Light-induced selectivity in an exemplary photodimerization reaction of varied azaanthracenes.

Currently, there is intense interest in light-driven chemical reactions, including photocatalytic processes, photopolymerization and photodimerization. The need for regiocontrol in such reactions is obvious, especially in cases where many products can potentially be formed. Here, the photodimerization involving various azaanthracenes is presented for the first time.

Comparative Analysis of Metal Electrodeposition Rates towards Formation of High-Entropy WFeCoNiCu Alloy.

This study presents a calculation and comparison of Fe, Co, Ni and Cu deposition rates in the tungsten codeposition process based on the electrodeposition of numerous tungsten alloys. Eight different tungsten alloys containing from two to five metals were electrodeposited in constant conditions in order to compare the exact reduction rates. The calculated rates enabled control of the alloy composition precise enough to obtain a high-entropy WFeCoNiCu alloy with a well-balanced composition.

Non-uniform orientation of H2 molecules in a magnetic field as a critical condition for the appearance of partially negative NMR lines of o-H2 in hyperpolarization experiments using p-H2.

In hyperpolarization experiments using parahydrogen, a partially negative line (PNL) of o-H2 is occasionally spotted in the nuclear magnetic resonance (NMR) spectra. This is a manifestation of the two-spin order (TSO) of the proton spins, appearing transiently in o-H2 molecules freshly derived from p-H2. For the TSO to be observable, the o-H2 NMR signal must be split into a doublet.

A Straightforward Method for the Generation of Hyperpolarized Orthohydrogen with a Partially Negative Line.

The hydrogen molecule, which exists in two spin isomers (ortho- and parahydrogen), is a highly studied system due to its fundamental properties and practical applications. Parahydrogen is used for Nuclear Magnetic Resonance signal enhancement, which is hyperpolarization of other molecules, including biorelevant ones. Hyperpolarization can be achieved by using Signal Amplification by Reversible Exchange (SABRE).

A modular design approach to polymer-coated ZnO nanocrystals.

Hybrid materials based on inorganic nanocrystals with organic polymers feature peculiar and fascinating properties and various applications. However, there is still a need for simple synthesis procedures that provide precise control over the polymer/nanocrystal microstructure of these materials. Herein, a novel organometallic approach to polymer-coated ZnO nanocrystals was developed.

Deeper Insight into Photopolymerization: The Synergy of Time-Resolved Nonuniform Sampling and Diffusion NMR.

The comprehensive real-time in situ monitoring of chemical processes is a crucial requirement for the in-depth understanding of these processes. This monitoring facilitates an efficient design of chemicals and materials with the precise properties that are desired. This work presents the simultaneous utilization and synergy of two novel time-resolved NMR methods, i.

Deactivation of catalysts in simultaneous reversible and irreversible parahydrogen NMR signal enhancement, and the role of co-ligands in the stabilization of the reversible method.

Signal Amplification by Reversible Exchange (SABRE) and hydrogeneable Parahydrogen Induced Polarization (hPHIP) can enhance weak NMR signals, and thus increase the range of NMR applications. Here, using an N-heterocyclic carbene Ir-based catalyst, simultaneous SABRE and hPHIP was achieved for the compound with an N-donor site and an acetylene triple bond. It was demonstrated that the interplay between SABRE and hPHIP can be manipulated.

Nuclear Charge Radii of the Nickel Isotopes ^{58-68,70}Ni.

Collinear laser spectroscopy is performed on the nickel isotopes ^{58-68,70}Ni, using a time-resolved photon counting system. From the measured isotope shifts, nuclear charge radii R_{c} are extracted and compared to theoretical results. Three ab initio approaches all employ, among others, the chiral interaction NNLO_{sat}, which allows an assessment of their accuracy.

Triptycene Derivatives: From Their Synthesis to Their Unique Properties.

Since the first preparation of triptycene, great progress has been made with respect to its synthesis and the understanding of its properties. Interest in triptycene-based systems is intense; in recent years, advances in the synthetic methodology and properties of new triptycenes have been reported by researchers from various fields of science. Here, an account of these new developments is given and placed in reference to earlier pivotal works that underpin the field.

