Carbon-Centered Reactivity in Carbodiphosphorane-Based Ligands Allowing for Redox-Non-Innocent Ligand/Ligand Dual Bond-Activation.

A pronounced nucleophilicity in combination with a distinct redox non-innocence is a unique feature of a coordinated ligand, which in the current case, leads to unprecedented carbon-centered reactivity patterns: A carbodiphosphorane-based (CDP) pincer-type rhodium complex allows to cleave two C-Cl-bonds of geminal dichlorides via two consecutive S.

Toward Molecular Textiles: Synthesis and Characterization of Molecular Patches.

This works describes a new step into the assembly of molecular textiles by the use of covalent templating. To establish a well-founded base and to tackle pre-mature obstacles, expected during the fabrication of the desired 2D-material, we opted to investigate the in-solution synthesis of molecular patches e. g.

Synthesis of Dinuclear Cobalt Silylene Complexes and Their Catalytic Activity for Alkene Hydrosilylation Reactions.

A novel dinuclear silylene cobalt complex [((MeP)Co)(PMe)(CoCl(PMe))(Si(NCHPPh)CH)] () supported by the [PSi(silylene)P] ligand was prepared through the reaction of N-heterocyclic [PSiP] pincer ligand (HSiCl(NCHPPh)CH) with Co(PMe). Complex [((MeP)Co)(Si(NCHPPh)CH)] () was formed through the reaction of complex with MeLi. To the best of our knowledge, complexes and are the first examples of dinuclear silylene cobalt complexes supported by the [PSi(silylene)P] ligand.

Cleaning validation for blister packaging machines in hospital-supplying pharmacies.

Objective: To ensure quality-assured care for patients, validation of a cleaning process for blister machines is essential. Due to the high operating costs of maintaining high-performance liquid chromatography (HPLC) which is mainly used for this type of analysis, a new, quick and cost-effective analysis method using UV-Vis spectroscopy has been developed.

Method: Marker substances (metamizole (dipyrone) and paracetamol tablets) were packed in blisters.

Introduction of Unit-Dose Care in the 1,125 Bed Teaching Hospital: Practical Experience and Time Saving on Wards.

Purpose: The shortage of nursing staff as well as the slow progress in the German health care system's digitalisation has gained much attention due to COVID-19. Patient-specific medication management using the unit-dose dispensing system (UDDS) has the potential for a lasting and positive influence on both digitalisation and the relief of nursing staff.

Methods: Nursing staff UDDS-acceptance was determined via a validated online survey.

We Ask and Listen: A Group-Wide Retrospective Survey on Satisfaction with Digital Medication Software.

Purpose: Computerized physician order entry (CPOE) and clinical decision support systems (CDSS) are used internationally since the 1980s. These systems reduce costs, enhance drug therapy safety, and improve quality of care. A few years ago, there was a growing effort to digitize the healthcare sector in Germany.

Circularly Polarized Luminescence of Thiophene-Bridged Macrocyclic pseudo-meta [2.2]Paracyclophanes.

Chiral organic molecules possessing high quantum yields, circular dichroism, and circularly polarized luminescence values have great potential as optically active materials for future applications. Recently, the identification of a promising class of inherently chiral compounds was reported, namely macrocyclic 1,3-butadiyne-linked pseudo-meta[2.2]paracyclophanes, displaying high circular dichroism and related g values albeit modest quantum yields.

Comparing the burden of illness in patients with alopecia areata vs atopic dermatitis in the US population from a payer perspective.

Alopecia areata (AA) is an autoimmune disease characterized by nonscarring hair loss. AA frequently co-occurs with other inflammatory autoimmune conditions, presenting a significant clinical burden. To compare the burden of illness, direct and indirect costs in adult patients with AA vs atopic dermatitis (AD).

Ion-Selective Assembly of Supertetrahedral Selenido Germanate Clusters for Alkali Metal Ion Capture and Separation.

Supertetrahedral chalcogenido (semi)metalate cluster-based frameworks possess high selectivity for alkali metal cations, matching the specific charge density of their inner surfaces, which enables their use as ion-exchange materials. Aggregates of the supertetrahedral chalcogenido metalate cluster offer even new perspectives for metal ion capture and separation. Herein, we report on ionothermal preparation of two corresponding model compounds, (CCIm)[Cs@Ge(GeSe)] () and (CCIm)[Na(CN)@Cu(GeSe)(Cu)] ().

Intense Molar Circular Dichroism in Fully Conjugated All-Carbon Macrocyclic 1,3-Butadiyne Linked pseudo-meta [2.2]Paracyclophanes.

