Experimental and Theoretical Insights on the Structural, Electronic, and Magnetic Properties of the Quaternary Selenides EuPrCuSe3 and EuNdCuSe3.

Magnetic semiconductors EuPrCuSe3 and EuNdCuSe3 were obtained by using the halide flux method. Their crystal structures and magnetic properties were studied and discussed. Optical properties of the obtained selenides were studied by the means of diffuse reflectance spectroscopy, which revealed the values of 1.92/1.97 and 0.90/0.94 eV for the direct and indirect band gaps of Ln = Nd/Pr, respectively. The structural, electronic, and magnetic properties of the obtained compounds were additionally studied with spin-polarized density functional theory calculations, wherein both systems were found to be two new examples of semiconducting quaternary selenides with disperse conduction bands of Nd/Pr 5d character. The modeling showed that various magnetic orderings in the systems have subtle influences on the alignments/overlaps between the Se/Cu, Eu, and Pr/Nd bands, and that the spin-state energetics are very dependent upon the treatment of electron correlation, but a distinguishing feature in the case of ferromagnetic coupling is that the spin density on the Se atoms is maximized. Overall, the calculations are in good agreement with the experimental characterization of ferromagnetism in the bulk crystals, wherein the ferromagnetic transition occurs at temperatures of about 2.5 K for EuPrCuSe3 and about 3 K for EuNdCuSe3.

Influence of O-H⋠⋠⋠Pt interactions on photoluminescent response in the (Et4N)2{[Pt(bph)(CN)2][phenylene-1,4-diresorcinol]} framework.

Tunable photoluminescence (PL) is one of the hot topics in current materials science, and research performed on the molecular phases is at the forefront of this field. We present the new (Et4N)2[PtII(bph)(CN)2]⋅rez3⋅1/3H2O (Pt2rez3) (bph=biphenyl-2,2'-diyl; rez3=3,3",5,5"-tetrahydroxy-1,1':4',1"-terphenyl, phenylene-1,4-diresorcinol coformer, a linear quaternary hydrogen bond donor) co-crystal salt based on the recently appointed promising [PtII(bph)(CN)2]2- luminophore. Within the extended hydrogen-bonded subnetwork [PtII(bph)(CN)2]2- complexes and rez3 coformer molecules form two types of contacts: the rez3O-H⋅⋅⋅Ncomplex ones in the equatorial plane of the complex and non-typical rez3O-H⋅⋅⋅Pt ones along its axial direction. The combined structural, PL, and DFT approach identified the rez3O-H⋅⋅⋅Pt synthons to be crucial in promoting the noticeable uniform redshift of bph ligand centered (LC) emission compared to the LC emission of the (Et4N)2[PtII(bph)(CN)2]⋅H2O (Pt2) precursor, owing to the direct interference of the phenol group with the PtII-bph orbital system via altering the CT processes within. The high-resolution emission spectra for Pt2 and Pt2rez3 were successfully reproduced at 77 K by using the Franck-Cordon expressions. The possibility to tune PL properties along the plausible continuum of rez3O-H⋅⋅⋅Pt synthons is indicated, considering various scenarios of molecular occupation of the space above and below the complex plane.

Synchronous Switching of Dielectric Constant and Photoluminescence in Cyanidonitridorhenate-Based Crystals.

Switching of multiple physical properties by external stimuli in dynamic materials enables applications in, e.g., smart sensors, biomedical tools, as well as data-storage devices. Among stimuli-responsive materials, inorganic-organic molecular hybrids exhibiting thermal order-disorder phase transitions were tested as promising molecular switches of electrical characteristics, including dielectric constant. We aimed at broadening the multifunctional potential of such hybrid materials towards the switching of not only electrical but also other physical properties, e.g., light emission. We report two ionic salts based on luminescent tetracyanidonitridorhenate(V) anions bearing two different diamine ligands, 1,2-diaminoethane (1) and 1,3-diaminopropane (2), both crystallizing with polar N-methyl-dabconium cations. They exhibit an order-disorder phase transition related to the heating-induced turning-on of the rotation of polar cations. This leads to a unique synchronous switching of the dielectric constant as well as metal-complex-centered photoluminescence, as demonstrated by changes in, e.g., emission lifetime. The roles of organic cations, non-trivial Re(V) complexes, and their interaction in achieving the coupled thermal switching of electrical and optical properties are discussed utilizing experimental and theoretical approaches.

