Intramolecular Energy Transfer Competing with Light-Driven Intermolecular Proton Transfer in an Iron(II)-NHC Complex? A Query into the Role of Photobasic Ligands and MLCT States.

Inorganic photoacids and photobases comprising of photoactive transition metal complexes (TMCs) offer the ability to modulate proton transfer reactions through light irradiation, while utilizing the excellent optical properties of the latter. This provides a powerful tool for precise control over chemical reactions and processes, with implications for both fundamental science and practical applications. In this contribution, we present a novel molecular architecture amending an Fe-NHC complex with a pendant quinoline, as a prototypical photobase, as a representative earth-abundant TMC based inorganic photobase. We characterize the excited-state properties and proton-transfer dynamics using steady-state absorption and emission spectroscopy as well as pump wavelength dependent transient absorption spectroscopy in various protic solvents. The kinetics and thermodynamics of proton transfer in the quinoline moiety are influenced by both the presence of the metal center and the choice of the solvent. Furthermore, we see indications of intramolecular energy transfer from the quinoline to the MLCT state as a limiting factor for panchromatic photobasicity of the complex.

Photophysical Study on the Rigid Pt(II) Complex [Pt(naphen)(Cl)] (Hnaphen = Naphtho[1,2-b][1,10]Phenanthroline and Derivatives.

The electrochemistry and photophysics of the Pt(II) complexes [Pt(naphen)(X)] (Hnaphen = naphtho[1,2-b][1,10]phenanthroline, X = Cl or C≡CPh) containing the rigid tridentate C^N^N-coordinating pericyclic naphen ligand was studied alongside the complexes of the tetrahydro-derivative [Pt(thnaphen)(X)] (Hthnaphen = 5,6,8,9-tetrahydro-naphtho[1,2-b][1,10]phenanthroline) and the N^C^N-coordinated complex [Pt(bdq)(Cl)] (Hbdq = benzo[1,2-h:5,4-h']diquinoline. The cyclic voltammetry showed reversible reductions for the C^N^N complexes, with markedly fewer negative potentials (around -1.6 V vs. ferrocene) for the complexes containing the naphen ligand compared with the thnaphen derivatives (around -1.9 V). With irreversible oxidations at around +0.3 V for all of the complexes, the naphen made a difference in the electrochemical gap of about 0.3 eV (1.9 vs. 2.2 eV) compared with thnaphen. The bdq complex was completely different, with an irreversible reduction at around -2 V caused by the N^C^N coordination pattern, which lacked a good electron acceptor such as the phenanthroline unit in the C^N^N ligand naphen. Long-wavelength UV-Vis absorption bands were found around 520 to 530 nm for the C^N^N complexes with the C≡CPh coligand and were red-shifted when compared with the Cl derivatives. The N^C^N-coordinated bdq complex was markedly blue-shifted (493 nm). The steady-state photoluminescence spectra showed poorly structured emission bands peaking at around 630 nm for the two naphen complexes and 570 nm for the thnaphen derivatives. The bdq complex showed a pronounced vibrational structure and an emission maximum at 586 nm. Assuming mixed 3LC/3MLCT excited states, the vibronic progression for the N^C^N bdq complex indicated a higher LC character than assumed for the C^N^N-coordinated naphen and thnaphen complexes. The blue-shift was a result of the different N^C^N vs. C^N^N coordination. The photoluminescence lifetimes and quantum yields ΦL massively increased from solutions at 298 K (0.06 to 0.24) to glassy frozen matrices at 77 K (0.80 to 0.95). The nanosecond time-resolved study on [Pt(naphen)(Cl)] showed a phosphorescence emission signal originating from the mixed 3LC/3MLCT with an emission lifetime of around 3 µs.

Noble Metal Complexes of a Bis-Caffeine Containing NHC Ligand.

