetism from mixed-valence dilanthanide complexes with metal-metal bonding.

Magnetic effects of lanthanide bonding Lanthanide coordination compounds have attracted attention for their persistent magnetic properties near liquid nitrogen temperature, well above alternative molecular magnets. Gould et al. report that introducing metal-metal bonding can enhance coercivity. Reduction of iodide-bridged terbium or dysprosium dimers resulted in a single electron bond between the metals, which enforced alignment of the other valence electrons. The resultant coercive fields exceeded 14 tesla below 50 and 60 kelvin for the terbium and dysprosium compounds, respectively. ­JSY

Isolation of a triplet benzene dianion.

Baird's rule predicts that molecules with 4n π electrons should be aromatic in the triplet state, but the realization of simple ring systems with such an electronic ground state has been stymied by these molecules' tendency to distort into structures bearing a large singlet-triplet gap. Here, we show that the elusive benzene diradical dianion can be stabilized through creation of a binucleating ligand that enforces a tightly constrained inverse sandwich structure and direct magnetic exchange coupling. Specifically, we report the compounds [K(18-crown-6)(THF)2]2[M2(BzN6-Mes)] (M = Y, Gd; BzN6-Mes = 1,3,5-tris[2',6'-(N-mesityl)dimethanamino-4'-tert-butylphenyl]benzene), which feature a trigonal ligand that binds one trivalent metal ion on each face of a central benzene dianion. Antiferromagnetic exchange in the Gd3+ compound preferentially stabilizes the triplet state such that it becomes the molecular ground state. Single-crystal X-ray diffraction data and nucleus-independent chemical shift calculations support aromaticity, in agreement with Baird's rule.

Structural Effects of Ammonia Binding to the Mn4CaO5 Cluster of Photosystem II.

The Mn4CaO5 oxygen-evolving complex (OEC) of photosystem II catalyzes the light-driven oxidation of two substrate waters to molecular oxygen. ELDOR-detected NMR along with computational studies indicated that ammonia, a substrate analogue, binds as a terminal ligand to the Mn4A ion trans to the O5 µ4 oxido bridge. Results from electron spin echo envelope modulation (ESEEM) spectroscopy confirmed this and showed that ammonia hydrogen bonds to the carboxylate side chain of D1-Asp61. Here we further probe the environment of OEC with an emphasis on the proximity of exchangeable protons, comparing ammonia-bound and unbound forms. Our ESEEM and electron nuclear double resonance (ENDOR) results indicate that ammonia substitutes for the W1 terminal water ligand without significantly altering the electronic structure of the OEC.

"Split them!" smaller item sizes of cookies lead to a decrease in energy intake in children.

OBJECTIVE: Examine the influence of altering the size of snack food (ie, small vs large cookies) on short-term energy intake. METHODS: First- and sixth-graders (n = 77) participated in a between-subjects experimental design. All participants were offered the same gram weight of cookies during an afternoon tea at their school. For half of the participants, food was cut in 2 to make the small item size. Food intake (number of cookies, gram weight, and energy intake) was examined using ANOVA. RESULTS: Decreasing the item size of food led to a decrease of 25% in gram weight intake, corresponding to 68 kcal. Appetitive ratings and subject and food characteristics had no moderating effect. CONCLUSIONS AND IMPLICATIONS: Reducing the item size of food could prove a useful dietary prevention strategy based on decreased consumption, aimed at countering obesity-promoting eating behaviors favored by the easy availability of large food portions.

Smaller food item sizes of snack foods influence reduced portions and caloric intake in young adults.

Studies considering the impact of food-size variations on consumption have predominantly focused on portion size, whereas very little research has investigated variations in food-item size, especially at snacking occasions, and results have been contradictory. This study evaluated the effect of altering the size of food items (ie, small vs large candies) of equal-size food portions on short-term energy intake while snacking. The study used a between-subjects design (n=33) in a randomized experiment conducted in spring 2008. In a psychology laboratory (separate cubicles), participants (undergraduate psychology students, 29 of 33 female, mean age 20.3±2 years, mean body mass index 21.7±3.7) were offered unlimited consumption of candies while participating in an unrelated computerized experiment. For half of the subjects, items were cut in two to make the small food-item size. Food intake (weight in grams, kilocalories, and number of food items) was examined using analysis of variance. Results showed that decreasing the item size of candies led participants to decrease by half their gram weight intake, resulting in an energy intake decrease of 60 kcal compared to the other group. Appetite ratings and subject and food characteristics had no moderating effect. A cognitive bias could explain why people tend to consider that one unit of food (eg, 10 candies) is the appropriate amount to consume, regardless of the size of the food items in the unit. This study suggests a simple dietary strategy, decreasing food-item size without having to alter the portion size offered, may reduce energy intake at snacking occasions.