Adsorption of Pb(II) and Cu(II) on α-quartz from aqueous solutions: influence of pH, ionic strength, and complexing ligands

Adsorption of aqueous Pb(II) and Cu(II) on α-quartz was studied as a function of time, system surface area, and chemical speciation. Experimental systems contained sodium as a major cation, hydroxide, carbonate, and chloride as major anions, and covered the pH range 4 to 8. In some cases citrate and EDTA were added as representative organic complexing agents. The adsorption equilibria were reached quickly, regardless of the system surface area. The positions of the adsorption equilibria were found to be strongly dependent on pH, ionic strength and concentration of citrate and EDTA. The addition of these non-adsorbing ligands resulted in a competition between chelation and adsorption. The experimental work also included the examination of the adsorption behavior of the doubly charged major cations Ca(II) and Mg(II) as a function of pH.

The theoretical description of the experimental systems was obtained by means of chemical equilibrium-plus-adsorption computations using two adsorption models: one mainly electrostatic (the James-Healy Model), and the other mainly chemical (the Ion Exchange-Surface Complex Formation Model). Comparisons were made between these two models.

The main difficulty in the theoretical predictions of the adsorption behavior of Cu(II) was the lack of the reliable data for the second hydrolysis constant(*β_2) The choice of the constant was made on the basis of potentiometric titratlons of Cu^(2+)

The experimental data obtained and the resulting theoretical observations were applied in models of the chemical behavior of trace metals in fresh oxic waters, with emphasis on Pb(II) and Cu(II).

I. The effects of variations in certain parameters upon the efficiency of in vivo hemodialysis with a Kiil dialyzer. II. Interfacial structure of concurrent air-water flow in a two-inch diameter horizontal tube.

Part I

Regression analyses are performed on in vivo hemodialysis data for the transfer of creatinine, urea, uric acid and inorganic phosphate to determine the effects of variations in certain parameters on the efficiency of dialysis with a Kiil dialyzer. In calculating the mass transfer rates across the membrane, the effects of cell-plasma mass transfer kinetics are considered. The concept of the effective permeability coefficient for the red cell membrane is introduced to account for these effects. A discussion of the consequences of neglecting cell-plasma kinetics, as has been done to date in the literature, is presented.

A physical model for the Kiil dialyzer is presented in order to calculate the available membrane area for mass transfer, the linear blood and dialysate velocities, and other variables. The equations used to determine the independent variables of the regression analyses are presented. The potential dependent variables in the analyses are discussed.

Regression analyses were carried out considering overall mass-transfer coefficients, dialysances, relative dialysances, and relative permeabilities for each substance as the dependent variables. The independent variables were linear blood velocity, linear dialysate velocity, the pressure difference across the membrane, the elapsed time of dialysis, the blood hematocrit, and the arterial plasma concentrations of each substance transferred. The resulting correlations are tabulated, presented graphically, and discussed. The implications of these correlations are discussed from the viewpoint of a research investigator and from the viewpoint of patient treatment.

Recommendations for further experimental work are presented.

Part II

The interfacial structure of concurrent air-water flow in a two-inch diameter horizontal tube in the wavy flow regime has been measured using resistance wave gages. The median water depth, r.m.s. wave height, wave frequency, extrema frequency, and wave velocity have been measured as functions of air and water flow rates. Reynolds numbers, Froude numbers, Weber numbers, and bulk velocities for each phase may be calculated from these measurements. No theory for wave formation and propagation available in the literature was sufficient to describe these results.

The water surface level distribution generally is not adequately represented as a stationary Gaussian process. Five types of deviation from the Gaussian process function were noted in this work. The presence of the tube walls and the relatively large interfacial shear stresses precludes the use of simple statistical analyses to describe the interfacial structure. A detailed study of the behavior of individual fluid elements near the interface may be necessary to describe adequately wavy two-phase flow in systems similar to the one used in this work.

