Observation of fragile-to-strong dynamic crossover in protein hydration water

At low temperatures, proteins exist in a glassy state, a state that has no conformational flexibility and shows no biological functions. In a hydrated protein, at temperatures greater-- similar 220 K, this flexibility is restored, and the protein is able to sample more conformational substates, thus becoming biologically functional. This "dynamical" transition of protein is believed to be triggered by its strong coupling with the hydration water, which also shows a similar dynamic transition. Here we demonstrate experimentally that this sudden switch in dynamic behavior of the hydration water on lysozyme occurs precisely at 220 K and can be described as a fragile-to-strong dynamic crossover. At the fragile-to-strong dynamic crossover, the structure of hydration water makes a transition from predominantly high-density (more fluid state) to low-density (less fluid state) forms derived from the existence of the second critical point at an elevated pressure.     

Indications for draining a parapneumonic effusion: an evidence-based approach

A patient with pneumonia who develops a parapneumonic effusion challenges the physician to determine the need for pleural fluid drainage. This determination is influenced by multiple factors including the patient's general state of health, the existence of comorbidities, the virulence of the underlying pathogen, and the extent of the pneumonia that dictate clinical outcome and the relative risks and benefits of drainage. The presence of intrapleural pus represents the only factor that clearly establishes the need for drainage, although most experts recommend draining pleural fluid that is positive by Gram's stain or culture for a pathogen. Other factors such as the extent of the patient's pneumonia, severity of systemic signs of inflammation, radiographic features of the effusion, and pleural fluid chemical profile assist clinical decision making. The fundamental principle that guides therapy is the need to promptly and effectively drain pleural fluid whenever it appears likely that it will progress to a frank empyema with antibiotic therapy alone.     

A van der Waals-type equation of state for fluids with associating molecules

The basic assumptions of van der Waals theory are contained in two well-known concepts: excluded volume (repulsive forces) and a homogeneous, isotropic field potential (attractive forces). We have superimposed on these, one more well-known concept: the existence of dimers, trimers, etc., at chemical equilibrium. With reasonable simplifying assumptions, we obtain a closed-form equation of state, applicable to all fluid densities, and potentially useful for fluids containing strongly polar or hydrogen-bonded molecules. At all temperatures and at high densities, the equation of state suggests a phase transition where, because of extensive association, a new (solid-like) phase is in equilibrium with a “normal” fluid phase. The boundary between these phases has no critical point.     

Evolution of laboratory parameters during sickle cell painful crisis: evidence compatible with dense red cell sequestration without thrombosis

We find that during 51 episodes of sickle cell painful crisis indirect bilirubin fell 52% from its steady state value of 2.3 +/- 1.9 mg% to a value of 1.1 +/- 0.37 mg% at the end of crisis (p less than .00000085). The indirect bilirubin decline correlates with a decrease in the dense sickle cells during crisis (r = .31, p less than .0009). During steady state, both indirect bilirubin and lactic acid dehydrogenase correlate significantly with number of dense red cells (r = .62, p less than .000002 and r = .32, p less than .02 respectively). Platelet counts, beta-thromboglobulin, Platelet Factor 4, and Fibrinopeptide A levels all were elevated during steady state and did not change during the evolution of crisis. These data demonstrate that elevated indices usually associated with platelet activation are a feature of the steady state of sickle cell disease but argue against thrombosis as a factor in the progression of a sickle cell painful crisis episode. The parallel decline of both dense cells and bilirubin during painful crises indicates that the disappearance of dense cells during crisis is not caused by hemolysis and supports the hypothesis that dense red cell sequestration, in the absence of evidence of thrombosis, is an intrinsic component of the evolution of sickle cell painful crisis.     

Improved Anti-Vulcanization and Bonding Performance of a Silver Alloy Bonding Wire by a Cathodic Passivation Treatment with Palladium

As a traditional interconnect material, silver alloy bonding wires are widely used in electronic packaging, but their propensity to vulcanize quickly has not been sufficiently addressed. The current surface anti-oxidation and anti-sulfidation treatments are often accompanied by a decline in bonding performance, which hinders the use of silver alloy bonding wires in new applications. In the present paper, we develop a new cathodic passivation treatment in a Pd-containing solution for silver bonding wires, which not only significantly improves their vulcanization resistance, but also maintains their bonding performance. The surface of the treated wires remains unaffected after vulcanization in 0.3 μg/m³ of ammonium sulfide for 60 min. Compared to a Pd-free passivation treatment, the bonding strength of the wire passivated with the Pd-containing solution improves from 0.20 to 0.27 N. XPS analysis confirms the existence of Pd on the surface of the wire. The solder ball formed an obtuse angle instead of a sharp angle on the pad, which is beneficial for bonding strength.     

