Inverse mass ratio batteries: An in situ energy source generated from motive proton delivery gradients

Inverse mass ratio batteries: An in situ energy source generated from motive proton delivery gradients

Nano Energy (2012) 1, 309–315 Available online at www.sciencedirect.com journal homepage: www.elsevier.com/locate/nanoenergy RAPID COMMUNICATION I...

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Nano Energy (2012) 1, 309–315

Available online at www.sciencedirect.com

journal homepage: www.elsevier.com/locate/nanoenergy

RAPID COMMUNICATION

Inverse mass ratio batteries: An in situ energy source generated from motive proton delivery gradients Wayne K. Auge IIn Department of Research and Development, NuOrtho Surgical, Inc. at the Advanced Technology & Manufacturing Center, University of Massachusetts Dartmouth, 151 Martine Street, Fall River, MA 02723, USA Received 27 October 2011; received in revised form 20 December 2011; accepted 22 December 2011 Available online 8 January 2012

KEYWORDS

Abstract

Engineered irrigants; Charge movement; AC redox magnetohydrodynamics; Battery

Nanometer level surgical work requires novel energy sources to extend the therapeutic potential of medical devices. Inverse mass ratio batteries are an advance in energy production that deploy an ‘‘irrigant within water’’ designed from the scientific discipline of Engineered Irrigants. This report discusses the derivation of inverse mass ratio batteries from alternating current redox magnetohydrodynamics as developed to power the physiochemical scalpel; a tissue rescue energy-based device system for wound healing that enables precision resection, advantageous extracellular matrix modifications, and initiation of biosynthetic tissue assembly. & 2012 Elsevier Ltd. All rights reserved.

Introduction The development of novel energy sources designed to power nanometer level surgical work constitutes a vibrant investigative area in medical therapeutics. One such energy source that has fostered significant therapeutic advances is the inverse mass ratio battery [1–3] used to accomplish various tissue rescue treatments, which include precision resection; microfluidic mixing, stirring, and pumping; facilitative colloidal crystal, hydro- and sol–gel self-assembly; electrolyzable interfacing agent modification; charged species injection and migration; electromagnetic induction coupling; electro-wetting, -formation, and -swelling; n

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micelle and coascervate formation; pharmaceutical agent delivery; electromagnetic phoresis; extracellular matrix modification; and biosynthetic transcription initiation. These advances have been applied to tissue surface based medical conditions for wound healing because of well established endoscopic access procedures that utilize saline solutions comparable to that within which biologic tissue resides [2]. The inverse mass ratio battery is an energy source generated in situ during treatment by inducing charged specie separation in saline solutions through an energy conversion process patterned after common biologic electron transport chain mechanisms that form proton gradients. Using the water molecule as an energy transducer, the technique involves positioning localized alternating current circuits in saline solutions containing electroactive species to move electrons between device electrodes utilizing electron donor and acceptor carriers within the host fluid to liberate stored

W.K. Auge II

310 intermolecular bond energy [1–3]. This electron transport produces fuel cell like reversible redox reaction pairs associated with charged specie intermediaries formed above baseline solution dissociation rates upon which the attendant alternating current non-ionizing electromagnetic field quanta influence the reaction dynamics. These influences include charged fluid acceleration that create magnetohydrodynamic propulsive thrust currents. Although originally used to propel the originating source, by changing the observational reference frame, the thrust currents are adapted for medical therapeutics as irrigants. These ‘‘irrigants within water’’ are comprised of regional structure altered molecular water [3] exhibiting differential charged specie separation that results in a sequestered energy source contained within the irrigant that is useful for surgical work. The energy conversion process from electron transport to charged specie separation within the attendant non-ionizing electromagnetic environment is governed by the charge-tomass ratio (Q/m) profile of saline solution constituents whereby those species with the highest Q/m generally travel furthest in host media. The inverse mass ratio battery is a unique subset of Engineered Irrigants in that it is generated by a proton gradient formed in saline solutions, which predominantly contain charge equivalent monovalent anions and cations. For instance, sodium (or potassium) chloride solutions contain predominantly Cl, OH, Na + (or K + ), H + , and H3O + for which the charge magnitude of the Q/m ratio is eliminated during differential charge specie separation analyses of alternating current redox magnetohydrodynamic phenomena [3]. This elimination enables the design formulation of irrigant differential charge specie movement to be based upon mass only, a feature that led to these energy sources being designated as inverse mass ratio batteries. The physiochemical scalpel [4] functions as an alternating current redox magnetohydrodynamic proton pump form of energy sequestration that maintains regional proton gradients within saline solutions ambient to biologic tissues (Figs. 1 and