N-Heterocyclic carbenes (NHCs) have seen more and more use over the years. The go-to systems that are usually considered are derivatives of benzimidazole or imidazole. Caffeine possesses an imidazole unit and was already utilized as a carbene-type ligand; however, its use within a tridentate bis-NHC system has-to the best of our knowledge-not been reported so far. The synthesis of the ligand is straightforward and metal complexes are readily available via silver-salt metathesis. A platinum(II) and a palladium(II) complex were isolated and a crystal structure of the former was examined. For the Pt(II) complex, luminescence is observed in solid state as well as in solution.

Hydrodynamic Characteristics and Conformational Parameters of Ferrocene-Terpyridine-Based Polymers.

Nowadays, the study of metallopolymers is one of the fastest growing areas of polymer science. Metallopolymers have great potential for application in multiple technological and various biomedical processes. The macromolecules with the possibility of varying the number and type of metal ions along the entire length of the polymer chain are of particular interest. In this regard, this study presents results on two successfully synthesized homopolymers, random and block copolymers based on PMMA, containing ferrocene and terpyridine moieties in the side chain. Different architectures of copolymers may attribute interesting properties when creating complexes with various metal ions. A detailed hydrodynamic study of these structures was carried out, the consistency of hydrodynamic data was established using the concept of a hydrodynamic invariant, the absolute values of the molar masses of the studied objects were calculated, and the conformational parameters of macromolecules were determined. Using the Fixman-Stockmayer theory, the equilibrium rigidities of the studied systems were calculated and the relationship between the chemical structure and conformational characteristics was established. The studied copolymers can be attributed to the class of flexible-chain macromolecules. An increase in the equilibrium rigidity value with an increase of the side chain, which is characteristic of comb-shaped polymers, was determined.

Activation of indistinguishability-based quantum coherence for enhanced metrological applications with particle statistics imprint.

SignificanceQuantum coherence has a fundamentally different origin for nonidentical and identical particles since for the latter a unique contribution exists due to indistinguishability. Here we experimentally show how to exploit, in a controllable fashion, the contribution to quantum coherence stemming from spatial indistinguishability. Our experiment also directly proves, on the same footing, the different role of particle statistics (bosons or fermions) in supplying coherence-enabled advantage for quantum metrology. Ultimately, our results provide insights toward viable quantum-enhanced technologies based on tunable indistinguishability of identical building blocks.

Two-Dimensional Photosensitizer Nanosheets via Low-Energy Electron Beam Induced Cross-Linking of Self-Assembled RuII Polypyridine Monolayers.

Artificial photosynthesis for hydrogen production is an important element in the search for green energy sources. The incorporation of photoactive units into mechanically stable 2D materials paves the way toward the realization of ultrathin membranes as mimics for leaves. Here we present and compare two concepts to introduce a photoactive RuII polypyridine complex into ≈1 nm thick carbon nanomembranes (CNMs) generated by low-energy electron irradiation induced cross-linking of aromatic self-assembled monolayers. The photoactive units are either directly incorporated into the CNM scaffold or covalently grafted to its surface. We characterize RuII CNMs using X-ray photoelectron, surface-enhanced Raman, photothermal deflection spectroscopy, atomic force, scanning electron microscopy, and study their photoactivity in graphene field-effect devices. Therewith, we explore the applicability of low-energy electron irradiation of metal complexes for photosensitizer nanosheet formation.

Metallo-Supramolecular Complexation Behavior of Terpyridine- and Ferrocene-Based Polymers in Solution-A Molecular Hydrodynamics Perspective.

The contribution deals with the synthesis of the poly(methacrylate)-based copolymers, which contain ferrocene and/or terpyridine moieties in the side chains, and the subsequent analysis of their self-assembly behavior upon supramolecular/coordination interactions with Eu3+ and Pd2+ ions in dilute solutions. Both metal ions provoke intra and inter molecular complexation that results in the formation of large supra-macromolecular assembles of different conformation/shapes. By applying complementary analytical approaches (i.e., sedimentation-diffusion analysis in the analytical ultracentrifuge, dynamic light scattering, viscosity and density measurements, morphology studies by electron microscopy), a map of possible conformational states/shapes was drawn and the corresponding fundamental hydrodynamic and macromolecular characteristics of metallo-supramolecular assemblies at various ligand-to-ion molar concentration ratios (M/L) in extremely dilute polymer solutions (c[η]≈0.006) were determined. It was shown that intramolecular complexation is already detected at (L≈0.1), while at M/L>0.5 solution/suspension precipitates. Extreme aggregation/agglomeration behavior of such dilute polymer solutions at relatively "high" metal ion content is explained from the perspective of polymer-solvent and charge interactions that will accompany the intramolecular complexation due to the coordination interactions.