Ochronotic arthropathy with calcium pyrophosphate crystal deposition a light and electron microscopic study

Synovial fluid from a patient with ochronotic arthropathy and calcification of the capsule of the right knee contained calcium pyrophosphate crystals and dark debris. Microscopic examination of an unstained fresh preparation showed these dark fragments to have a brown or golden brown color typical of ochronotic pigment. By electron microscopy there were identifiable cartilage fragments in the synovial fluid. These contained clumps of dense material deposited on the surface of collagen fibers. Similar brown staining and electron dense material probably representing ochronotic pigment was seen in synovial membrane and synovial fluid cells. Some of the intracellular calcium pyrophosphate crystals were in close relation with probable pigment.     

Hierarchies of networked phases induced by multiple liquid-liquid critical points

Nanoparticles and colloids functionalized by four single strands of DNA can be thought of as designed analogs to tetrahedral network-forming atoms and molecules, with a difference that the attached DNA strands allow for control of the length scale of bonding relative to the core size. We explore the behavior of an experimentally realized model for nanoparticles functionalized by four single strands of DNA (a tetramer), and show that this single-component model exhibits a rich phase diagram with at least three critical points and four thermodynamically distinct amorphous phases. We demonstrate that the additional critical points are part of the Ising universality class, like the ordinary liquid-gas critical point. The dense phases consist of a hierarchy of interpenetrating networks, reminiscent of a woven cloth. Thus, bonding specificity of DNA provides an effective route to generate new nano-networked materials with polyamorphic behavior. The concept of network interpenetration helps to explain the generation of multiple liquid phases in single-component systems, suggested to occur in some atomic and molecular network-forming fluids, including water and silica.     

Fabrication of Aluminum Foam-Filled Thin-Wall Steel Tube by Friction Welding and Its Compression Properties

Aluminum foam has received considerable attention in various fields and is expected to be used as an engineering material owing to its high energy absorption properties and light weight. To improve the mechanical properties of aluminum foam, combining it with dense tubes, such as aluminum foam-filled tubes, was considered necessary. In this study, an aluminum foam-filled steel tube, which consisted of ADC12 aluminum foam and a thin-wall steel tube, was successfully fabricated by friction welding. It was shown that a diffusion bonding layer with a thickness of approximately 10 μm was formed, indicating that strong bonding between the aluminum foam and the steel tube was realized. By the X-ray computed tomography observation of pore structures, the fabrication of an aluminum foam-filled tube with almost uniform pore structures over the entire specimen was confirmed. In addition, it was confirmed that the aluminum foam-filled steel tube exhibited mechanical properties superior to those of the ADC12 aluminum foam and steel tube. This is considered to be attributed to the combination of the aluminum foam and steel tube, which particularly prevents the brittle fracture and collapse of the ADC12 foam by the steel tube, along with the strong metal bonding between the aluminum foam and the steel tube.     

Fabrication of Aluminum Tubes Filled with Aluminum Alloy Foam by Friction Welding

Aluminum foam is usually used as the core of composite materials by combining it with dense materials, such as in Al foam core sandwich panels and Al-foam-filled tubes, owing to its low tensile and bending strengths. In this study, all-Al foam-filled tubes consisting of ADC12 Al-Si-Cu die-cast aluminum alloy foam and a dense A1050 commercially pure Al tube with metal bonding were fabricated by friction welding. First, it was found that the ADC12 precursor was firmly bonded throughout the inner wall of the A1050 tube without a gap between the precursor and the tube by friction welding. No deformation of the tube or foaming of the precursor was observed during the friction welding. Next, it was shown that by heat treatment of an ADC12-precursor-bonded A1050 tube, gases generated by the decomposition of the blowing agent expand the softened ADC12 to produce the ADC12 foam interior of the dense A1050 tube. A holding time during the foaming process of approximately t_H = 8.5 min with a holding temperature of 948 K was found to be suitable for obtaining a sound ADC12-foam-filled A1050 tube with sufficient foaming, almost uniform pore structures over the entire specimen, and no deformation and minimum reduction in the thickness of the tube.     

