Thermodynamic Principles for the Design of Polymers for Drug Formulations.

Polymers play an essential role in drug formulation and production of medical devices, implants, and diagnostics. Following drug discovery, an appropriate formulation is selected to enable drug delivery. This task can be exceedingly challenging owing to the large number of potential delivery methods and formulation and process variables that can interact in complex ways.

Chemistry of a 1,5-Oligosilanylene Dianion Containing a Disiloxane Unit.

Synthesis of a number of disiloxane containing cyclo- and bicyclooligosilanes is described starting from the dipotassium 1,5-oligosiloxanylene diide derived from 1,3-bis[tris(trimethylsilyl)silyl]tetramethyldisiloxane. In addition, the use of this particular fragment as ligand for zinc and group 4 metallocene complexes was studied. Both types of compounds exhibit marked structural differences compared to related compounds containing Si-Si-Si units instead of the Si-O-Si fragment.

Nonlinear dynamics underlying sensory processing dysfunction in schizophrenia.

Natural systems, including the brain, often seem chaotic, since they are typically driven by complex nonlinear dynamical processes. Disruption in the fluid coordination of multiple brain regions contributes to impairments in information processing and the constellation of symptoms observed in neuropsychiatric disorders. Schizophrenia (SZ), one of the most debilitating mental illnesses, is thought to arise, in part, from such a network dysfunction, leading to impaired auditory information processing as well as cognitive and psychosocial deficits.

Selective Formation of 4,4'-Biphenols by Anodic Dehydrogenative Cross- and Homo-Coupling Reaction.

A simple and selective electrochemical synthesis by dehydrogenative coupling of unprotected 2,6- or 2,5-substituted phenols to the desired 4,4'-biphenols is reported. Using electricity as the oxidizing reagent avoids pre-functionalization of the starting materials, since a selective activation of the substrates takes place. Without the necessity for metal-catalysts or the use of stoichiometric reagents it is an economic and environmentally friendly transformation.

Spectroscopic and Structural Study of Some Oligosilanylalkyne Complexes of Cobalt, Molybdenum and Nickel.

Metal induced stabilization of α-carbocations is well known for cobalt- and molybdenum complexed propargyl cations. The same principle also allows access to reactivity enhancement of metal coordinated halo- and hydrosilylalkynes. In a previous study, we have shown that coordination of oligosilanylalkynes to the dicobalthexacarbonyl fragment induces striking reactivity to the oligosilanyl part.

A guideline for reporting experimental protocols in life sciences.

Experimental protocols are key when planning, performing and publishing research in many disciplines, especially in relation to the reporting of materials and methods. However, they vary in their content, structure and associated data elements. This article presents a guideline for describing key content for reporting experimental protocols in the domain of life sciences, together with the methodology followed in order to develop such guideline.

Phase separation in mixed polymer brushes on nanoparticle surfaces enables the generation of anisotropic nanoarchitectures.

The preparation of nanoparticles and their targeted connection with other functional units is one key challenge in developing nanoscale devices. Herein, we report an experimental strategy toward the development of anisotropic nanoparticle architectures. Our approach is based on phase separation of binary mixed polymer brushes on gold nanoparticle surfaces leading to Janus-type structures, as revealed by scanning transmission electron microscopy and electron energy-loss spectroscopy and, additionally, corroborated by computer simulation.

Polymorphism of terthio-phene with surface confinement.

The origin of unknown polymorphic phases within thin films is still not well understood. This work reports on crystals of the molecule terthio-phene which were grown by thermal gradient crystallization using glass-plate substrates. The crystalline domains displayed a plate-like morphology with an extended lateral size of about 100 µm, but a thickness of only a few µm.

Tetraacylstannanes as Long-Wavelength Visible-Light Photoinitiators with Intriguing Low Toxicity.

The first tetraacylstannanes Sn[(CO)R] (R=2,4,6-trimethylphenyl (1 a) and 2,6-dimethylphenyl (1 b)), a class of highly efficient Sn-based photoinitiators, were synthesized. The formation of these derivatives was confirmed by NMR spectroscopy, mass spectrometry, and X-ray crystallography. The UV/Vis absorption spectra of 1 a, b reveal a significant redshift of the longest wavelength absorption compared to the corresponding germanium compounds.