Solution-Based Self-Assembly and Stability of Ruthenium(II) Tris-bipyridyl Monolayers on Gold.

Ruthenium(II) polypyridyl complexes are commonly applied as photosensitizers in the fields of artificial photosynthesis and light harvesting. Their immobilization on gold surfaces is also of interest for sensing and biological applications. Here, we report the self-assembly of [Ru(dmbpy)2(dcbpy)](PF6)2 complexes on gold substrates from solution (dmbpy: 4,4'-dimethyl-2,2'-bipyridine; dcbpy: 2,2'-bipyridine-4,4'-dicarboxylic acid). Applying X-ray photoelectron spectroscopy, we demonstrate the formation of self-assembled monolayers (SAMs) of the Ru(II) complexes upon loss of counterions with carboxylate groups oriented toward the gold surface. We investigate the stability of the formed SAMs toward the substitution in solvents with competing aliphatic and aromatic thiols such as 4'-nitro[1,1'-biphenyl]-4-thiol, [1,1'-biphenyl]-4-thiol, and 1-hexadecanethiol. We show that the exchange reactions may lead to both complete replacement of the Ru(II) complexes and controlled formation of mixed SAMs. Moreover, we demonstrate that thiol-based SAMs can also be replaced completely from gold via their immersion into solutions of [Ru(dmbpy)2(dcbpy)](PF6)2, indicating a relatively high stability for the Ru(II) complex SAMs. Our findings open up a variety of opportunities for applications of carboxylate-based SAMs on gold in nanotechnology.

Photoactive ultrathin molecular nanosheets with reversible lanthanide binding terpyridine centers.

In recent years, functional molecular nanosheets have attracted much attention in the fields of sensors and energy storage. Here, we present an approach for the synthesis of photoactive metal-organic nanosheets with ultimate molecular thickness. To this end, we apply low-energy electron irradiation induced cross-linking of 4'-(2,2':6',2''-terpyridine-4'-yl)-1,1'-biphenyl-4-thiol self-assembled monolayers on gold to convert them into functional ∼1 nm thick carbon nanomembranes possessing the ability to reversibly complex lanthanide ions (Ln-CNMs). The obtained Ln-CNMs can be prepared on a large-scale (>10 cm2) and inherit the photoactivity of the pristine terpyridine lanthanide complex (Ln(III)-tpy). Moreover, they possess mechanical stability as free-standing sheets over micrometer sized openings. The presented methodology paves a simple and robust way for the preparation of ultrathin nanosheets with tailored photoactive properties for application in photocatalytic and energy conversion devices.

Thermality versus Objectivity: Can They Peacefully Coexist?

Under the influence of external environments, quantum systems can undergo various different processes, including decoherence and equilibration. We observe that macroscopic objects are both objective and thermal, thus leading to the expectation that both objectivity and thermalisation can peacefully coexist on the quantum regime too. Crucially, however, objectivity relies on distributed classical information that could conflict with thermalisation. Here, we examine the overlap between thermal and objective states. We find that in general, one cannot exist when the other is present. However, there are certain regimes where thermality and objectivity are more likely to coexist: in the high temperature limit, at the non-degenerate low temperature limit, and when the environment is large. This is consistent with our experiences that everyday-sized objects can be both thermal and objective.

Removal of EpCAM-positive tumor cells from blood collected during major oncological surgery using the Catuvab device- a pilot study.