2). Because the intermolecular hydrogen bond stretching frequencies of water demonstrate a proton based femto- to pico-second oscillation period [5], electron movements associated with alternating current polarity changes are less rapid so that water protons in the irrigant experience direct current forces (1012–15 Hz oscillation rate versus 105–6 Hz circuit frequencies) during device activation. Accordingly, irrigant batteries generated through motive proton delivery gradients can be reduced to a direct current energy storage model capable of direct current discharge during contact with a specific therapeutic target [2]. The purpose of this report is to present the derivation outline of inverse mass ratio batteries as designed for the physiochemical scalpel.

Theory and calculation Alternating current redox magnetohydrodynamics Alternating current electron movement produces a repetitive molecular energy conversion loop fuel cell in saline solutions involving salt bridge catalyzed splitting and reconstitution of the water molecule [1]. The thermochemical redox reaction pair can be represented as energy

aH2 OðlÞ þ bXCL 2 ðabÞH2ðgÞ þ

ðabÞ O2ðgÞ þbHClðaqÞ þ bXOHðaqÞ 2

ð1Þ ðgdÞH2ðgÞ þ

ðgdÞ energy O2ðgÞ þdHClðaqÞ þ dXOHðaqÞ 2 gH2 OðlÞ þdXClðsÞ þD 2

ð2Þ with the variables a, b, g, and d as the molar quantities that satisfy the oxidation reduction requirements for the overall reaction set and D as the available heat and/or electrical energy. Attendant non-ionizing electromagnetic field quanta influence this redox reaction pair to move reactant and product charged species formed above baseline solution dissociation

Figure 1 Medical device alternating current redox magnetohydrodynamic proton pump producing an ‘‘irrigant within water’’. Note that the electrodes are comprised of stainless steel containing a small amount of titanium to prevent grain boundary carbide precipitation and corrosion in order to minimize electrode chemistry effects. The device plenum serves to inhibit electrode-to-tissue contact and form a partially constrained primary reaction zone protected from the convective and fluid flow forces of the surgical environment. Digitized videography of a physiochemical scalpel (Engineered IrrigantsTM and Ceruleaus; NuOrtho Surgical, Inc.; Fall River, MA). Reproduced with permission from McRury et al. [1].

Inverse mass ratio batteries

311 the intermolecular hydrogen bond stretching frequencies of water allow system treatment as a direct current model. As such, the low magnetic field curl component ðv  BÞ in this system,1 which is principally orthogonal to the electromotive force, can be condensed [6–8] so that charged specie movement is reduced to a single dimension model after Auge and McRury [3], which describes the therapeutically preferred domination reaction in this therapeutic application. By equating charged species acceleration and distance traveled QE m

ð6Þ

d ¼ at2

ð7Þ





QE 2 t m

ð8Þ

the relative scale travel distance between two different charged species, x and y, can be depicted as dx ðQx Et2 Þ=mx ¼ dy ðQy Et2 Þ=my

ð9Þ

Since Q, E, and t are the same for x and y as charge equivalent monovalent species, during reactions (1) and (2), relative scale travel distances can be represented as the inverse mass ratio defined as Figure 2 Representative Poynting vector illustration demonstrating field-force summations. Magnetohydrodynamic propagation forces N are applied to working fluids that enters the device plenum at point E so that charged specie and host fluid carrier momentum thrusts in the exit direction of the plenum opening face. The vector field lines N0 depict overall trajectories due to charge density variances between the electrode edge versus its face. Note that the angular momenta and associated torque force densities about the propagation axis are not shown. The plenum opening egress/ingress dimension area ratio as depicted is 2.16.

rates away from the device electrodes and directionalized by a plenum. Without reconciling reference frame transformations, when charged species move in electric and magnetic fields, the Lorentz force can be equated into inertial terms as follows F ¼ Q ðE þ v  BÞ F ¼ ma ¼ m

dv dt

  m a ¼ E þv  B Q

ð3Þ ð4Þ

ð5Þ

where F is the force applied, E is the electric field, B is the magnetic field, t is time, and v, m, a, and Q are the velocity, mass, acceleration, and charge of the species, respectively.