Study of the effect of alcohol on single human red blood cells using near-infrared laser tweezers Raman spectroscopy

The effect of alcohol solution on single human red blood Cells (RBCs) was investigated using near-infrared laser tweezers Raman spectroscopy (LTRS). In our system, a low-power diode laser at 785 nm was applied for the trapping of a living cell and the excitation of its Raman spectrum. Such a design could simultaneously reduce the photo-damage to the cell and suppress the interference from the fluorescence on the Raman signal. The denaturation process of single RBCs in 20% alcohol solution was investigated by detecting the time evolution of the Raman spectra at the single-cell level. The vitality of RBCs was characterized by the Raman band at 752 cm(-1), which corresponds to the porphyrin breathing mode. We found that the intensity of this band decreased by 34.1% over a period of 25 min after the administration of alcohol. In a further study of the dependence of denaturation on alcohol concentration, we discovered that the decrease in the intensity of the 752 cm(-1) band became more rapid and more prominent as the alcohol concentration increased. The present LTRS technique may have several potential applications in cell biology and medicine, including probing dynamic cellular processes at the single cell level and diagnosing cell disorders in real time. Copyright (c) 2005 John Wiley T Sons, Ltd.

Simulation of shock-induced bubble collapse with application to vascular injury in shockwave lithotripsy

Shockwave lithotripsy is a noninvasive medical procedure wherein shockwaves are repeatedly focused at the location of kidney stones in order to pulverize them. Stone comminution is thought to be the product of two mechanisms: the propagation of stress waves within the stone and cavitation erosion. However, the latter mechanism has also been implicated in vascular injury. In the present work, shock-induced bubble collapse is studied in order to understand the role that it might play in inducing vascular injury. A high-order accurate, shock- and interface-capturing numerical scheme is developed to simulate the three-dimensional collapse of the bubble in both the free-field and inside a vessel phantom. The primary contributions of the numerical study are the characterization of the shock-bubble and shock-bubble-vessel interactions across a large parameter space that includes clinical shockwave lithotripsy pressure amplitudes, problem geometry and tissue viscoelasticity, and the subsequent correlation of these interactions to vascular injury. Specifically, measurements of the vessel wall pressures and displacements, as well as the finite strains in the fluid surrounding the bubble, are utilized with available experiments in tissue to evaluate damage potential. Estimates are made of the smallest injurious bubbles in the microvasculature during both the collapse and jetting phases of the bubble's life cycle. The present results suggest that bubbles larger than 1 μm in diameter could rupture blood vessels under clinical SWL conditions.

MEMS for Diabetic Retinopathy

As the worldwide prevalence of diabetes mellitus continues to increase, diabetic retinopathy remains the leading cause of visual impairment and blindness in many developed countries. Between 32 to 40 percent of about 246 million people with diabetes develop diabetic retinopathy. Approximately 4.1 million American adults 40 years and older are affected by diabetic retinopathy. This glucose-induced microvascular disease progressively damages the tiny blood vessels that nourish the retina, the light-sensitive tissue at the back of the eye, leading to retinal ischemia (i.e., inadequate blood flow), retinal hypoxia (i.e., oxygen deprivation), and retinal nerve cell degeneration or death. It is a most serious sight-threatening complication of diabetes, resulting in significant irreversible vision loss, and even total blindness.

Unfortunately, although current treatments of diabetic retinopathy (i.e., laser therapy, vitrectomy surgery and anti-VEGF therapy) can reduce vision loss, they only slow down but cannot stop the degradation of the retina. Patients require repeated treatment to protect their sight. The current treatments also have significant drawbacks. Laser therapy is focused on preserving the macula, the area of the retina that is responsible for sharp, clear, central vision, by sacrificing the peripheral retina since there is only limited oxygen supply. Therefore, laser therapy results in a constricted peripheral visual field, reduced color vision, delayed dark adaptation, and weakened night vision. Vitrectomy surgery increases the risk of neovascular glaucoma, another devastating ocular disease, characterized by the proliferation of fibrovascular tissue in the anterior chamber angle. Anti-VEGF agents have potential adverse effects, and currently there is insufficient evidence to recommend their routine use.

In this work, for the first time, a paradigm shift in the treatment of diabetic retinopathy is proposed: providing localized, supplemental oxygen to the ischemic tissue via an implantable MEMS device. The retinal architecture (e.g., thickness, cell densities, layered structure, etc.) of the rabbit eye exposed to ischemic hypoxic injuries was well preserved after targeted oxygen delivery to the hypoxic tissue, showing that the use of an external source of oxygen could improve the retinal oxygenation and prevent the progression of the ischemic cascade.

The proposed MEMS device transports oxygen from an oxygen-rich space to the oxygen-deficient vitreous, the gel-like fluid that fills the inside of the eye, and then to the ischemic retina. This oxygen transport process is purely passive and completely driven by the gradient of oxygen partial pressure (pO₂). Two types of devices were designed. For the first type, the oxygen-rich space is underneath the conjunctiva, a membrane covering the sclera (white part of the eye), beneath the eyelids and highly permeable to oxygen in the atmosphere when the eye is open. Therefore, sub-conjunctival pO₂ is very high during the daytime. For the second type, the oxygen-rich space is inside the device since pure oxygen is needle-injected into the device on a regular basis.