BACKGROUND: Intraoperative blood salvage (IBS) is regarded as an alternative to allogeneic blood transfusion excluding the risks associated with allogeneic blood. Currently, IBS is generally avoided in tumor surgeries due to concern for potential metastasis caused by residual tumor cells in the erythrocyte concentrate. METHODS: The feasibility, efficacy and safety aspects of the new developed Catuvab procedure using the bispecific trifunctional antibody Catumaxomab was investigated in an ex-vivo pilot study in order to remove residual EpCAM positive tumor cells from the autologous erythrocyte concentrates (EC) from various cancer patients, generated by a IBS device. RESULTS: Tumor cells in intraoperative blood were detected in 10 of 16 patient samples in the range of 69-2.6 × 105 but no residual malignant cells in the final erythrocyte concentrates after Catuvab procedure. IL-6 and IL-8 as pro-inflammatory cytokines released during surgery, were lowered in mean 28-fold and 52-fold during the Catuvab procedure, respectively, whereas Catumaxomab antibody was detected in 8 of 16 of the final EC products at a considerable decreased and uncritical residual amount (37 ng in mean). CONCLUSION: The preliminary study results indicate efficacy and feasibility of the new medical device Catuvab allowing potentially the reinfusion of autologous erythrocyte concentrates (EC) produced by IBS device during oncological high blood loss surgery. An open-label, multicenter clinical study on the removal of EpCAM-positive tumor cells from blood collected during tumor surgery using the Catuvab device is initiated to validate these encouraging results.

Excitation Energy-Dependent Branching Dynamics Determines Photostability of Iron(II)-Mesoionic Carbene Complexes.

Photoactive metal complexes containing earth-abundant transition metals recently gained interest as photosensitizers in light-driven chemistry. In contrast to the traditionally employed ruthenium or iridium complexes, iron complexes developed to be promising candidates despite the fact that using iron complexes as photosensitizers poses an inherent challenge associated with the low-lying metal-centered states, which are responsible for ultrafast deactivation of the charge-transfer states. Nonetheless, recent developments of strongly σ-donating carbene ligands yielded highly promising systems, in which destabilized metal-centered states resulted in prolonged lifetimes of charge-transfer excited states. In this context, we introduce a series of novel homoleptic Fe-triazolylidene mesoionic carbene complexes. The excited-state properties of the complexes were investigated by time-resolved femtosecond transient absorption spectroscopy and quantum chemical calculations. Pump wavelength-dependent transient absorption reveals the presence of distinct excited-state relaxation pathways. We relate the excitation-wavelength-dependent branching of the excited-state dynamics into various reaction channels to solvent-dependent photodissociation following the population of dissociative metal centered states upon excitation at 400 nm.

The association between intraoperative cell salvage and red blood cell transfusion in cardiac surgery - an observational study in a patient blood management centre.

INTRODUCTION: Cell salvage (CS) is an integral part of patient blood management (PBM) and aims to reduce allogeneic red blood cell (RBC) transfusion. MATERIAL AND METHODS: This observational study analysed patients scheduled for elective cardiac surgery requiring cardiopulmonary bypass (CPB) between November 2015 and October 2018. Patients were divided into a CS group (patients receiving CS) and a control group (no CS). Primary endpoints were the number of patients exposed to allogeneic RBC transfusions and the number of RBC units transfused per patient. RESULTS: A total of 704 patients undergoing cardiac surgery were analysed, of whom 338 underwent surgery with CS (CS group) and 366 were without CS (control group). Intraoperatively, 152 patients (45%) were exposed to allogeneic RBC transfusions in the CS group and 93 patients (25%) in the control group (P < 0.001). Considering the amount of intraoperative blood loss, regression analysis revealed a significant association between blood loss and increased use of RBC units in patients of the control compared to the CS group (1000 mL: 1.0 vs. 0.6 RBC units; 2000 mL: 2.2 vs. 1.1 RBC units; 3000 mL: 3.4 vs. 1.6 RBC units). Thus, CS was significantly associated with a reduced number of allogeneic RBCs by 40% for 1000 mL, 49% for 2000 mL, and 52% for 3000 mL of blood loss compared to patients without CS. CONCLUSIONS: Cell salvage was significantly associated with a reduced number of allogeneic RBC transfusions. It supports the beneficial effect of CS in cardiac surgical patients as an individual measure in a comprehensive PBM program.