Clinical usefulness of determining beta-2-microglobulin concentration in thyroid cystic fluid

The main subject of the paper was to prove that beta-2-microglobulin (beta-2-m) exists in fluid taken from a thyroid gland cyst of the patients with non-toxic, nodular goitre with cysts and whether the confirmation of beta-2-m existence in fluid taken from a cyst may indicate the presence of autoimmunological process in thyroid glands. The research was carried out on a group of 36 patients operated on because of goitre. Patients with the thyroid cancer were except. The operations were carried out in the General Surgery Department of Hospital 1 in Sosnowiec from 1994 to 1999. The group of patients consisted of women aged between 13 to 75 years old (average 43 +/- 13.8 years). TSH, FT4 serum concentration in this investigated group were normal. The paper presents the beta-2-m existence in fluid taken from a thyroid gland cyst. It was confirmed that there was no differences between beta-2-m serum concentration in operated patients and in healthy controls. In 50% of patients operated on with thyroid cysts high antibody antithyroid peroxidase (antiTPO) serum concentration and in fluid taken from cyst was confirmed and statistically higher beta-2-m concentration in cyst fluid than beta-2-m concentration in serum. CONCLUSIONS: The increased antiTPO concentration in serum and in a fluid taken from cyst and beta-2-m existence in cyst fluid point to the autoimmunological process taking place in half of the patients with thyroid cysts.     

Pulmonary densities during anaesthesia. An experimental study on lung morphology and gas exchange

The nature of dense areas in dependent lung regions regularly seen in anaesthetized humans was examined in a sheep model. During anaesthesia with muscle paralysis and mechanical ventilation dense areas in dependent lung regions could be seen by means of computerized tomography (CT). They had the same location and the same attenuation as in anaesthetized humans. Gas exchange impairment tended to increase in proportion to the size of the dense area on the CT scan. Microscopy showed that the densities in the sheep were atelectatic lung regions, with no or little interstitial oedema and only minor vascular congestion. The atelectatic lung tissue was sharply demarcated and the lung tissue in the immediate vicinity was well aerated, or even hyperinflated. Gravimetry showed the same amount of extravascular fluid and blood per unit lung weight in the atelectatic lung and in the aerated lung region. It is concluded that the densities appearing in dependent lung regions during anaesthesia are caused by atelectasis.     

Structure and Thermodynamics of Silicon Oxycarbide Polymer-Derived Ceramics with and without Mixed-Bonding

Silicon oxycarbides synthesized through a conventional polymeric route show characteristic nanodomains that consist of sp² hybridized carbon, tetrahedrally coordinated SiO_4, and tetrahedrally coordinated silicon with carbon substitution for oxygen, called “mixed bonds.” Here we synthesize two preceramic polymers possessing both phenyl substituents as unique organic groups. In one precursor, the phenyl group is directly bonded to silicon, resulting in a SiOC polymer-derived ceramic (PDC) with mixed bonding. In the other precursor, the phenyl group is bonded to the silicon through Si-O-C bridges, which results in a SiOC PDC without mixed bonding. Radial breathing-like mode bands in the Raman spectra reveal that SiOC PDCs contain carbon nanoscrolls with spiral-like rolled-up geometry and open edges at the ends of their structure. Calorimetric measurements of the heat of dissolution in a molten salt solvent show that the SiOC PDCs with mixed bonding have negative enthalpies of formation with respect to crystalline components (silicon carbide, cristobalite, and graphite) and are more thermodynamically stable than those without. The heats of formation from crystalline SiO₂, SiC, and C of SiOC PDCs without mixed bonding are close to zero and depend on the pyrolysis temperature. Solid state MAS NMR confirms the presence or absence of mixed bonding and further shows that, without mixed bonding, terminal hydroxyls are bound to some of the Si-O tetrahedra. This study indicates that mixed bonding, along with additional factors, such as the presence of terminal hydroxyl groups, contributes to the thermodynamic stability of SiOC PDCs.     