Polyvalent Nano-Lectin Potently Neutralizes SARS-CoV-2 by Targeting Glycans on the Viral Spike Protein.

Mutations in spike (S) protein epitopes allow SARS-CoV-2 variants to evade antibody responses induced by infection and/or vaccination. In contrast, mutations in glycosylation sites across SARS-CoV-2 variants are very rare, making glycans a potential robust target for developing antivirals. However, this target has not been adequately exploited for SARS-CoV-2, mostly due to intrinsically weak monovalent protein-glycan interactions. We hypothesize that polyvalent nano-lectins with flexibly linked carbohydrate recognition domains (CRDs) can adjust their relative positions and bind multivalently to S protein glycans, potentially exerting potent antiviral activity. Herein, we displayed the CRDs of DC-SIGN, a dendritic cell lectin known to bind to diverse viruses, polyvalently onto 13 nm gold nanoparticles (named G13-CRD). G13-CRD bound strongly and specifically to target glycan-coated quantum dots with sub-nM Kd. Moreover, G13-CRD neutralized particles pseudotyped with the S proteins of Wuhan Hu-1, B.1, Delta variant and Omicron subvariant BA.1 with low nM EC50. In contrast, natural tetrameric DC-SIGN and its G13 conjugate were ineffective. Further, G13-CRD potently inhibited authentic SARS-CoV-2 B.1 and BA.1, with <10 pM and <10 nM EC50, respectively. These results identify G13-CRD as the 1st polyvalent nano-lectin with broad activity against SARS-CoV-2 variants that merits further exploration as a novel approach to antiviral therapy.

Polyvalent Glycan Functionalized Quantum Nanorods as Mechanistic Probes for Shape-Selective Multivalent Lectin-Glycan Recognition.

Multivalent lectin-glycan interactions (MLGIs) are widespread in biology and hold the key to many therapeutic applications. However, the underlying structural and biophysical mechanisms for many MLGIs remain poorly understood, limiting our ability to design glycoconjugates to potently target specific MLGIs for therapeutic intervention. Glycosylated nanoparticles have emerged as a powerful biophysical probe for MLGIs, although how nanoparticle shape affects the MLGI molecular mechanisms remains largely unexplored. Herein, we have prepared fluorescent quantum nanorods (QRs), densely coated with α-1,2-manno-biose ligands (QR-DiMan), as multifunctional probes to investigate how scaffold geometry affects the MLGIs of a pair of closely related, tetrameric viral receptors, DC-SIGN and DC-SIGNR. We have previously shown that a DiMan-capped spherical quantum dot (QD-DiMan) gives weak cross-linking interactions with DC-SIGNR but strong simultaneous binding with DC-SIGN. Against the elongated QR-DiMan, DC-SIGN retains similarly strong simultaneous binding of all four binding sites with a single QR-DiMan (apparent K d ≈ 0.5 nM, ∼1.8 million-fold stronger than the corresponding monovalent binding), while DC-SIGNR gives both weak cross-linking and strong individual binding interactions, resulting in a larger binding affinity enhancement than that with QD-DiMan. S/TEM analysis of QR-DiMan-lectin assemblies reveals that DC-SIGNR's different binding modes arise from the different nanosurface curvatures of the QR scaffold. The glycan display at the spherical ends presents too high a steric barrier for DC-SIGNR to bind with all four binding sites; thus, it cross-links between two QR-DiMan to maximize binding multivalency, whereas the more planar character of the cylindrical center allows the glycans to bridge all binding sites in DC-SIGNR. This work thus establishes glycosylated QRs as a powerful biophysical probe for MLGIs not only to provide quantitative binding affinities and binding modes but also to demonstrate the specificity of multivalent lectins in discriminating different glycan displays in solution, dictated by the scaffold curvature.