Spirocyclic germanes via transannular insertion reactions of vinyl germylenes into Si-Si bonds.

The reactions of two cyclic germylene phosphane adducts with monosubstituted acetylenes caused the formation of spirocyclic germanes, which is postulated to occur by double acetylene insertion into germylene attached bonds. Further insertion of the formed cyclic divinylgermylene into transannular Si-Si or Si-Ge bonds provides the spirocyclic germanes. Thermal treatment of two germacyclopropenes, formed by the reaction of the two cyclic germylene phosphane adducts with tolane, also produced spirocyclogermanes.

A Priori Prediction of Mass Spectrometric Product Patterns of Photoinitiated Polymerizations.

We introduce a method for the a priori prediction of mass spectra of complex poly(methyl methacrylate)s initiated by photoinitiators featuring multiple cleavage points. The method is based on permutation mathematics using multinomial coefficients to predict the probability of each poly(methyl methacrylate) species' isotopic pattern contribution to the overall mass spectrum. The method assumes a statistical behavior for the cleavage of the photoinitiator.

Recent Advances in Germanium-Based Photoinitiator Chemistry.

Acylgermanes provide an outstanding photoinduced reactivity at very useful absorption wavelengths. This encouraged multidisciplinary research groups to utilize them as highly effective and non-toxic photoinitiators particularly for medical applications. In this Minireview, we present the most recent breakthroughs to synthesize acylgermanes.

Spectral shift functions and Dirichlet-to-Neumann maps.

The spectral shift function of a pair of self-adjoint operators is expressed via an abstract operator-valued Titchmarsh-Weyl -function. This general result is applied to different self-adjoint realizations of second-order elliptic partial differential operators on smooth domains with compact boundaries and Schrödinger operators with compactly supported potentials. In these applications the spectral shift function is determined in an explicit form with the help of (energy parameter dependent) Dirichlet-to-Neumann maps.

Speeding up NMR by in Situ Photo-Induced Reversible Acceleration of T -Relaxation (PIRAT).

Increasing the signal-to-noise ratio is one of the major goals in the field of NMR spectroscopy. In this proof of concept, we accelerate relaxation during an NMR pulse sequence using photo-generated paramagnetic states of an inert sensitizer. For the follow-up acquisition period, the system is converted to a diamagnetic state.

Copper(II) complexes based on tripodal pyrazolyl amines: Synthesis, structure, magnetic properties and anticancer activity.

The Cu(II) complexes [Cu(bpdmpz)Cl]ClO (1), [Cu(bdmpzp)Cl]ClO (2-ClO), [Cu(bdmpzp)Cl]PF (2-PF) and [Cu(tdmpza)Cl]ClO (3), bpdmpzp=[bis[((2-pyridylmethyl)-di(3,5-dimethyl-1H-pyrazolyl)methyl)]amine, bdmpzp=[bis((di(3,5-dimethyl-1H-pyrazolyl)methyl)-(2-pyridylmethyl)]amine and tdmpza=tris[di(3,5-dimethyl-1H-pyrazolyl)-methyl)]amine were synthesized and characterized by elemental analysis, magnetic and conductivity measurements, electrospray-ionization mass spectrometry, infrared and electronic spectroscopy, and X-ray crystallography. The magnetic properties of the complexes, measured at variable temperature, revealed weak antiferromagnetic intermolecular interactions. The cytotoxicity of the complexes 1, 2-ClO, 3, and 4 ([Cu(bedmpzp)Cl]PF, where bedmpzp=[bis(3,5-dimethyl-1H-pyrazol-1-yl-1-ethyl)-(2-pyridylmethyl)]amine), was investigated against four human cancer cell lines: A2780 (ovarian), A2780R (cisplatin-resistant variant), HOS (aggressive bone tumors), CaCo2 (epithelial colorectal adenocarcinoma) and on healthy human hepatocytes.

Branched Hydrosilane Oligomers as Ideal Precursors for Liquid-Based Silicon-Film Deposition.