Tunnel model for hard-sphere bosons in their ground state

In the tunnel model, a fluid is regarded as being composed of rows of molecules, which move almost in one dimension along lines or tunnels, the walls of which are formed by neighboring rows of molecules. This model provides a simple and reliable theory for a classical system of dense hard spheres. The tunnel model has also been applied to quantum hard spheres. However, until recently, there have been no reliable results for dense quantum hard spheres, so that the accuracy of the quantum tunnel model could not be judged. Comparison with a recent variational determination of the ground-state energy of a system of hard spheres shows that the tunnel model is reliable for this system.     

Protein electrophoretic patterns of bovine and porcine ovarian follicular fluid

Sodium Dodecyl Sulphate polyacrylamide electrophoresis (SDS-PAGE) was used to reveal changes in the protein pattern of porcine and bovine ovarian follicular fluid at different maturational stages. Separate pools were made of follicles with a diameter of 1-2, 3-4, 5-6, 7-8, 9-10 and greater than 11 mm excluding hemorrhagic and cystic follicles. Prior to electrophoresis, estradiol-17 beta and androstenedione were analyzed to define the atresic or healthy state of the follicular. Glucose and total protein content of follicles fluid were determined to assess follicular metabolism. Densitometric analysis of both pig and cow follicular fluids from 3-4 mm follicles revealed a distinct band which was absent in other follicle sizes. On the other hand the protein pattern of follicular fluid of cow and pig showed differences in zones of molecular weight higher than 150,000 and lower than 30,000 dalton. This study suggests the possible existence of a common protein to both species which determines the follicle destiny towards ovulation or atresia.     

Concentration and relative distribution of low-density lipoprotein subfractions in patients with metabolic syndrome defined according to the National Cholesterol Education Program criteria

It has been proposed that the most common lipid abnormalities associated with the metabolic syndrome are elevated triglyceride and low high-density lipoprotein concentrations as well as the existence of small, dense low-density lipoprotein (LDL) particles. However, so far there are only limited clinical data concerning the distribution of LDL particles in patients with this syndrome. The aim of our study was to directly determine the concentration and relative distribution of LDL subfractions in patients with metabolic syndrome. One hundred seventy-five individuals were included. Patients with metabolic syndrome (n = 105) exhibited higher concentrations of dense LDL particles and lower mean LDL particle size than the control population (n = 70). Both of these parameters were significantly correlated with the number of components of metabolic syndrome. Multivariate analysis revealed that serum triglyceride concentration was the most important determinant of the presence of small, dense LDL particles. In conclusion, patients with metabolic syndrome exhibit higher concentrations of small, dense LDL subfractions than individuals who do not fulfill the criteria for the diagnosis of this syndrome. This increase is directly related to the number of components of metabolic syndrome and is mainly determined by the serum concentrations of triglycerides.     

Monitoring Carbon in Electron and Ion Beam Deposition within FIB-SEM

It is well known that carbon present in scanning electron microscopes (SEM), Focused ion beam (FIB) systems and FIB-SEMs, causes imaging artefacts and influences the quality of TEM lamellae or structures fabricated in FIB-SEMs. The severity of such effects depends not only on the quantity of carbon present but also on its bonding state. Despite this, the presence of carbon and its bonding state is not regularly monitored in FIB-SEMs. Here we demonstrated that Secondary Electron Hyperspectral Imaging (SEHI) can be implemented in different FIB-SEMs (ThermoFisher Helios G4-CXe PFIB and Helios Nanolab G3 UC) and used to observe carbon built up/removal and bonding changes resulting from electron/ion beam exposure. As well as the ability to monitor, this study also showed the capability of Plasma FIB Xe exposure to remove carbon contamination from the surface of a Ti6246 alloy without the requirement of chemical surface treatments.     

Experimental and Numerical Investigations of Cement Bonding Properties at Elevated Temperatures—The Effect of Sample Cooling

