Interface Amorphization of Two-Dimensional Black Phosphorus upon Treatment with Diazonium Salts

Two-dimensional (2D) black phosphorus (BP) represents one of the most appealing 2D materials due to its electronic, optical, and chemical properties. Many strategies have been pursued to face its environmental instability, covalent functionalization being one of the most promising. However, the extremely low functionalization degrees and the limitations in proving the nature of the covalent functionalization still represent challenges in many of these sheet architectures reported to date. Here we shine light on the structural evolution of 2D-BP upon the addition of electrophilic diazonium salts. We demonstrated the absence of covalent functionalization in both the neutral and the reductive routes, observing in the latter case an unexpected interface conversion of BP to red phosphorus (RP), as characterized by Raman, ³¹P-MAS NMR, and X-ray photoelectron spectroscopies (XPS). Furthermore, thermogravimetric analysis coupled to gas chromatography and mass spectrometry (TG-GC-MS), as well as electron paramagnetic resonance (EPR) gave insights into the potential underlying radical mechanism, suggesting a Sandmeyer-like reaction.     

Strong Asymptotics of the Orthogonal Polynomials with Respect to a Measure Supported on the Plane

We consider the orthogonal polynomials with respect to the measure over the whole complex plane. We obtain the strong asymptotic of the orthogonal polynomials in the complex plane and the location of their zeros in a scaling limit where n grows to infinity with N . The asymptotics are described in terms of three (probability) measures associated with the problem. The first measure is the limit of the counting measure of zeros of the polynomials, which is captured by the g‐function much in the spirit of ordinary orthogonal polynomials on the real line. The second measure is the equilibrium measure that minimizes a certain logarithmic potential energy, supported on a region K of the complex plane. The third measure is the harmonic measure of K ^c with a pole at ∞ . This appears as the limit of the probability measure given (up to the normalization constant) by the squared modulus of the n^th orthogonal polynomial times the orthogonality measure, i.e., The compact region K that is the support of the second measure undergoes a topological transition under the variation of the parameter in a double scaling limit near the critical point given by we observe the Hastings‐McLeod solution to Painlevé II in the asymptotics of the orthogonal polynomials. © 2014 Wiley Periodicals, Inc.     

Capillary zone electrophoresis of proteins applying ionic liquids for dynamic coating and as background electrolyte component

The use of ionic liquids in capillary electrophoresis, either as coating material or as components of the background electrolyte needs systematic standardization to set up optimal conditions. Excellent separation of the proteins was achieved using 1-ethyl-3-methylimidazolium tetrafluoroborate ([emim][BF₄]) or 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF₄]) ionic liquids using the properly made ionic-liquid–water binary mixtures for the experiments. The binary mixture has a distinctly stable and well perceptible low pH, which depends on the concentration of the ionic liquid, and on the preparation time of the mixture. Optimal conditions for the electrophoretic separation were obtained upon a multivariate analysis of the experimental parameters (applied voltage, migration time, concentration, and type of the ionic liquid). The standardized condition provides a low electroendosmotic flow toward the anode, which, however, did not hinder the proteins to migrate toward the cathode. The migration of cytochrome c, lysozyme, myoglobin, trypsin, and apo-transferrin at a pH around 2, far below the isoelectric points of the proteins, showed RSD values of the migration times less than 7.5% and less than 6.5% when using [emim][BF₄] or [bmim][BF₄], respectively, either in run-to-run or day-to-day experiments. The determination of the extent of the EOF is not possible with the commonly used EOF markers, due to interaction with the ionic-liquid constituents. The interaction of the ionic liquids with the proteins influences the migration order in zone electrophoresis. This method has been applied successfully for the analyses of real biological samples such as proteins from egg whites and human tears.     

Age-Related Absorption of the Human Lens in the Near-Ultraviolet Range

The purpose of the present study was to determine the age dependence of the ultraviolet (UV) absorption of the different parts of the human crystalline lens. Cryostat sections of human cadaveric lenses (60 μm) were cut. The UV absorbance of nine samples, derived from different parts of the lens, was determined using a Shimadzu scanning spectrophotometer. The absorbance of the anterior and posterior lens capsules was measured separately. The absorption coefficients were calculated from the measured absorbance and values taken at 280 as well as at 360 nm were compared statistically. ANCOVA analysis of the values taken at 280 and at 360 nm wavelengths shows that correlation between the absorption coefficients and age can be found only in the case of the posterior layers. These results suggest a differential age-dependent increase of the UV absorption of the posterior layers compared to the anterior ones and can be related to the differential protein expression in the anterior and posterior parts. Posterior crystalline lens capsules have higher absorption coefficients than the anterior ones regardless of age.     