Photoreactivity of an Exemplary Anthracene Mixture Revealed by NMR Studies, including a Kinetic Approach.

Anthracenes are an important class of acenes. They are being utilized more and more often in chemistry and materials sciences, due to their unique rigid molecular structure and photoreactivity. In particular, photodimerization can be harnessed for the fabrication of novel photoresponsive materials.

NMR Crystallography Enhanced by Quantum Chemical Calculations and Liquid State NMR Spectroscopy for the Investigation of Se-NHC Adducts*.

N-heterocyclic carbene ligands (NHC) are widely utilized in catalysis and material science. They are characterized by their steric and electronic properties. Steric properties are usually quantified on the basis of their static structure, which can be determined by X-ray diffraction.

Interactions of Eu(TTA)(HO) with Latent Fingermark Components-A Time-Gated Visualization of Latent Fingermarks on Paper.

We introduce a new latent fingermark (LFM) development method, where compounds showing long lifetime luminescence are generated in situ by the reactions of Eu(TTA)(HO) with LFM components. Until now, time-gated imaging could not be used to develop LFM on porous surfaces due to the difficulties with selective binding of the developing agents to the fingermark ridges. The nature of the interactions of Eu(TTA)(HO) with the LFM material has been investigated for three model compounds commonly found in the LFM composition-oleic acid, l-serine, and squalene.

Magnetic Resonance Signal Amplification by Reversible Exchange of Selective PyFALGEA Oligopeptide Ligands Towards Epidermal Growth Factor Receptors.

The biorelevant PyFALGEA oligopeptide ligand, which is selective towards the epidermal growth factor receptor (EGFR), has been successfully employed as a substrate in magnetic resonance signal amplification by reversible exchange (SABRE) experiments. It is demonstrated that PyFALGEA and the iridium catalyst IMes form a PyFALGEA:IMes molecular complex. The interaction between PyFALGEA:IMes and H results in a ternary SABRE complex.

Noble Metal Nanoparticles in Pectin Matrix. Preparation, Film Formation, Property Analysis, and Application in Electrocatalysis.

Stable polymeric materials with embedded nano-objects, retaining their specific properties, are indispensable for the development of nanotechnology. Here, a method to obtain Pt, Pd, Au, and Ag nanoparticles (ca. 10 nm, independent of the metal) by the reduction of their ions in pectin, in the absence of additional reducing agents, is described.

A new Collinear Apparatus for Laser Spectroscopy and Applied Science (COALA).

We present a new collinear laser spectroscopy setup that has been designed to overcome systematic uncertainty limits arising from high-voltage and frequency measurements, beam superposition, and collisions with residual gas that are present in other installations utilizing this technique. The applied methods and experimental realizations are described, including an active stabilization of the ion-source potential, new types of ion sources that have not been used for collinear laser spectroscopy so far, dedicated installations for pump-and-probe measurements, and a versatile laser system referenced to a frequency comb. The advanced setup enables us to routinely determine transition frequencies, which was so far demonstrated only for a few cases and with lower accuracy at other facilities.

Charge Radius of the Short-Lived ^{68}Ni and Correlation with the Dipole Polarizability.

We present the first laser spectroscopic measurement of the neutron-rich nucleus ^{68}Ni at the N=40 subshell closure and extract its nuclear charge radius. Since this is the only short-lived isotope for which the dipole polarizability α_{D} has been measured, the combination of these observables provides a benchmark for nuclear structure theory. We compare them to novel coupled-cluster calculations based on different chiral two- and three-nucleon interactions, for which a strong correlation between the charge radius and dipole polarizability is observed, similar to the stable nucleus ^{48}Ca.

Blue-Shift Hydrogen Bonds in Silyltriptycene Derivatives: Antibonding σ* Orbitals of the Si-C Bond as Effective Acceptors of Electron Density.