Polyvalent Glycan Quantum Dots as a Multifunctional Tool for Revealing Thermodynamic, Kinetic, and Structural Details of Multivalent Lectin-Glycan Interactions.

Multivalent lectin-glycan interactions (MLGIs) are widespread and vital for biology. Their binding biophysical and structural details are thus highly valuable, not only for the understanding of binding affinity and specificity mechanisms but also for guiding the design of multivalent therapeutics against specific MLGIs. However, effective techniques that can reveal all such details remain unavailable. We have recently developed polyvalent glycan quantum dots (glycan-QDs) as a new probe for MLGIs. Using a pair of closely related tetrameric viral-binding lectins, DC-SIGN and DC-SIGNR, as model examples, we have revealed and quantified their large affinity differences in glycan-QD binding are due to distinct binding modes: with simultaneous binding for DC-SIGN and cross-linking for DC-SIGNR. Herein, we further extend the capacity of the glycan-QD probes by investigating the correlation between binding mode and binding thermodynamics and kinetics and further probing a structural basis of their binding nature. We reveal that while both lectins' binding with glycan-QDs is enthalpy driven with similar binding enthalpy changes, DC-SIGN pays a lower binding entropy penalty, resulting in a higher affinity than DC-SIGNR. We then show that DC-SIGN binding gives a single second-order kon rate, whereas DC-SIGNR gives a rapid initial binding followed by a much slower secondary interaction. We further identify a structural element in DC-SIGN, absent in DC-SIGNR, that plays an important role in maintaining DC-SIGN's MLGI character. Its removal switches the binding from being enthalpically to entropically driven and gives mixed binding modes containing both simultaneous and cross-linking binding behavior, without markedly affecting the overall binding affinity and kinetics.

Toward high-throughput oligomer detection and classification for early-stage aggregation of amyloidogenic protein.

Aggregation kinetics of proteins and peptides have been studied extensively due to their significance in many human diseases, including neurodegenerative disorders, and the roles they play in some key physiological processes. However, most of these studies have been performed as bulk measurements using Thioflavin T or other fluorescence turn-on reagents as indicators of fibrillization. Such techniques are highly successful in making inferences about the nucleation and growth mechanism of fibrils, yet cannot directly measure assembly reactions at low protein concentrations which is the case for amyloid-ß (Aß) peptide under physiological conditions. In particular, the evolution from monomer to low-order oligomer in early stages of aggregation cannot be detected. Single-molecule methods allow direct access to such fundamental information. We developed a high-throughput protocol for single-molecule photobleaching experiments using an automated fluorescence microscope. Stepwise photobleaching analysis of the time profiles of individual foci allowed us to determine stoichiometry of protein oligomers and probe protein aggregation kinetics. Furthermore, we investigated the potential application of supervised machine learning with support vector machines (SVMs) as well as multilayer perceptron (MLP) artificial neural networks to classify bleaching traces into stoichiometric categories based on an ensemble of measurable quantities derivable from individual traces. Both SVM and MLP models achieved a comparable accuracy of more than 80% against simulated traces up to 19-mer, although MLP offered considerable speed advantages, thus making it suitable for application to high-throughput experimental data. We used our high-throughput method to study the aggregation of Aß40 in the presence of metal ions and the aggregation of α-synuclein in the presence of gold nanoparticles.

Fast-track recovery program after cardiac surgery in a teaching hospital: a quality improvement initiative.

OBJECTIVE: Fast-track cardiac anesthesia (FTCA) is a technique that may improve patient access to surgery and maximize workforce utilization. However, feasibility and factors impacting FTCA implementation remain poorly explored both locally and internationally. We describe the specific intraoperative and postoperative protocols for our FTCA program, assess protocol compliance and identify reasons for FTCA failure. RESULTS: We tested the program in 16 patients undergoing elective cardiac surgery requiring cardiopulmonary bypass. There was 100% compliance with the FTCA protocols. Four (25%) patients successfully completed the FTCA protocol (extubated < 4 h postoperatively and discharged from the intensive care unit on the same operative day).