To prevent too fast or too slow permeation of oxygen through the device that is made of parylene and silicone (two widely used biocompatible polymers in medical devices), the material properties of the hybrid parylene/silicone were investigated, including mechanical behaviors, permeation rates, and adhesive forces. Then the thicknesses of parylene and silicone became important design parameters that were fine-tuned to reach the optimal oxygen permeation rate.

The passive MEMS oxygen transporter devices were designed, built, and tested in both bench-top artificial eye models and in-vitro porcine cadaver eyes. The 3D unsteady saccade-induced laminar flow of water inside the eye model was modeled by computational fluid dynamics to study the convective transport of oxygen inside the eye induced by saccade (rapid eye movement). The saccade-enhanced transport effect was also demonstrated experimentally. Acute in-vivo animal experiments were performed in rabbits and dogs to verify the surgical procedure and the device functionality. Various hypotheses were confirmed both experimentally and computationally, suggesting that both the two types of devices are very promising to cure diabetic retinopathy. The chronic implantation of devices in ischemic dog eyes is still underway.

The proposed MEMS oxygen transporter devices can be also applied to treat other ocular and systemic diseases accompanied by retinal ischemia, such as central retinal artery occlusion, carotid artery disease, and some form of glaucoma.

Technology for Single Cell Protein Analysis in Immunology and Cancer Prognostics

The first chapter of this thesis deals with automating data gathering for single cell microfluidic tests. The programs developed saved significant amounts of time with no loss in accuracy. The technology from this chapter was applied to experiments in both Chapters 4 and 5.

The second chapter describes the use of statistical learning to prognose if an anti-angiogenic drug (Bevacizumab) would successfully treat a glioblastoma multiforme tumor. This was conducted by first measuring protein levels from 92 blood samples using the DNA-encoded antibody library platform. This allowed the measure of 35 different proteins per sample, with comparable sensitivity to ELISA. Two statistical learning models were developed in order to predict whether the treatment would succeed. The first, logistic regression, predicted with 85% accuracy and an AUC of 0.901 using a five protein panel. These five proteins were statistically significant predictors and gave insight into the mechanism behind anti-angiogenic success/failure. The second model, an ensemble model of logistic regression, kNN, and random forest, predicted with a slightly higher accuracy of 87%.

The third chapter details the development of a photocleavable conjugate that multiplexed cell surface detection in microfluidic devices. The method successfully detected streptavidin on coated beads with 92% positive predictive rate. Furthermore, chambers with 0, 1, 2, and 3+ beads were statistically distinguishable. The method was then used to detect CD3 on Jurkat T cells, yielding a positive predictive rate of 49% and false positive rate of 0%.

The fourth chapter talks about the use of measuring T cell polyfunctionality in order to predict whether a patient will succeed an adoptive T cells transfer therapy. In 15 patients, we measured 10 proteins from individual T cells (~300 cells per patient). The polyfunctional strength index was calculated, which was then correlated with the patient's progress free survival (PFS) time. 52 other parameters measured in the single cell test were correlated with the PFS. No statistical correlator has been determined, however, and more data is necessary to reach a conclusion.

Finally, the fifth chapter talks about the interactions between T cells and how that affects their protein secretion. It was observed that T cells in direct contact selectively enhance their protein secretion, in some cases by over 5 fold. This occurred for Granzyme B, Perforin, CCL4, TNFa, and IFNg. IL- 10 was shown to decrease slightly upon contact. This phenomenon held true for T cells from all patients tested (n=8). Using single cell data, the theoretical protein secretion frequency was calculated for two cells and then compared to the observed rate of secretion for both two cells not in contact, and two cells in contact. In over 90% of cases, the theoretical protein secretion rate matched that of two cells not in contact.

ph eta kontzentrazioaren eragina, erretxina kelanteen gainean egindako ioi trukaketa prozesuan

