High-Temperature Solid-State Post-Synthetic Modification of Highly Luminescent Cu(I) Metallacycles toward New Luminescent Thermic Tracers.

A new luminescent Cu(I) tetrametallic metallacycle B is reported that features very rare semi-bridging aqua ligands. When heated markedly above room temperature, this compound undergoes a post-synthetic transformation in the solid-state, affording the new luminescent metallacycle C. Thermogravimetric analysis, IR spectroscopy and single-crystal X-ray diffraction reveal that this alteration preserves the gross tetrametallic macrocycle structure, but is caused by the release of the coordinated water molecules with the concomitant formation of cuprophilic interactions.

Singlet oxygen is an emissive ligand.

Unprecedented experimental evidence shows that gaseous singlet oxygen (O) acts as an emissive ligand following collisional photosensitization. This evidence was obtained by monitoring O phosphorescence intensity at ≈1275-1280 nm and the excited state lifetime of singlet oxygen generated by known tetraphenylporphyrin photosensitizers, while varying the atmospheric environment.

Membrane association of active genes organizes the chloroplast nucleoid structure.

DNA is organized into chromatin-like structures that support the maintenance and regulation of genomes. A unique and poorly understood form of DNA organization exists in chloroplasts, which are organelles of endosymbiotic origin responsible for photosynthesis. Chloroplast genomes, together with associated proteins, form membrane-less structures known as nucleoids.

Rapid mortality in captive bush dogs () caused by influenza A of avian origin (H5N1) at a wildlife collection in the United Kingdom.

Europe has suffered unprecedented epizootics of high pathogenicity avian influenza (HPAI) clade 2.3.4.

Truxene-to-Fluorenone Energy Transfer in a Robust Mesoporous Zn-MOF.

A new metal-organic framework (MOF; [ZnO()()()]; ) constructed on chromophoric ligands 5,5',10,10',15,15'-hexaethyltruxene-2,7,12-triacetate (), 9-fluorenone-2,7-dicarboxylate (), terephthalate (), and the ZnO node has been prepared and identified by powder X-ray diffraction. This luminescent MOF exhibits large mesoporous pores of 2.7 nm based on computer modeling using density functional theory (DFT) calculations.

Statistical Analysis of Copper(I) Iodide and Bis(Diphenylphosphino)alkane-Based Complexes and Coordination Polymers.

The prediction of the metal cluster within a coordination polymer or complex, as well as the dimensionality of the resulting polymer or complex (i.e., 0D, 1D, 2D, or 3D), is often challenging.

Strong Host-Guest Dependence on the Emissive Properties of MOF-5 and [Zn(BTTB)(DMF)•(HO)].

3D-[ZnO(1,4-BDC)•(solvent)] (; BDC = benzodicarboxylate) and -[Zn(BTTB)(DMF)•(HO)] (; BTTB = 4,4',4″,4‴-benzene-1,2,4,5-tetrayltetrabenzoate) have been investigated by means of steady-state UV-visible and fluorescence and time-resolved emission spectroscopy, as a function of solvent and power of the excitation irradiation. The low-temperature X-ray structures (173 K) were permitted to locate solvent molecules (here HO) in the lattice. They were found distributed in the middle in the voids with no evidence of specific interactions (H-bond, coulombic, and dipole-dipole) with the framework.

S-Heptazine N-ligand based luminescent coordination materials: synthesis, structural and luminescent studies of lanthanide-cyamelurate networks.

Various series of lanthanide metal-organic networks denoted Ln- (Ln = La, Ce, Pr, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb), were synthesized under solvothermal conditions using potassium cyamelurate (K) and lanthanide nitrate salts. All obtained materials were fully characterized, and their crystal structures were solved by single-crystal X-ray diffraction. Four types of coordination modes were elucidated for the Ln- series with different Ln coordination geometries.

Anti-Xa Directed Thromboprophylaxis in Critically Ill Patients with Coronavirus Disease 2019.

To compare Anti-Xa directed thromboprophylaxis using low molecular weight heparin (LMWH) (anti-Xa peak goal 0.2-0.5 IU/mL) to alternative anticoagulation strategies in critically ill COVID-19 patients.

