Increasing correlation length in bulk supercooled H2O, D2O, and NaCl solution determined from small angle x-ray scattering

Using small angle x-ray scattering, we find that the correlation length of bulk liquid water shows a steep increase as temperature decreases at subzero temperatures (supercooling) and that it can, similar to the thermodynamic response functions, be fitted to a power law. This indicates that the anomalous properties of water are attributable to fluctuations between low- and high-density regions with rapidly growing average size upon supercooling. The substitution of H(2)O with D(2)O, as well as the addition of NaCl salt, leads to substantial changes of the power law behavior of the correlation length. Our results are consistent with the proposed existence of a liquid-liquid critical point in the deeply supercooled region but do not exclude a singularity-free model.     

Selective heterolytic P-P bond cleavage of white phosphorus by a frustrated carbene-borane Lewis pair

Frustrated carbene-borane Lewis pairs are able to affect the selective cleavage of one of the six P-P bonds in white phosphorus (P(4)) to afford an adduct, in which an abnormal carbene of the imidazolium-4-yl type and B(C(6)F(5))(3) are bound in a trans,trans fashion to a butterfly-like bicyclo[1.1.0]tetraphosphabutane moiety.     

Oxidation of Pt(111) under near-ambient conditions

The oxidation of Pt(111) at near-ambient O2 pressures has been followed in situ using x-ray photoelectron spectroscopy (XPS) and ex situ using x-ray absorption spectroscopy (XAS). Polarization-dependent XAS signatures at the O K edge reveal significant temperature- and pressure-dependent changes of the Pt-O interaction. Oxide growth commences via a PtO-like surface oxide that coexists with chemisorbed oxygen, while an ultrathin α-PtO2 trilayer is identified as the precursor to bulk oxidation. These results have important implications for understanding the chemical state of Pt in catalysis.     

Elemental composition of fine particulate matter (PM2.5) in Skopje,FYR of Macedonia

Aerosol samples were collected at an urban background site in Skopje, Former Yugoslavic Republic of Macedonia, during four measurement campaigns from December 2006 to October 2007. An impactor was used to collect particulate matter (PM_2.5) aerosol particles and the samples were analyzed for the concentrations of particulate mass, black carbon (BC), and 17 elements. The 12‐h average PM_2.5 concentrations varied in the range 10–140 µg m^?3 with the highest concentrations measured during wintertime pollution episodes and during the summer period. Pair‐wise correlations and crustal enrichment were studied and the data set was analyzed by factor analysis and positive matrix factorization. Major aerosol components were identified as mineral dust (main observed tracers Si, K, Ca, Ti, Fe, Sr, and Rb), combustion (BC, S, K, V, and Ni), traffic‐related aerosol (Pb and Zn), and secondary sulfate combined with mineral dust. Combustion sources dominated during wintertime and were likely due to heavy oil combustion, biomass burning, and other industrial activities within the city area. Mineral dust was observed throughout the year, but the concentrations peaked during the unusually hot and dry summer of 2007. It is concluded that Skopje suffers from serious air pollution due to central and residential heating, the transport sector, and industrial activities within the city, and contributions from mineral dust increase the PM_2.5 concentrations under dry periods. Topography and meteorological conditions aggravate the problems and make the air quality comparable with the conditions in other highly polluted cities in Southern Europe and worldwide. Copyright © 2011 John Wiley & Sons, Ltd.     

A Note on Toeplitz’ Conjecture

In 1911, Toeplitz made a conjecture asserting that every Jordan curve in $\mathbb{R}^{2}$ contains four points forming the corners of a square. Here Conjecture C is presented, which states that the side length of the largest square on a closed curve that consists of edges of an n×n grid is at least $1/\sqrt{2}$ times the side length of the largest axis-aligned square contained inside the curve. Conjecture C implies Toeplitz’ conjecture and is verified computationally for n≤13.     

High Loading Efficiency and Controlled Release of Bioactive Immunotherapeutic Proteins Using Vaterite Nanoparticles

Nanoparticles may limit off-tumor/on-target ubiquitous activation of signaling by protein-based drugs. However, many challenges still exist in the design of a nanoparticle for protein delivery. In this study, conditions to establish vaterite nanoparticles as a pH-sensitive drug delivery system (DDS) for encapsulated protein drugs are comprehensively evaluated. Low coprecipitation pH of vaterite and protein prevents protein denaturation and yields high loading efficiency. Unprotected vaterite recrystallizes in aqueous solutions within 3 h to calcite and releases the loaded protein completely, but surface-modified particles with carboxyl groups containing polymers prove stable for more than 5 months. Notably, modification of vaterite with sulfonated polymers increases the loading of cationic proteins by a multiple. A system is developed for vaterite exposure to (pH) conditions under body-like-flow rates, with the dissolution of vaterite and simultaneous release of active proteins at tumor microenvironmental pH reaching up to 80% and only 20% at physiological pH within 2 h. Importantly, the immunomodulatory protein tumor necrosis factor preserves its native structure and fully retains functional activity in vitro after release from the particles. In conclusion, the studies described here provide a framework for the development of vaterite-based DDS as a carrier for bioactive protein-based therapeutics.     

A microfluidic system enabling Raman measurements of the oxygenation cycle in single optically trapped red blood cells

Using a lab-on-a-chip approach we demonstrate the possibility of selecting a single cell with certain properties and following its dynamics after an environmental stimulation in real time using Raman spectroscopy. This is accomplished by combining a micro Raman set-up with optical tweezers and a microfluidic system. The latter gives full control over the media surrounding the cell, and it consists of a pattern of channels and reservoirs defined by electron beam lithography that is moulded into rubber silicon (PDMS). Different buffers can be transported through the channels using electro-osmotic flow, while the resonance Raman response of an optically trapped red blood cell (RBC) is simultaneously registered. This makes it possible to monitor the oxygenation cycle of the cell in real time and to investigate effects like photo-induced chemistry caused by the illumination. The experimental set-up has high potential for in vivo monitoring of cellular drug response using a variety of spectroscopic probes.     

Conformational energies and rotational barriers in 3-methyl-1-butene and 1-butene: An ab initio and molecular mechanics study

The calculated result obtained with MM2(87) for the rotation of the isopropyl group in 3-methyl-1-butene is not in agreement with experimental data. In order to reparametrize the C_sp2-C_sp3-C_sp-C_sp3 torsional angle, 3-methyl-1-butene and 1-butene have been studied by molecular mechanics (MM2(87)) and ab initio (MP2/6-31G* and MP3/6-31G*) calculations. The reparametrization of the torsional angle gives calculated results from MM2(87) in agreement with experimental data and ab initio calculations for both 3-methyl-1-butene and 1-butene. The calculated barriers for the rotation of alkyl groups in alkylbenzenes are improved with these new parameters.