Well integrity is currently defined through the concept of well barriers, in which one or more barriers are used to prevent unwanted fluid flow. Many papers have highlighted that the casing–cement interfacial bonding is critical for well integrity, but many discrepancies between laboratory experiments and field data have been noticed. The use of finite element analysis is now established as an alternative to complex in situ tests, but these simulations are sensitive to the input parameters, which results in many discrepancies across published works. Currently, the cohesive zone material (CZM) method is considered to offer good results if the correct parameters are selected or experimentally determined. The novelty of this paper lies in the development of a better workflow that enables the simulation of three processes that are acting on the laboratory-scale casing–cement system: temperature changes, debonding, and post-debonding behavior. The aim of this paper is to fully understand the debonding process within laboratory-scale samples, and thus to eventually enable upscaling in the near future. The paper presents a new workflow generated using FEM that allows us to determine the contact stresses at the casing–cement interface during temperature changes at the moment of debonding and post-debonding. The results presented within this paper show that temperature samples tested according to the push-down setup will provide similar interfacial bonding shear strength values; however, post-debonding, there is a remaining frictional force slightly higher than that of the room-temperature samples. In this case, the results are within a 5% error of the average field data, which is slightly higher than in our previous experiments, where only room temperature data were considered. A major outcome of our paper is the demonstration of the existence of friction forces after debonding, which are a result of radial stresses induced during the debonding process.     

A Unique Synaptosomal Fraction, Which Accumulates Glutamic and Aspartic Acids, in Brain Tissue

Subcellular fractionation of rat cerebral cortical slices on sucrose density gradients provides evidence for the existence of a unique synaptosomal fraction (enriched in pinched-off nerve endings) that selectively accumulates glutamic and aspartic acids. The particles in this fraction sediment to a less dense portion of sucrose gradients than do particles that accumulate aromatic, basic, and neutral (large and small) amino acids. Particles that store gamma-aminobutyric acid are even less dense than those that contain exogenous glutamic and aspartic acids. The distribution of endogenous glutamic acid encompasses both that of exogenous glutamic acid and that of the neutral and basic amino acids. These findings provide neurochemical support for the suggestion that glutamic and/or aspartic acid has a specialized synaptic function, perhaps as a neurotransmitter, in the mammalian brain.     

Cross-reactivity and conformational multiplicity of an anti-polycyclic aromatic hydrocarbon mAb

Cross-reactivity and multispecific functionality of antibodies play a central role in the immune system. The Ab's promiscuity is attributed to structural flexibility and conformational multiplicity of its binding sites governed by the rearrangement of hydrogen bonding centers. However, antibodies whose recognition and binding rely on less directional hydrophobic interactions might follow different interaction pathways. We investigated interaction of anti-polycyclic aromatic hydrocarbon mAb with two biologically important cross-reactants, pyrene and benzo(a)pyrene. Complex formation was characterized by means of low-temperature laser-induced fluorescence spectroscopy in both low- and high-resolution fluorescence line-narrowing (FLN) modes. It is shown that the FLN spectroscopy can identify various haptens cross-reacted with an Ab, as well as simultaneously differentiate between free and immunocomplexed haptens. In addition, our results suggest an interesting case of an Ab binding a particular cross-reactant by adopting two distinct conformations of its binding sites. The existence of the multiple conformations for anti-polycyclic aromatic hydrocarbon mAb that are trapped at low temperature can be rationalized through the existing models for Ab binding. Finally, as revealed by FLN spectra of immunocomplexed chromophores, pi-pi interactions, rather than hydrogen bonding, play the central role in complex formation.     

The ultrastructure of the Schistosoma mansoni egg

Helminth eggs have resisted analysis by electron microscopy because fixatives, dehydrating agents, and embedding media penetrate these eggs poorly. Slam-freezing at liquid nitrogen temperature followed by freeze-substitution and Spurr's medium embedment provides preservation of the internal structure of the Schistosoma mansoni egg shell, developing miracidium, and perimiracidial structures. The egg shell consists of the three previously described layers (outer microspinous, middle intermediately dense, and inner dense layers) with cribriform pores. A newly described layer (Reynolds' layer) develops subjacent the egg shell and is comprised of densely-packed branching filaments. A single layer of squamous cells (von Lichtenberg's envelope) closely adheres to Reynolds' layer. Between von Lichtenberg's envelope and the embryo is a space (Lehman's lacuna); this space is initially filled with electron-lucent fluid, but subsequently masses of granulofloccular material (Cheever bodies) develop; Cheever bodies are partially membrane bound. Epidermal plates differentiate from superficial cells of the embryonal cell mass, while epidermal ridges differentiate from cells just below the surface of the embryonal cell mass. The cytoplasmic layer (von Lichtenberg's envelope) interposed between the host extracellular fluid and the developing miracidia effect a barrier against a simple passive diffusion; this infers that complex macromolecules, such as schistosomal egg antigen, undergo active, and perhaps selective, transport in or out of the egg.