Reference Frames Which Separately Store Noncommuting Conserved Quantities.

Even in the presence of conservation laws, one can perform arbitrary transformations on a system if given access to a suitable reference frame, since conserved quantities may be exchanged between the system and the frame. Here we explore whether these quantities can be separated into different parts of the reference frame, with each part acting as a "battery" for a distinct quantity. For systems composed of spin-1/2 particles, we show that the components of angular momentum S_{x}, S_{y}, and S_{z} (noncommuting conserved quantities) may be separated in this way, and also provide several extensions of this result. These results also play a key role in the quantum thermodynamics of noncommuting conserved quantities.

Is electron ping-pong limiting the catalytic hydrogen evolution activity in covalent photosensitizer-polyoxometalate dyads?

Understanding the limitations of catalytic processes enables the design of optimized catalysts. Here, femtosecond transient absorption spectroelectrochemistry is used to explore the photophysics of polyoxometalate-based covalent photosensitizer-hydrogen evolution catalyst dyads. The study shows that the presence of light-driven forward and backward electron transfer, i.e. "electron ping-pong", is a limiting factor for charge accumulation on the polyoxometalate. Based on this insight, chemical means of optimizing catalyst performance are proposed.

Smart Molecular Nanosheets for Advanced Preparation of Biological Samples in Electron Cryo-Microscopy.

Transmission electron cryo-microscopy (cryoEM) of vitrified biological specimens is a powerful tool for structural biology. Current preparation of vitrified biological samples starts off with sample isolation and purification, followed by the fixation in a freestanding layer of amorphous ice. Here, we demonstrate that ultrathin (∼10 nm) smart molecular nanosheets having specific biorecognition sites embedded in a biorepulsive layer covalently bound to a mechanically stable carbon nanomembrane allow for a much simpler isolation and structural analysis. We characterize in detail the engineering of these nanosheets and their biorecognition properties employing complementary methods such as X-ray photoelectron and infrared spectroscopy, atomic force microscopy as well as surface plasmon resonance measurements. The desired functionality of the developed nanosheets is demonstrated by in situ selection of a His-tagged protein from a mixture and its subsequent structural analysis by cryoEM.

Proton and Li-Ion Permeation through Graphene with Eight-Atom-Ring Defects.

Defect-free graphene is impermeable to gases and liquids but highly permeable to thermal protons. Atomic-scale defects such as vacancies, grain boundaries, and Stone-Wales defects are predicted to enhance graphene's proton permeability and may even allow small ions through, whereas larger species such as gas molecules should remain blocked. These expectations have so far remained untested in experiment. Here, we show that atomically thin carbon films with a high density of atomic-scale defects continue blocking all molecular transport, but their proton permeability becomes ∼1000 times higher than that of defect-free graphene. Lithium ions can also permeate through such disordered graphene. The enhanced proton and ion permeability is attributed to a high density of eight-carbon-atom rings. The latter pose approximately twice lower energy barriers for incoming protons compared to that of the six-atom rings of graphene and a relatively low barrier of ∼0.6 eV for Li ions. Our findings suggest that disordered graphene could be of interest as membranes and protective barriers in various Li-ion and hydrogen technologies.

Electrochemical delamination assisted transfer of molecular nanosheets.