Binding of anionic Pt(ii) complexes in a dedicated organic matrix: towards new binary crystalline composites.

The square-planar [PtX4]2- complexes (X = Cl, Br) were successfully incorporated into preprogrammed hybrid organic-inorganic systems, exploiting their expected strong anion-π interactions with π-acidic hexaazaphenylenehexacarbonitrile, HAT(CN)6. The formation and properties of {[PtCl4]2-; HAT(CN)6} aggregates in MeCN solution were evaluated based on their UV-Vis spectra to reveal the approximate binding constant KCT = 7.9(2) × 102 dm3 mol-1, molar absorption coefficient εCT = 1.47(2) × 103 dm3 mol-1 cm-1, extent of electronic coupling HCT = 2.18 × 103 cm-1, and electron delocalization α2 = 1.75 × 10-2 (α = 0.13). Strong [PtCl4]2-HAT(CN)6 interactions in such adducts were also confirmed by the distinct shifts |Δδiso| = 0.4 ppm of 13C NMR peaks, when compared to the π-acid alone. The crystal structures of the resulting (PPh4)2[PtX4][HAT(CN)6]·3MeCN (1-Cl- and 1-Br-) solids are isomorphous with (PPh4)2[Pt(CN)4][HAT(CN)6]·3MeCN (1-CN-) reported by us previously. The halogenoplatinates occupy exactly the same nodes in the supramolecular network as cyanoplatinate, forming stacked {[PtX4]2-;HAT(CN)6}∞ columns that are stabilized by [PPh4]+ cations. However, contrary to the pale yellow coloration of the [Pt(CN)4]2-/HAT(CN)6 systems, currently the dark violet or dark green coloration of solutions and crystalline phases were noted owing to the intense absorption in almost the whole visible region. DFT calculations reproduced the UV-Vis spectroscopic characteristics and linked it with the enhanced charge-transfer of the [PtX4]2-HAT(CN)6 electronic interactions. Based on the isomorphism of all three (PPh4)2[PtL4][HAT(CN)6]·3MeCN congeners we constructed and characterized the unprecedented, first ever anion-π-based binary rod-like core-shell crystalline composites 1-X@1-CN.

Glycan-Gold Nanoparticles as Multifunctional Probes for Multivalent Lectin-Carbohydrate Binding: Implications for Blocking Virus Infection and Nanoparticle Assembly.

Multivalent lectin-glycan interactions are widespread in biology and are often exploited by pathogens to bind and infect host cells. Glycoconjugates can block such interactions and thereby prevent infection. The inhibition potency strongly depends on matching the spatial arrangement between the multivalent binding partners. However, the structural details of some key lectins remain unknown and different lectins may exhibit overlapping glycan specificity. This makes it difficult to design a glycoconjugate that can potently and specifically target a particular multimeric lectin for therapeutic interventions, especially under the challenging in vivo conditions. Conventional techniques such as surface plasmon resonance (SPR) and isothermal titration calorimetry (ITC) can provide quantitative binding thermodynamics and kinetics. However, they cannot reveal key structural information, e.g., lectin's binding site orientation, binding mode, and interbinding site spacing, which are critical to design specific multivalent inhibitors. Herein we report that gold nanoparticles (GNPs) displaying a dense layer of simple glycans are powerful mechanistic probes for multivalent lectin-glycan interactions. They can not only quantify the GNP-glycan-lectin binding affinities via a new fluorescence quenching method, but also reveal drastically different affinity enhancing mechanisms between two closely related tetrameric lectins, DC-SIGN (simultaneous binding to one GNP) and DC-SIGNR (intercross-linking with multiple GNPs), via a combined hydrodynamic size and electron microscopy analysis. Moreover, a new term, potential of assembly formation (PAF), has been proposed to successfully predict the assembly outcomes based on the binding mode between GNP-glycans and lectins. Finally, the GNP-glycans can potently and completely inhibit DC-SIGN-mediated augmentation of Ebola virus glycoprotein-driven cell entry (with IC50 values down to 95 pM), but only partially block DC-SIGNR-mediated virus infection. Our results suggest that the ability of a glycoconjugate to simultaneously block all binding sites of a target lectin is key to robust inhibition of viral infection.