Triptycene derivatives are widely utilized in different fields of chemistry and materials sciences. Their physicochemical properties, often of pivotal importance for the rational design of triptycene-based functional materials, are influenced by noncovalent interactions between substituents mounted on the triptycene skeleton. Herein, a unique interaction between electron-rich substituents in the peri position and the silyl group located on the bridgehead sp -carbon is discussed on the example of 1,4-dichloro-9-(p-methoxyphenyl)-silyltriptycene (TRPCl) which exists in solution in the form of two rotamers differing by dispositions, syn or anti, of the Si-C (the C atom is from the p-methoxyphenyl group) bond against the peri-Cl atom.

Application of the Continuous Stern-Gerlach Effect for Laser Spectroscopy of the ^{40}Ar^{13+} Fine Structure in a Penning Trap.

We report on the successful demonstration of a novel scheme for detecting optical transitions in highly charged ions. We applied it to determine the frequency of the dipole-forbidden 2p ^{2}P_{1/2}-^{2}P_{3/2} transition in the fine structure of ^{40}Ar^{13+} using a single ion stored in the harmonic potential of a Penning trap. Our measurement scheme does not require detection of fluorescence, instead it makes use of the continuous Stern-Gerlach effect.

Towards Extended Zinc Ethylsulfinate Networks by Stepwise Insertion of Sulfur Dioxide into Zn-C Bonds.

The ability to utilize polluting gases in efficient metal-mediated transformations is one of the most pressing challenges of modern chemistry. Despite numerous studies on the insertion of SO into M-C bonds, the chemical reaction of SO with organozinc compounds remains little explored. To fill this gap, we report here the systematic study of the reaction of Et Zn towards SO as well as the influence of Lewis bases on the reaction course.

Monitoring Hydrogenation Reactions using Benchtop 2D NMR with Extraordinary Sensitivity and Spectral Resolution.

Low-field benchtop nuclear magnetic resonance (BT-NMR) spectrometers with Halbach magnets are being increasingly used in science and industry as cost-efficient tools for the monitoring of chemical reactions, including hydrogenation. However, their use of low-field magnets limits both resolution and sensitivity. In this paper, we show that it is possible to alleviate these two problems through the combination of parahydrogen-induced polarization (PHIP) and fast correlation spectroscopy with time-resolved non-uniform sampling (TR-NUS).

Photo-induced interfacial electron transfer of ZnO nanocrystals to control supramolecular assembly in water.

Herein, we show how the inherent light-induced redox properties of semiconducting nanocrystals (NCs) can be utilized for the photo-driven reversible modulation of dynamic supramolecular systems formed at their interfaces that, on their own, do not respond to light. This was achieved by the unprecedented combination of photoactive zinc oxide NCs (ZnO NCs) with a host-guest chemistry of cucurbit[8]uril (CB[8]) providing a route to the semiconductor-assisted light modulation of supramolecular assemblies (SALSA), here mediated by the photo-generation of viologen radical cations (MV˙) at the NC corona and their further dimerization enhanced by CB[8] macrocycles. The reported SALSA strategy was successfully applied for light-controlled reversible assembly processes at NC interfaces enabling light-triggered release of guest molecules from surface confined discrete CB[8] host-guest complexes.

Frozen Rotation of the Ammonium Group Observed for the First Time in Liquid-Phase NMR Spectra.

Hindered rotation of the -NH group in a sterically crowded molecular environment was frozen on the NMR time scale. These effects were observed for solutions of 1,2,3,4-tetrabromotriptycyl-9-ammonium tetrafluoroborate in tetrahydrofuran with and without excess of HBF. In the absence of acid, the hindered rotation is accompanied by a number of other effects originating in part from practically nonremovable traces of water in the solvent.

The optical properties and quantum chemical calculations of thienyl and furyl derivatives of pyrene.

A detailed electrochemical, photophysical and theoretical study is presented for various new thienyl and furyl derivatives of pyrene. Their optical properties are described based on UV-VIS absorption and both steady-state and time-resolved fluorescence spectroscopy. DFT and TDDFT calculations are also presented to support experimental data.

NMR signal enhancement by effective SABRE labeling of oligopeptides.

Signal amplification by reversible exchange (SABRE) can enhance nuclear magnetic resonance signals by several orders of magnitude. However, until now this was limited to a small number of model target molecules. Here, a new convenient method for SABRE activation applicable to a variety of synthetic model oligopeptides is demonstrated.