Delamination and transfer of two-dimensional (2D) materials from their synthesis substrates onto target substrates is an important task for their implementation in both fundamental and applied research. To this end, the electrochemical delamination based transfer has been successfully applied to a variety of inorganic 2D materials grown on conductive substrates. However, this promising method has not yet been demonstrated for organic 2D materials, which have recently gained significant importance in the 2D materials family. Here, we present a transfer method of molecular nanosheets covalently bonded to metal substrates based on electrochemical delamination, which involves the cleavage of an Au-S bond and hydrogen evolution. We demonstrate a successful transfer of different types of carbon nanomembranes (CNMs) - about 1 nm thick molecular nanosheets - synthesized from aromatic thiol-based self-assembled monolayers on various polycrystalline gold substrates, onto new target substrates such as SiO2/Si wafers and transmission electron microscopy grids. We analyze the subsequent nanofabrication steps, and chemical and structural characteristics of the transferred supported and suspended CNMs by X-ray photoelectron spectroscopy (XPS), optical microscopy, atomic force microscopy (AFM) and scanning electron microscopy (SEM). The XPS analysis enables us to reveal the chemical mechanisms during the delamination process, whereas the complementary microscopy measurements confirm a high structural integrity of the transferred molecular nanosheets. We expect that the developed methodology can be applied to a broad variety of organic 2D materials synthesized on conductive substrates.

Optically Triggered Control of the Charge Carrier Density in Chemically Functionalized Graphene Field Effect Transistors.

Field effect transistors (FETs) based on 2D materials are of great interest for applications in ultrathin electronic and sensing devices. Here we demonstrate the possibility to add optical switchability to graphene FETs (GFET) by functionalizing the graphene channel with optically switchable azobenzene molecules. The azobenzene molecules were incorporated to the GFET channel by building a van der Waals heterostructure with a carbon nanomembrane (CNM), which is used as a molecular interposer to attach the azobenzene molecules. Under exposure with 365 nm and 455 nm light, azobenzene molecules transition between cis and trans molecular conformations, respectively, resulting in a switching of the molecular dipole moment. Thus, the effective electric field acting on the GFET channel is tuned by optical stimulation and the carrier density is modulated.

Collision cross-section analysis of self-assembled metallomacrocycle isomers and isobars via ion mobility mass spectrometry.

RATIONALE: Coordinatively driven self-assembly of transition metal ions and bidentate ligands gives rise to organometallic complexes that usually contain superimposed isobars, isomers, and conformers. In this study, the double dispersion ability of ion mobility mass spectrometry (IM-MS) was used to provide a comprehensive structural characterization of the self-assembled supramolecular complexes by their mass and charge, revealed by the MS event, and their shape and collision cross-section (Ω), revealed by the IM event. METHODS: Self-assembled complexes were synthesized by reacting a bis(terpyridine) ligand exhibiting a 60o dihedral angle between the two ligating terpyridine sites (T) with divalent Zn, Ni, Cd, or Fe. The products were isolated as (Metal2+ [T])n (PF6 )2n salts and analyzed using IM-MS after electrospray ionization (ESI) which produced several charge states from each n-mer, depending on the number of PF6 - anions lost upon ESI. Experimental Ω data, derived using IM-MS, and computational Ω predictions were used to elucidate the size and architecture of the complexes. RESULTS: Only macrocyclic dimers, trimers, and tetramers were observed with Cd2+ , whereas Zn2+ formed the same plus hexameric complexes. These two metals led to the simplest product distributions and no linear isomers. In sharp contrast, Ni2+ and Fe2+ formed all possible ring sizes from dimer to hexamer as well as various linear isomers. The experimental and theoretical Ω data indicated rather planar macrocyclic geometries for the dimers and trimers, twisted 3D architectures for the larger rings, and substantially larger sizes with spiral conformation for the linear congeners. Adding PF6 - to the same complex was found to mainly cause size contraction due to new stabilizing anion-cation interactions. CONCLUSIONS: Complete structural identification could be accomplished using ESI-IM-MS. Our results affirm that self-assembly with Cd2+ and Zn2+ proceeds through reversible equilibria that generate the thermodynamically most stable structures, encompassing exclusively macrocyclic architectures that readily accommodate the 60o ligand used. In contrast, complexation with Ni2+ and Fe2+ , which form stronger coordinative bonds, proceeds through kinetic control, leading to more complex mixtures and kinetically trapped less stable architectures, such as macrocyclic pentamers and linear isomers.