Resonance Assisted Hydrogen Bonding Phenomenon Unveiled through Both Experiments and Theory: A New Family of Ethyl N-Salicylideneglycinate Dyes.

Extensive experimental and theoretical investigations are reported on the nature of resonance-assisted hydrogen bonding phenomenon (RAHB) and its influence on photophysical properties of the newly designed dyes differing in donor-acceptor properties, namely ethyl N-salicylideneglycinate (1), ethyl N-(5-methoxysalicylidene)glycinate (2), ethyl N-(5-bromosalicylidene)glycinate (3) and ethyl N-(5-nitrosalicylidene)glycinate (4). All compounds are thermochromic in the solid state and they contain a typical intramolecular O-H⋅⋅⋅N hydrogen bond formed between the hydroxyl hydrogen atom and the imine nitrogen atom, yielding the enol form in the solid state. It is unveiled, that the magnitude of RAHB effect fine tunes the strength of the O-H⋅⋅⋅N bonding and accordingly the relative populations of the enol, cis-keto and trans-keto forms leading to variation of the photophysical properties of 1-4. It is determined, that the electron-withdrawing NO2 in 4 amplifies the most RAHB effect causing the breaking of the O-H⋅⋅⋅N hydrogen bond and accordingly formation of the dominant cis-keto isomer in both the solid state and EtOH. To this end, the UV/Vis spectra of 1-3 in EtOH revealed the exclusive presence of the enol form, while the prevalent contribution of the cis-keto form was found for 4. Furthermore, only compound 4 is emissive in the solid state in ambient condition due to dual emission arising from the cis-keto* and trans-keto* forms, while 2 was found to be highly emissive in EtOH. It is revealed qualitatively and quantitatively, based on the ETS-NOCV charge and energy decomposition scheme and the EDDB population-based method, that RAHB is strongly a non-local phenomenon based on electrons pumping or sucking through both the π- and σ-channels, which accordingly exerts chemical bonding changes at both the phenyl ring and predominantly a distant O-H⋅⋅⋅N area.

Urban Particulate Matter-Induced Decomposition of S-Nitrosoglutathione Relevant to Aberrant Nitric Oxide Biological Signaling.

Exposure to airborne particulate matter (PM) is associated with hazardous effects on human health. Soluble constituents of PM may be released in biological fluids and disturb the precisely tuned nitric oxide signaling processes. The influence of aqueous extracts from two types of airborne urban PM (SRM 1648a, a commercially available sample, and KR PM2.5, a sample collected "in-house" in Krakow, Poland) on the stability of S-nitrosoglutathione (GSNO) was investigated. The particle interfaces had no direct effect on the studied reaction, but extracts obtained from both samples facilitated NO release from GSNO. The effectiveness of NO release was significantly affected by glutathione (GSH) and ascorbic acid (AscA). Examination of the combined influence of Cu2+ , Fe3+ , and reductants on GSNO stability revealed copper to be the main GSNO decomposing species. Computational models of nitrosothiols interacting with metal oxide substrates and solvated metal ions support these claims. The study stresses the importance of the interplay between metal ions and biological reductants in S-nitrosothiols decomposition.

Molecular Deformation, Charge Flow, and Spongelike Behavior in Anion-π {[M(CN)4 ]2- ;[HAT(CN)6 ]}∞ (M=Ni, Pd, Pt) Supramolecular Stacks.