Inverse mass ratio and relative scale travel distances On examining the molecular dynamics of an irrigant proton transport gradient that results in energy sequestration,

dx my ¼ : dy mx

ð10Þ

Table 1 presents inverse mass ratios of predominant charged species in a sodium chloride solution reflecting the formation of a proton gradient based upon differential charged species movement.

Electrochemical potential As regional proton concentration differentials increase above normal solution dissociation rates due to the magnetohydrodynamic pumping mechanism, including refreshing the primary reaction zone from bulk solution, an electrochemical gradient develops from the resultant charge separation. In settings like this wherein protons are available for movement, pH is a useful in situ measure of electrochemical potential as it can be monitored by practitioners in order to titrate effect during treatment. Accordingly, Fig. 3 depicts experimental data of irrigant electrochemical potential versus power delivery as a function of pH and is in agreement with the relative scale travel distances as modeled in Table 1. Because the electrochemical potential is representative of differential 1 Alternating current redox magnetohydrodynamic systems deploy electromagnetism (variable field magnetics) rather than permanent magnetism as utilized in other magnetohydrodynamic system configurations; therefore, the magnetic component can be varied based upon electric current amount, damping, or duty cycle utilized. Depending upon desired energy configurations, the magnetic curl component can be inconsequential to treatment venue as in some proton gradient delivery systems, or in other instances, can induce therapeutic eddy current stirring functions that would require mixed modeling techniques not considered in this report.

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312

Table 1 Inverse mass ratio and relative scale travel distances between predominant charge equivalent monovalent species present in sodium chloride solutions. Relative travel distance is presented as a unitless differential value. Note that evaluation of an x2 + species would require reintroduction of Q. NA is Avogadro’s number. Reproduced with permission from Auge and McRury [3].

the sum of the pH gradient and resultant voltage potential Dp ¼

ð2:303RTDpHÞ þ Dc nF

ð11Þ

and the total Gibbs free energy available from a proton gradient irrigant in an open system is Di G ¼ 2:303RTDpH þ nFDc

ð12Þ 3

Charged species

Inverse mass ratio (Atomic weight per NA)

Relative travel distance

dH dOH

2:83  1026 kg

17.0

1:67  1027 kg 3:82  1026 kg

22.9

dH dNa dH dCl dH dH3 O

27

1:67  10 kg 5:89  1026 kg

35.3

27

1:67  10 kg 3:16  1026 kg 1:67  10

27

18.9

kg

where R is the universal gas constant (8.315  10 kJ/ mol K), T is the absolute temperature (K), n is the number of electrons transferred; F is the Faraday constant (96.48 kJ/ V mol), and c is the voltage gradient or voltage potential. Like biologic energy management systems, the relative contributions between the pH gradient (DpH) and the voltage potential (Dc) for overall DiG is specific for particular Engineered Irrigants. In an illustrative treatment setting that generates an irrigant pH gradient of 0.10 and voltage potential of 0.010 V at a room temperature of 25 1C, the inverse mass ratio battery would yield a free energy change of 0.57 kJ/mol for the maintained pH gradient and 0.97 kJ/mol for the created voltage gradient. Combined, the total 1.54 kJ/mol reflects the D of Eq. (2) for a particular redox reaction pair conversion loop that generates a proton gradient. For a practitioner who titrates the pH gradient from a to b during treatment, DpH is directly proportional to the irrigant DiG being deployed DpHa Di Ga nFDca ¼ DpHb Di Gb nFDcb

ð13Þ

whereas for device system irrigants displaying a primary protonation feature (see below), DpH can be equated to DiG by capacitive balancing Dca and Dcb to that of tissue surface interfacial Dct such that DcaffiDcbffiDct during treatment and DpHa Di Ga ffi DpHb Di Gb