Invited for the cover of this issue is the group of Marcel Mayor at the University of Basel with co-workers Olaf Fuhr and Dieter Fenske from Karlsruhe Institute of Technology. The image depicts the studied all-carbon polygon shaped macrocycles along with their intense circular dichroism spectra in the background. The bright light within the macrocycles displays its efficient conjugation.

Geländer Molecules with Orthogonal Joints: Synthesis of Macrocyclic Dimers.

Orthogonal joints, understood as connections with an angle of 90°, were introduced in the design of the "Geländer" model compounds 1 and 2. The banister, consisting of a conjugated carbazole dimer linked by either 1,3-butadiyne (2) or a single thiophene (1), wraps around an axis composed of a phthalimide dimer due to the dimensional mismatch of both subunits, which are interconnected by phenylene rungs. The "Geländer" structure was assembled from a monomer comprising the 1,4-diaminobenzene rung with one amino substituent as part of a 4-bromo phthalimide subunit forming the orthogonal junction to the axis, and the other as part of a masked 2-ethynyl carbazole as orthogonal joint to the banister.

Nitro-Decorated Microporous Covalent Organic Framework (TpPa-NO) for Selective Separation of CH from a CH/CH/CO Mixture and CO Capture.

A nitro-decorated microporous covalent organic framework, TpPa-NO, has been synthesized in a gram scale with a one-pot reaction. It can effectively selectively separate CH from a CH/CH/CO mixture and capture CO from CO/N based on ideal adsorption solution theory calculations and transient breakthrough experiments. Theoretical calculations illustrated that the hydrogen atoms of imine bonds, carbonyl oxygen, and nitro group show high affinity toward CH and CO, playing vital roles in efficient separation.

Intense Molar Circular Dichroism in Fully Conjugated All-Carbon Macrocyclic 1,3-Butadiyne Linked pseudo-meta [2.2]Paracyclophanes.

The synthetic access to macrocyclic molecular topologies with interesting photophysical properties has greatly improved thanks to the successful implementation of organic and inorganic corner units. Based on recent reports, we realized that pseudo-meta [2.2]paracyclophanes (PCPs) might serve as optimal corner units for constructing 3D functional materials, owing to their efficient electronic communication, angled substituents and planar chirality.

A Rare Flexible Metal-Organic Framework Based on a Tailorable Mn -Cluster Showing Smart Responsiveness to Aromatic Guests and Capacity for Gas Separation.

The design and creation of soft porous crystals combining regularity and flexibility may promote potential applications for gas storage and separation due to their deformable framework's responsiveness to external stimuli. The flexibility of metal-organic frameworks (MOFs) relies on alterable degrees of freedom that are mainly provided by organic linkers or the junctions linking organic and inorganic building units. Herein, we report a new dynamic MOF whose flexibility originates from an unprecedented tailorable Mn O -cluster and shows simultaneous coordination geometry changes and ligand migration that are reversibly driven by guest exchange.

Synthesis of silyl iron dinitrogen complexes for activation of dihydrogen and catalytic silylation of dinitrogen.

Three novel iron dinitrogen hydrides, [FeH(Pr-PSiP)(N)(PMe)] (1), [FeH(Pr-PSiP)(N)(PMe)] (2), and [FeH(Pr-PSi)(N)(PMe)] (3), supported by a silyl ligand are synthesized for the first time by changing the electronic effect and steric hindrance of the ligands through the reaction of ligands L1-L3 with Fe(PMe) in a nitrogen atmosphere. The ligands containing an electron-donating group with large steric hindrance on the phosphorus atom are beneficial for the formation of dinitrogen complexes. A penta-coordinate iron hydride [FeH(Pr-PSi)(PMe)] (4) was formed through the reaction of ligand L3 with Fe(PMe) in an argon atmosphere under the same conditions.

Alopecia Areata Treatment Patterns, Healthcare Resource Utilization, and Comorbidities in the US Population Using Insurance Claims.

Introduction: Alopecia areata (AA) is an autoimmune disorder causing sudden, non-scarring hair loss. There are currently no drugs approved for AA treatment. This study assessed prevalence of comorbidities, treatments, and healthcare costs and resource utilization among patients with AA in the USA.

Selectivity Reverse of Hydrosilylation of Aryl Alkenes Realized by Pyridine N-Oxide with [PSiP] Pincer Cobalt(III) Hydride as Catalyst.