The synthesis, crystal structures, spectroscopic characterization, and comprehensive quantum-chemical calculations for a novel series of anion-π hybrid salts (XPh4 )2 [M(CN)4 ][HAT(CN)6 ]⋅3 MeCN (X=P, M=NiII (1), PdII (3), PtII (5); X=As, M=NiII (2), PdII (4), PtII (6); HAT(CN)6 =1,4,5,8,9,11-hexaazatriphenylenehexacarbonitrile) are presented. The systems comprise 1D {[M(CN)4 ]2- ;[HAT(CN)6 ]}∞ stacks, in which the electron-rich metal complexes adjust their orientation to match the electron-deficient areas of HAT(CN)6 . Electronic charge-transfer interactions along the stacks result in polarization of electron density within HAT(CN)6 and in perturbations along the {[M(CN)4 ]2- ;[HAT(CN)6 ]}∞ contacts. Electronic structure analysis suggests, for example, a relocation of 0.1-0.2 e per molecule from [M(CN)4 ]2- to HAT(CN)6 and anion-π interaction energies of around -65 kcal mol-1 . A reversible structural single-crystal-to-single-crystal transformation, through desolvation/resolvation processes in the solid state, is also reported and a scheme for the formation of anion-π [M(CN)4 ]2- /HAT(CN)6 adducts in MeCN is proposed.

On the Border between Low-Nuclearity and One-Dimensional Solids: A Unique Interplay of 1,2,4-Triazolyl-Based {CuII5(OH)2} Clusters and MoVI-Oxide Matrix.

A pentanuclear CuII5-hydroxo cluster possessing an unusual linear-shaped configuration was formed and crystallized under hydrothermal conditions as a result of the unique cooperation of bridging 1,2,4-triazole ligand ( trans-1,4-cyclohexanediyl-4,4'-bi(1,2,4-triazole) ( tr2 cy)), MoVI-oxide, and CuSO4. This structural motif can be rationalized by assuming in situ generation of {Cu2Mo6O22}4- anions, which represent heteroleptic derivatives of γ-type [Mo8O26]4- further interlinked by [Cu3(OH)2]4+ cations through [ N- N] bridges. The framework structure of the resulting compound [Cu5(OH)2( tr2 cy)2Mo6O22]·6H2O (1) is thus built up from neutral heterometallic {Cu5(OH)2Mo6O22} n layers pillared with tetradentate tr2 cy. Quantum-chemical calculations demonstrate that the exclusive site of the parent γ-[Mo8O26]4- cluster into which CuII inserts corresponds with the site that has the lowest defect ("MoO2 vacancy") formation energy, demonstrating how the local metal-polyoxomolybdate chemistry can express itself in the final crystal structure. Magnetic susceptibility measurements of 1 show strong antiferromagnetic coupling within the Cu5 chain with exchange parameters J1 = -500(40) K (-348(28) cm-1), J2 = -350(10) K (-243(7) cm-1) and g = 2.32(2), χ2 = 6.5 × 10-4. Periodic quantum-chemical calculations reproduce the antiferromagnetic character of 1 and connect it with an effective ligand-mediated spin coupling mechanism that comes about from the favorable structural arrangement between the Cu centers and the OH-, O2-, and tr2 cy bridging ligands.

Plasma-Lyte 148 vs. Hartmann's solution for cardiopulmonary bypass pump prime: a prospective double-blind randomized trial.

BACKGROUND: The mechanisms of acid-base changes during cardiopulmonary bypass (CPB) remain unclear. We tested the hypothesis that, when used as CPB pump prime solutions, Plasma-Lyte 148 (PL) and Hartmann's solution (HS) have differential mechanisms of action in their contribution to acid-base changes. METHODS: We performed a prospective, double-blind, randomized trial in adult patients undergoing elective cardiac surgery with CPB. Participants received a CPB prime solution of 2000 mL, with either PL or HS. The primary endpoint was the standard base excess (SBE) value measured at 60 minutes after full CPB flows (SBE60min). Secondary outcomes included changes in SBE, pH, chloride, sodium, lactate, gluconate, acetate, strong ion difference and strong ion gap at two (T2min), five (T5min), ten (T10min), thirty (T30min) and sixty (T60min) minutes on CPB. The primary outcome was measured using a two-tailed Welch's t-test. Repeated measures ANOVA was used to test for differences between time points. RESULTS: Twenty-five participants were randomized to PL and 25 to HS. Baseline characteristics, EURO and APACHE scores, biochemistry, hematology and volumes of cardioplegia were similar. Mean (SD) SBE at T60min was -1.3 (1.4) in the PL group and -0.1 (2.7) in the HS group; p=0.55. No significant differences in SBE between the groups was observed during the first 60 minutes (p=0.48). During CPB, there was hyperacetatemia and hypergluconatemia in the PL group and hyperlactatemia and hyperchloremia in the HS group. No significant difference between the groups in plasma bicarbonate levels and total weak acid levels were found. Complications and intensive care unit and hospital length of stays were similar. CONCLUSIONS: During CPB, PL and HS did not cause a significant metabolic acidosis. There was hyperacetatemia and hypergluconatemia with PL and hyperchloremia and hyperlactatemia with HS. These physiochemical effects appear clinically innocuous.