Azken urte hauetan industriak izan duen garapenak, onura asko ekarri ditu, hala nola, bizi maila eta kalitatea gora egin dute. Baina dena ez dira alde onak, izan ere, prozesu honek, kutsagarriak eta oso konplexuak diren hondakinak sortu ditu. Kutsadura hau ez du soilik oreka ekologikoa n kalte egiten, izan ere, kutsadura hau dagoen guneetan ere eragin handia dauka. Hori dela eta , ingurumenaren babesa gero eta garrantzi handiagoa hartzen ari da. Horretarako, industriak sortzen dituen hondakinen tratamendurako prozesuetan, inbertsio ekonomiko handiak egin behar dira. Hau ez da soilik legea betetzeko egin behar, baizik eta, indus tria merkatuan dagoen konpetentzian toki on bat lortzeko oso garrantzitsua da. Jariakinen tratamenduaren xedea dituzten araztegiak duten arazo printzipala, jariakin hauetan dauden metal astunen presentzia da. Metal hauek, araztegi hauetan ematen diren pro zesu biologikoen zai ltasuna bermatzen dute eta animali, landare eta giza osasunean efektu toxikoak izaten dituzte. Baimenduta dauden kontzentrazioen limitea betetzeko, industriak normalean isurketan egin baino lehen, aurretratamendu bat egitera behartuta ikusten dira, toxikoak diren edo oso oldarkorrak diren produktuak kentzeko. Adibidez, Industria Hidrometalurgiakoak , oso kontzentrazio baxuetan metal astunak isurtzen ditu, baina kantitate hauek baimenduta daude, industria hau erabiltzen dituen emari handiak direla eta. Normalean hondakin industrialetatik kanpora isurt zen diren metal astunak , kontzentrazio baxuetan eg ot en dira . Honek, errentagarritasun positiboa du ten araztegi tekniken aplikazioa ahalbideratzen du. Kutsadura hau sortzen dituzten prozesu industrial mota asko existitzen direnez, metal hauek, oso diluituak dauden disoluzioetatik banatu behar dira. Horretara ko, metal baliotsuen errekuperazioa eta isurketa industrialaren legeak betetzea bermatzen duten, banaketa prozesuak sortu behar izan d ira. Jarraian, helburu hau duten teknika batzuk azaltzen dira

Hypoxic and low pH water in the nearshore marine environments of Monterey Bay, California: characterizing a decade of oxygen and pH, and drivers of variability.

A decade-long time series recorded in southern Monterey Bay, California demonstrates that the shallow, near-shore environment (17 m depth) is regularly inundated with pulses of cold, hypoxic and low pH water. During these episodes, oxygen can drop to biologically threatening levels, and pH levels were lower than expected. Weekly water chemistry monitoring revealed that the saturation state of aragonite (the more soluble form of calcium carbonate) was often below saturation and had a moderate positive relationship with pH, however, analytical and human error could be high. Pulses of hypoxia and low pH water with the greatest intensity arise at the onset of the spring upwelling season, and fluctuations are strongly semidurnal (tidal) and diurnal. Arrival of cold, hypoxic water on the inner shelf typically occurs 3 days after the arrival of a strong upwelling event and appears to be driven by upwelling modulated by internal tidal fluctuations. I found no relationship between the timing of low-oxygen events and the diel solar cycle nor with terrestrial nutrient input. These observations are consistent with advection of hypoxic water from the deep, offshore environment where water masses experience a general decline of temperature, oxygen and pH with depth, and inconsistent with biochemical forcing. Comparisons with concurrent temperature and oxygen time series taken ~20 km away at the head of the Monterey Canyon show similar patterns but even more intense hypoxic events due to stronger semidiurnal forcing there. Analysis of the durations of exposure to low oxygen levels establishes a framework for assessing the ecological relevance of these events. Increasing oceanic hypoxia and acidification of both surface and deep waters may increase the number, intensity, duration and spatial extent of future intrusions along the Pacific coast. Evaluation of the resiliency of nearshore ecosystems such as kelp forests, rocky reefs and sandy habitats, will require consideration of these events.

A behavior model for blood donors and marketing strategies to retain and attract them

Objective: analyze and propose a theoretical model that describes blood donor decisions to help staff working in blood banks (nurses and others) in their efforts to capture and retain donors. Methods: analysis of several studies on the motivations to give blood in Spain over the last six years, as well as past literature on the topic, the authors' experiences in the last 25 years in over 15 Non Governmental Organizations with different levels of responsibilities, their experiences as blood donors and the informal interviews developed during those 25 years. Results: a model is proposed with different internal and external factors that influence blood donation, as well as the different stages of the decision-making process. Conclusion: the knowledge of the donation process permits the development of marketing strategies that help to increase donors and donations.