Chain Length Effect on the Structural and Emission Properties of the CuI/Bis((4-methoxyphenyl)thio)alkane Coordination Polymers.

A systematic chain length variation of the ligand -MeOCHS(CH)SCHOMe (1 ≤ ≤ 8) was performed to study its effect on the structures and photophysical properties of the coordination polymers (CP) when reacted with CuI. Indeed, direct correlations are noted between these features and . When is an odd number, the secondary building unit is systematically the common closed-cubane CuI cluster, rendering the material strongly luminescent (, emission quantum yield, Φ > 20%), and the CP is one-dimensional (1D).

A Fused Poly(truncated rhombic dodecahedron)-Containing 3D Coordination Polymer: A Multifunctional Material with Exceptional Properties.

The design of new and inexpensive metal-containing functional materials is of great interest. Herein is reported a unique thermochromic near-IR emitting coordination polymer, 3D-[CuI()], , which is formed when ArS(CH)SAr (, Ar = 4-CHOMe) reacts with 2 equiv of CuI in EtCN. In MeCN, ([CuI()(MeCN)], consisting of an alternating [-CuI--CuI--] chain where the CuI cubane units bear two metal-bound MeCN molecules, is formed.

New phosphorescent iridium(III) dipyrrinato complexes: synthesis, emission properties and their deep red to near-infrared OLEDs.

A series of heteroleptic Ir(iii) complexes composed of two cyclometalated C^N ligands and one dipyrrinato ligand used as an ancillary ligand are synthesized and characterized. With the introduction of a fluorine atom, phenyl ring or diphenylamino group into both C^N ligands and by keeping the ancillary ligand unchanged, these Ir(iii) dipyrrinato phosphors do not show an obvious shift in their emission bands. They exhibit emissions extending well into the near-infrared region with an intense band located at around 685 nm in both photo- and electroluminescence spectra, and the deep red to near-infrared organic light emitting diodes (OLEDs) based on them afforded a maximum external quantum efficiency of 2.

Porphyrin-Containing MOFs and COFs as Heterogeneous Photosensitizers for Singlet Oxygen-Based Antimicrobial Nanodevices.

Visible-light irradiation of porphyrin and metalloporphyrin dyes in the presence of molecular oxygen can result in the photocatalytic generation of singlet oxygen (O). This type II reactive oxygen species (ROS) finds many applications where the dye, also called the photosensitizer, is dissolved (i.e.

The TDDFT Excitation Energies of the BODIPYs; The DFT and TDDFT Challenge Continues.

The derivatives of 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) are pivotal ingredients for a large number of functional, stimuli-responsive materials and therapeutic molecules based on their photophysical properties, and there is a urgent need to understand and predict their optical traits prior to investing a large amount of resources in preparing them. Density functional theory (DFT) and time-dependent DFT (TDDFT) computations were performed to calculate the excitation energies of the lowest-energy singlet excited state of a large series of common BODIPY derivatives employing various functional aiming at the best possible combination providing the least deviations from the experimental values. Using the common "fudge" correction, a series of combinations was investigated, and a methodology is proposed offering equal or better performances than what is reported in the literature.

Design of P-Chirogenic Aminophosphine-Phosphinite Ligands at Both Phosphorus Centers: Origin of Enantioselectivities in Pd-Catalyzed Allylic Reactions.

We have recently patented an unprecedented stereospecific N → O phosphinyl migration process which transforms P-chirogenic aminophosphines into phosphinites. A fine design of aminophosphine phosphinite ligands (AMPP*) derived from ephedrine and bearing a P-chirogenic center either at the aminophosphine or phosphinite moiety was performed. The synthesis of AMPP* ligands with a P-chirogenic aminophosphine moiety was based on the well-established stereospecific reaction of oxazaphospholidine borane with organolithium reagents, followed by trapping with a chlorophosphine and borane decomplexation.

From Short-Bite Ligand Assembled Ribbons to Nanosized Networks in Cu(I) Coordination Polymers Built Upon Bis(benzylthio)alkanes (BzS(CH)SBz; = 1-9).