Locking and Unlocking the Molecular Spin Crossover Transition.

The Fe(II) spin crossover complex [Fe{H2 B(pz)2 }2 (bipy)] (pz = pyrazol-1-yl, bipy = 2,2'-bipyridine) can be locked in a largely low-spin-state configuration over a temperature range that includes temperatures well above the thermal spin crossover temperature of 160 K. This locking of the spin state is achieved for nanometer thin films of this complex in two distinct ways: through substrate interactions with dielectric substrates such as SiO2 and Al2 O3 , or in powder samples by mixing with the strongly dipolar zwitterionic p-benzoquinonemonoimine C6 H2 (-⋯ NH2 )2 (-⋯ O)2 . Remarkably, it is found in both cases that incident X-ray fluences then restore the [Fe{H2 B(pz)2 }2 (bipy)] moiety to an electronic state characteristic of the high spin state at temperatures of 200 K to above room temperature; that is, well above the spin crossover transition temperature for the pristine powder, and well above the temperatures characteristic of light- or X-ray-induced excited-spin-state trapping. Heating slightly above room temperature allows the initial locked state to be restored. These findings, supported by theory, show how the spin crossover transition can be manipulated reversibly around room temperature by appropriate design of the electrostatic and chemical environment.

Anion-π recognition between [M(CN)6]3- complexes and HAT(CN)6: structural matching and electronic charge density modification.

Hexacyanidometalates (M = FeIII, CoIII) and multisite anion receptor HAT(CN)6 (1,4,5,8,9,11-hexaazatriphenylenehexacarbonitrile) recognize each other in acetonitrile solution and self-assemble into the novel molecular networks (PPh4)3[M(CN)6][HAT(CN)6] (M = Fe, 1; Co, 2) and (AsPh4)3[M(CN)6][HAT(CN)6]·2MeCN·H2O (M = Fe, 3; Co, 4). 1-4 contain the stacked columns {[M(CN)6]3-;[HAT(CN)6]}∞ separated by the organic cations. All of the M-C[triple bond, length as m-dash]N vectors point collectively towards the centroids of pyrazine rings on neighboring HAT(CN)6 molecules, with Ncyanidecentroidpyrazine distances that are under 3 Å. The directional character and structural parameters of the new supramolecular synthons correspond to collective triple anion-π interactions between the CN- ligands of the metal complexes and the π-deficient areas of HAT(CN)6. Physicochemical characterisation (IR spectroscopy, UV-Vis spectroscopy, cyclic voltammetry) and dispersion-corrected DFT studies reveal the dominating charge-transfer (CT) and polarisation characters of the interactions. The electronic density flow occurs from the CN- ligands of [M(CN)6]3- to the HAT(CN)6 orbital systems and further, toward the peripheral -CN groups of HAT(CN)6. Solid-state DFT calculations determined the total interaction energy of HAT(CN)6 to be ca. -125 kcal mol-1, which gives ca. -15 kcal mol-1 per one CN-HAT(CN)6 contact after subtraction of the interaction with organic cations. The UV-Vis electronic absorption measurements prove that the intermolecular interactions persist in solution and suggest a 1 : 1 composition of the anion-π {[M(CN)6]3-;[HAT(CN)6]} chromophore, with the formation constant Kadd = (5.8 ± 6) × 102 dm3 mol-1 and the molar absorption coefficient εadd = 180 ± 9 cm-1 dm3 mol-1 at 600 nm, as estimated from concentration-dependent studies.