Herein a convenient synthetic method to obtain 2,2,3,3-tetrasilyltetrasilane 3 and 2,2,3,3,4,4-hexasilylpentasilane 4 on a multigram scale is presented. Proton-coupled Si NMR spectroscopy and single-crystal X-ray crystallography enabled unequivocal structural assignment. Owing to their unique properties, which are reflected in their nonpyrophoric character on contact with air and their enhanced light absorption above 250 nm, 3 and 4 are valuable precursors for liquid-phase deposition (LPD) and the processing of thin silicon films.

Late Neoproterozoic seawater oxygenation by siliceous sponges.

The Cambrian explosion, the rapid appearance of most animal phyla in the geological record, occurred concurrently with bottom seawater oxygenation. Whether this oxygenation event was triggered through enhanced nutrient supply and organic carbon burial forced by increased continental weathering, or by species engaging in ecosystem engineering, remains a fundamental yet unresolved question. Here we provide evidence for several simultaneous developments that took place over the Ediacaran-Cambrian transition: expansion of siliceous sponges, decrease of the dissolved organic carbon pool, enhanced organic carbon burial, increased phosphorus removal and seawater oxygenation.

Tuning the Si-N Interaction in Metalated Oligosilanylsilatranes.

Most known silatrane chemistry is concerned with examples where the attached silatrane substituent atom is that of an element more electronegative than silicon. The current study features silylated silatranes with a range of electropositive elements attached to the silyl group. The resulting compounds show different degrees of electron density on the silatrane-substituted silicon atom.

Using Functionalized Silyl Ligands To Suppress Solvent Coordination to Silyl Lanthanide(II) Complexes.

The reaction of the potassium 1,3-trisilanediide MeSi[Si(MeSi)K] with SmI and YbI was found to give the respective disilylated complexes MeSi[Si(MeSi)]Sm·2THF and MeSi[Si(MeSi)]Yb·2THF. Desolvation of coordinated solvent molecules in these complexes made their handling difficult. However, using a number of functionalized silanide ligands, complexes with a diminished number or even no coordinated solvent molecules were obtained ((RSi)Ln(THF) (x = 0-3)).

Integrated process development of a reactive extraction concept for itaconic acid and application to a real fermentation broth.

Itaconic acid (IA) has a high potential to be used as a bio-based platform chemical and its biocatalytic production via fermentation has significantly improved within the last decade. Additionally downstream processing using reactive extraction (RE) was described, potentially enabling a more efficient sustainable bioprocess producing IA. The bottleneck to overcome is the connection of up- and downstream processing, caused by lack of biocompatibility of the RE systems and direct application to fermentation broth.

Uniform Distance Scaling Behavior of Planet-Satellite Nanostructures Made by Star Polymers.

Planet-satellite nanostructures from RAFT star polymers and larger (planet) as well as smaller (satellite) gold nanoparticles are analyzed in experiments and computer simulations regarding the influence of arm number of star polymers. A uniform scaling behavior of planet-satellite distances as a function of arm length was found both in the dried state (via transmission electron microscopy) after casting the nanostructures on surfaces and in the colloidally dispersed state (via simulations and small-angle X-ray scattering) when 2-, 3-, and 6-arm star polymers were employed. This indicates that the planet-satellite distances are mainly determined by the arm length of star polymers.

Tetraacylgermanes: Highly Efficient Photoinitiators for Visible-Light-Induced Free-Radical Polymerization.

In this contribution a convenient synthetic method to obtain tetraacylgermanes Ge[C(O)R] (R=mesityl (1 a), phenyl (1 b)), a previously unknown class of highly efficient Ge-based photoinitiators, is described. Tetraacylgermanes are easily accessible via a one-pot synthetic protocol in >85 % yield, as confirmed by NMR spectroscopy, mass spectrometry, and X-ray crystallography. The efficiency of 1 a,b as photoinitiators is demonstrated in photobleaching (UV/Vis), time-resolved EPR (CIDEP), and NMR/CIDNP investigations as well as by photo-DSC studies.

Electron Transfer and Modification of Oligosilanylsilatranes and Related Derivatives.

Several silatranyl -substituted oligosilanes were prepared starting from bis(trimethylsilyl)silatranylsilanide. Electrochemical and theoretical investigations of some oligosilanes revealed that electrooxidation occurs by formation of a short-lived cation radical. This species undergoes structural relaxation to form a pair of conformers, with endo and exo relationships with respect to the Si-N interaction.