Six silyl cobalt(III) hydrides - with [PSiP] pincer ligands having different substituents at the P and Si atoms ([(2-PhPCH)MeSiCo(H)(Cl)(PMe)] (), [(2-PhPCH)HSiCo(H)(Cl)(PMe)] (), [(2-PhPCH)PhSiCo(H)(Cl)(PMe)] (), [(2-PrPCH)HSiCo(H)(Cl)(PMe)] (), [(2-PrPCH)MeSiCo(H)(Cl)(PMe)] (), and [(2-PrPCH)PhSiCo(H)(Cl)(PMe)] ()) were synthesized through the reactions of the ligands (-) with CoCl(PMe) via Si-H bond cleavage. Compounds - have catalytic activity for alkene hydrosilylation, and among them, complex is the best catalyst with excellent -Markovnikov regioselectivity. A silyl dihydrido cobalt(III) complex from the reaction of with PhSiH was isolated, and its catalytic activity is equivalent to that of complex .

Synthesis and Transport Studies of a Cofacial Porphyrin Cyclophane.

Porphyrin cyclophane , consisting of two rigidly fixed but still movable cofacial porphyrins and exposing acetate-masked thiols in opposed directions of the macrocycle, is designed, synthesized, and characterized. The functional cyclophane , as pioneer of mechanosensitive 3D materials, forms stable single-molecule junctions in a mechanically controlled break-junction setup. Its reliable integration in a single-molecule junction is a fundamental prerequisite to explore the potential of these structures as mechanically triggered functional units and devices.

The Effect of Substituents on the Formation of Silyl [PSiP] Pincer Cobalt(I) Complexes and Catalytic Application in Both Nitrogen Silylation and Alkene Hydrosilylation.

Four different [PSiP]-pincer ligands - ((2-PhPCH)SiHR (R = H () and Ph ()) and (2-PrPCH)SiHR' (R' = Ph () and H ()) were used to investigate the effect of substituents at P and/or Si atom of the [PSiP] pincer ligands on the formation of silyl cobalt(I) complexes by the reactions with CoMe(PMe) via Si-H cleavage. Two penta-coordinated silyl cobalt(I) complexes, (2-PhPCH)HSiCo(PMe) () and (2-PhPCH)PhSiCo(PMe) (), were obtained from the reactions of and with CoMe(PMe), respectively. Under similar reaction conditions, a tetra-coordinated cobalt(I) complex (2-PrPCH)PhSiCo(PMe) () was isolated from the interaction of with CoMe(PMe).

The periodic law of the chemical elements: '' [1].

The historical roots, the discovery and the modern relevance of Dmitri Mendeleev's remarkable advance have been the subject of numerous scholarly works. Here, with a brief overview, we hope to provide a link into the contents of this special issue honouring the great scientist. Mendeleev's advance, announced in March 1869, as he put it in 1889, to the '…', first set out the very basis of the periodic law of the chemical elements, the natural relation between the properties of the elements and their atomic weights.

Correction: Pyridine N-oxide promoted hydrosilylation of carbonyl compounds catalyzed by [PSiP]-pincer iron hydrides.

Correction for 'Pyridine N-oxide promoted hydrosilylation of carbonyl compounds catalyzed by [PSiP]-pincer iron hydrides' by Guoliang Chang et al., Dalton Trans., 2020, 49, 9349-9354, DOI: 10.

Pyridine N-oxide promoted hydrosilylation of carbonyl compounds catalyzed by [PSiP]-pincer iron hydrides.

Five [PSiP]-pincer iron hydrides 1-5, [(2-Ph2PC6H4)2HSiFe(H)(PMe3)2 (1), (2-Ph2PC6H4)2MeSiFe(H)(PMe3)2 (2), (2-Ph2PC6H4)2PhSiFe(H)(PMe3)2 (3), (2-(iPr)2PC6H4)2HSiFe(H)(PMe3) (4), and (2-(iPr)2PC6H4)2MeSiFe(H)(PMe3)2 (5)], were used as catalysts to study the effects of pyridine N-oxide and the electronic properties of [PSiP]-ligands on the catalytic hydrosilylation of carbonyl compounds. It was proved for the first time that this catalytic process could be promoted with pyridine N-oxide as the initiator at 30 °C because the addition of pyridine N-oxide is beneficial for the formation of an unsaturated hydrido iron complex, which is the key intermediate in the catalytic mechanism. Complex 4 as the best catalyst shows excellent catalytic performance.

Novel double functional protection of cephalostatin analogues using a gas-free chlorination method.

Herewith, we report on a method that allows to simultaneously protect both the ∆ bond and the carbonyl group of the symmetrical bis-steroidal diketone . We found that environmentally friendly and gas-free chlorination is ideally suited to achieve this goal. This method was discovered during our efforts to methoxylate in a solution of dichloromethane and basic methanol in the presence of diacetoxy iodobenzene.