Graphene-like Boron-Carbon-Nitrogen Monolayers.

A strategy to synthesize a 2D graphenic but ternary monolayer containing atoms of carbon, nitrogen, and boron, h-BCN, is presented. The synthesis utilizes bis-BN cyclohexane, B2N2C2H12, as a precursor molecule and relies on thermally induced dehydrogenation of the precursor molecules and the formation of an epitaxial monolayer on Ir(111) through covalent bond formation. The lattice mismatch between the film and substrate causes a strain-driven periodic buckling of the film. The structure of the film and its corrugated morphology is discussed based on comprehensive data from molecular-resolved scanning tunneling microscopy imaging, X-ray photoelectron spectroscopy, low-energy electron diffraction, and density functional theory. First-principles calculations further predict a direct electronic band gap that is intermediate between gapless graphene and insulating h-BN.

Quiet eye facilitates sensorimotor preprograming and online control of precision aiming in golf putting.

An occlusion protocol was used to elucidate the respective roles of preprograming and online control during the quiet eye period of golf putting. Twenty-one novice golfers completed golf putts to 6-ft and 11-ft targets under full vision or with vision occluded on initiation of the backswing. Radial error (RE) was higher, and quiet eye was longer, when putting to the 11-ft versus 6-ft target, and in the occluded versus full vision condition. Quiet eye durations, as well as preprograming, online and dwell durations, were longer in low-RE compared to high-RE trials. The preprograming component of quiet eye was significantly longer in the occluded vision condition, whereas the online and dwell components were significantly longer in the full vision condition. These findings demonstrate an increase in preprograming when vision is occluded. However, this was not sufficient to overcome the need for online visual control during the quiet eye period. These findings suggest the quiet eye period is composed of preprograming and online control elements; however, online visual control of action is critical to performance.

Contrast enhancement of carotid adventitial vasa vasorum as a biomarker of radiation-induced atherosclerosis.

PURPOSE: Abnormal proliferation of adventitial vasa vasorum (vv) occurs early at sites of atherosclerosis and is thought to be an early biomarker of vascular damage. Contrast-enhanced ultrasound (CEUS) can detect this process. Its usefulness in irradiated arteries as a measure of accelerated atherosclerosis is unknown. This study investigates contrast intensity in carotid adventitia as an early marker of radiation-induced damage in head and neck cancer (HNC) patients. MATERIALS/METHODS: Patients with HNC treated with a wedged-pair and matched neck technique or hemi-neck radiotherapy (RT) (unirradiated side as control) at least 2years previously were included. Patients had been prescribed a dose of at least 50Gy to the neck. CEUS was performed on both carotid arteries and a region of interest was selected in the adventitia of the far wall of both left and right distal common carotid arteries. Novel quantification software was used to compare the average intensity per pixel between irradiated and unirradiated arteries. RESULTS: 48 patients (34 males) with median age of 59.2years (interquartile range (IQR) 49.2-64.2) were included. The mean maximum point dose to the irradiated artery was 61.2Gy (IQR 52.6-61.8) and 1.1Gy (IQR 1.0-1.8Gy) to the unirradiated side. The median interval from RT was 59.4months (IQR 41-88.7). There was a significant difference in the mean (SD) contrast intensity per pixel on the irradiated side (1.1 (0.4)) versus 0.96 (0.34) on the unirradiated side (p=0.01). After attenuation correction, the difference in mean contrast intensity per pixel was still significant (1.4 (0.58) versus 1.2 (0.47) (p=0.02). Previous surgery or chemotherapy had no effect on the difference in contrast intensity between the 2 sides of the neck. Mean intensity per pixel did not correlate to traditional risk prediction models (carotid intima-medial thickness, QSTROKE score). CONCLUSIONS: Proliferation of vv is demonstrated by increased contrast intensity in irradiated carotid arteries. This may be a useful, independent biomarker of radiation-induced carotid atherosclerosis when used as a tool to quantify neovascularization.