Quadruplex–Duplex Junction: A High-Affinity Binding Site for Indoloquinoline Ligands

A parallel quadruplex derived from the Myc promoter sequence was extended by a stem-loop duplex at either its 5′- or 3′-terminus to mimic a quadruplex–duplex (Q–D) junction as a potential genomic target. High-resolution structures of the hybrids demonstrate continuous stacking of the duplex on the quadruplex core without significant perturbations. An indoloquinoline ligand carrying an aminoalkyl side chain was shown to bind the Q–D hybrids with a very high affinity in the order K_a≈10⁷ m ⁻¹ irrespective of the duplex location at the quadruplex 3′- or 5′-end. NMR chemical shift perturbations identified the tetrad face of the Q–D junction as specific binding site for the ligand. However, calorimetric analyses revealed significant differences in the thermodynamic profiles upon binding to hybrids with either a duplex extension at the quadruplex 3′- or 5′-terminus. A large enthalpic gain and considerable hydrophobic effects are accompanied by the binding of one ligand to the 3′-Q–D junction, whereas non-hydrophobic entropic contributions favor binding with formation of a 2:1 ligand-quadruplex complex in case of the 5′-Q–D hybrid.     

Annealing of the β-modification of polypropylene

Expressive memory effect has been proven in the course of the annealing of the β-modification of polypropylene (β-PP). The character of the structural changes taking place in β-PP during annealing strongly depends on the thermal history. In dependence on the thermal history βα or ββ-recrystallization takes place during thermal treatment. In case the annealing starts from the crystallization temperature β-PP is recrystallized into a more perfect structure with higher melting point - similarly to thermodynamically stable modifications. The samples cooled below a certain temperature before subjected to annealing transform partly or fully into the α-modification. The βα-recrystallization tendency prevalent on the effect of recooling can be reduced or eliminated with the aid of stepwise annealing with decreasing temperature steps.     

Determination of the ratio of the shear modulus over the longitudinal modulus for swollen networks

The ratio of the shear modulus over the longitudinal osmotic modulus has been determined by different experimental methods. Osmotic deswelling, swelling kinetics as well as deswelling induced by unidirectional compression were performed. For the experiments chemically cross-linked poly(vinyl acetate) gels swollen in toluene and acetone (good solvents) and iso-propyl alcohol (poor solvent) have been used. The results are in agreement with the theoretical predictions.     

A New Oxygen Containing Pyclen-Type Ligand as a Manganese(II) Binder for MRI and 52Mn PET Applications: Equilibrium,Kinetic, Relaxometric,Structural and Radiochemical Studies

A new pyclen-3,9-diacetate derivative ligand (H₂3,9-OPC2A) was synthesized possessing an etheric O-atom opposite to the pyridine ring, to improve the dissociation kinetics of its Mn(II) complex (pyclen = 3,6,9,15-tetraazabicyclo(9.3.1)pentadeca-1(15),11,13-triene). The new ligand is less basic than the N-containing analogue (H₂3,9-PC2A) due to the non-protonable O-atom. In spite of its lower basicity, the conditional stability of the [Mn(3,9-OPC2A)] (pMn = −log(Mn(II)), c_L = c_Mn(II) = 0.01 mM. pH = 7.4) remains unaffected (pMn = 8.69), compared to the [Mn(3,9-PC2A)] (pMn = 8.64). The [Mn(3,9-OPC2A)] possesses one water molecule, having a lower exchange rate with bulk solvents (k_ex²⁹⁸ = 5.3 ± 0.4 × 10⁷ s⁻¹) than [Mn(3,9-PC2A)] (k_ex²⁹⁸ = 1.26 × 10⁸ s⁻¹). These mild differences are rationalized by density-functional theory (DFT) calculations. The acid assisted dissociation of [Mn(3,9-OPC2A)] is considerably slower (k₁ = 2.81 ± 0.07 M⁻¹ s⁻¹) than that of the complexes of diacetates or bisamides of various 12-membered macrocycles and the parent H₂3,9-PC2A. The [Mn(3,9-OPC2A)] is inert in rat/human serum as confirmed by ⁵²Mn labeling (nM range), as well as by relaxometry (mM range). However, a 600-fold excess of EDTA (pH = 7.4) or a mixture of essential metal ions, propagated some transchelation/transmetalation in 7 days. The H₂3,9-OPC2A is labeled efficiently with ⁵²Mn at elevated temperatures, yet at 37 °C the parent H₂3,9-PC2A performs slightly better. Ultimately, the H₂3,9-OPC2A shows advantageous features for further ligand designs for bifunctional chelators.     

Neutron scattering and swelling properties of end-linked polydimethylsiloxane networks

Small angle neutron scattering measurements were performed on polydimethylsiloxane-toluene solutions and gels at different degrees of swelling. The scattering signal of the gel was decomposed into a solution-like part and a static part. The thermodynamic information obtained from the solution-like part of the signal is compared with macroscopic swelling pressure observations.