With the objective to establish a correlation between the spacer distance and halide dependence on the structural features of coordination polymers (CPs) assembled by the reaction between CuX salts (X = Cl, Br, I) and dithioether ligands BzS(CH)SBz ( = 1-9; Bz = benzyl), a series of 26 compounds have been prepared and structurally investigated. A particular attention has been devoted to the design of networks with extremely long and flexible methylene spacer units between the SBz donor sites. Under identical conditions, CuI and CuBr react with BzSCHBz () affording respectively the one-dimensional (1D) CPs {Cu(μ-I)Cu}(μ-)] () and {Cu(μ-Br)Cu}(μ-)] (), which incorporate Cu(μ-X)Cu rhomboids as secondary building units (SBUs).

Use of Procalcitonin and a Respiratory Polymerase Chain Reaction Panel to Reduce Antibiotic Use via an Electronic Medical Record Alert.

Background: Respiratory tract infections are often viral and but are frequently treated with antibiotics, providing a significant opportunity for antibiotic de-escalation in patients. We sought to determine whether an automated electronic medical record best practice alert (BPA) based on procalcitonin and respiratory polymerase chain reaction (PCR) results could help reduce inappropriate antibiotic use in patients with likely viral respiratory illness.

Methods: This multisite, pre-post, quasi-experimental study included patients 18 years and older with a procalcitonin level <0.

Unusual triplet-triplet annihilation in a 3D copper(i) chloride coordination polymer.

A new coordination polymer (CP) defined as [CuCl(EtS(CH)SEt)] (CP2) was prepared by reacting EtS(CH)SEt with CuCl in acetonitrile in a 1 : 2 stoichiometric ratio. The X-ray structure reveals formation of non-porous 3D material composed of parallel 2D-[CuClS] layers of Cl-bridged Cu(μ-Cl) rhomboids assembled by EtS(CH)SEt ligands. A weak triplet emission (Φ < 0.

Defining genotype-phenotype relationships in patients with hypertrophic cardiomyopathy using cardiovascular magnetic resonance imaging.

Purpose: HCM is the most common inherited cardiomyopathy. Historically, there has been poor correlation between genotype and phenotype. However, CMR has the potential to more accurately assess disease phenotype.

Control of Structures and Emission Properties of (CuI) 2-Methyldithiane Coordination Polymers.

A structurally unique and strongly luminescent nonporous 3D coordination polymer (CP) [CuI(methyldithiane)] , CP3, has been prepared in a quasi-anticipated manner from 2-methyl-1,3-dithiane, L1, and CuI. This CP incorporates an unprecedented CuI cluster built upon two side-fused open cubanes. The crystal structure of CP3 has been determined at 100, 150, 200, 250, 300, 350, and 400 K to study the temperature dependence of the Cu···Cu distances.

Ferrocene-BODIPYmerocyanine dyads: new NIR absorbing platforms with optical properties susceptible to protonation.

Ferrocene-BODIPYmerocyanine dyads 5 and 6 were prepared and characterized by a variety of spectroscopic, electrochemical, and theoretical methods. Experimental and theoretical data on these NIR absorbing compounds are suggestive of unusual susceptibility (for BODIPY chromophores) of the delocalized π-system in 5 and 6 to protonation and low-potential oxidation of their π-systems.

Positive and negative ion formation in deep-core excited molecules: S 1s excitation in dimethyl sulfoxide.

The photo-fragmentation of the dimethyl sulfoxide (DMSO) molecule was studied using synchrotron radiation and a magnetic mass spectrometer. The total cationic yield spectrum was recorded in the photon energy region around the sulfur K edge. The sulfur composition of the highest occupied molecular orbital's and lowest unoccupied molecular orbital's in the DMSO molecule has been obtained using both ab initio and density functional theory methods.

K-shell x-ray spectroscopy of atomic nitrogen.

Absolute K-shell photoionization cross sections for atomic nitrogen have been obtained from both experiment and state-of-the-art theoretical techniques. Because of the difficulty of creating a target of neutral atomic nitrogen, no high-resolution K-edge spectroscopy measurements have been reported for this important atom. Interplay between theory and experiment enabled identification and characterization of the strong 1s → np resonance features throughout the threshold region.