ð14Þ

Discussion Figure 3 Electrochemical potential versus power delivery. R2 =0.311; po0.02. Note that the goodness-of-fit linear regression is better for the segment during which low level nonsoluble gas formation occurs (35–75 W) with increasing scatter as primary reaction zone turbulence increases within the device plenum. R2 values can be varied based upon plenum architectural design. Data from sodium chloride solutions (300 mOsm/L) at 20 1C with alternating current from 5 to 120 W with an 8500 V peak-to-peak setting (4250 peak voltage) and 390 kHz damped sinusoid bursts with a repetition frequency of 30 kHz into 500 ohms. Reproduced with permission from McRury et al. [1].

charged specie separation and directly correlates with power delivery, in situ measures of pH are associated with irrigant energy.

Irrigant battery energy The proton motive force or chemiosmotic potential that is generated by the proton gradient system is represented as

Alternating current redox magnetohydrodynamics is a significant electrosurgery advance for energy-based medical device systems since large generator power is not required and electric current deposition into tissue is avoided; features that eliminate the two most common causes of iatrogenic collateral tissue damage. The method is able to capture, direct, position, and move a fluid constituent(s) to tissue surfaces as a therapeutic agent without extended cumbersome channel structures for guidance. The transport is controlled with redox chemistry, which can be easily titrated, monitored, turned on and off strategically, and flushed away rapidly by the host bulk endoscopic saline solution at the practitioner’s convenience. These therapeutic advances are being applied to such conditions as osteoarthritis that display breaches in tissue surfaceconfined assemblies so as to reduce the disease burden associated with impaired wound healing [9,10]. Attendant non-ionizing electromagnetic field quanta superimposed upon alternating current formed charged species is an energy transfer process analogous to common biologic energy management methods whereby oxidation– reduction electron transport chain reactions enable certain

Inverse mass ratio batteries charge carriers to pump protons. In most biologic systems, the mechanisms for maintaining proton charge separation are physical membranes or boundary coascervates at which DpH and Dc may act independently or jointly depending upon the specific transport mechanisms in operation; characteristics perhaps not more clearly demonstrated by the differences between mitochondria and chloroplast membranes. While Engineered Irrigants use magnetohydrodynamics to maintain charge separation, differences in relative contribution from DpH and Dc to overall DiG can be likewise design formulated for specific indications. A significant advantage of the inverse mass ratio battery resides in a simplified proton pumping stoichiometry. Charge equivalent monovalent species uniquely relate to the Nernst n in Eqs. (11)–(13) so that the number of protons compared to the number of positive charges moved per electron transported (i.e. monovalent Goldman–Hodgkin–Katz treatment) during the alternating current half cycle more directly correlates with the in situ pH changes that are useful to monitor during treatment [11,12]. Multivalent species can have a profound effect on the ability to form and discharge a proton gradient; further, these species also effect tissue surfaces, much like their behavior at the electrical double layer that forms on micro- and nanofluidic device surfaces of conventional magnetohydrodynamic applications [13], by altering charge interactions and interfacial energy [2,14]. Normal tissue surfaces demonstrate tribochemical phasestate transition properties akin to this electric double layer [2], being comprised of a biologic exclusion zone proton gradient veneer [15–17] formed adjacent to hydrophilic laterally-bonded biohydrogel phospholipid oligolamellar lamina [18], which manage interstitial matrix wettability and surface charge barriers. Although generated by a different mechanism, the inverse mass ratio battery exhibits similar energy storage features to that of the biologic exclusion zone proton gradient; hence, irrigant proton gradient energy is designed to be of similar magnitude to normal tissue surface interfacial proton gradient energy so that varied capacitance between the two energy sources does not lead to significant discharge of either during treatment. While the interaction dynamics between irrigant and normal tissue interfacial energy sources is complex due to varied charging rates, non-equilibria conditions, cooperative hydrogen bonding, structural proton diffusion, and treatment site fluid dynamics, capacitance balancing is a trait-targeting mechanism that uses normal tissue surface interfacial proton gradients to direct irrigant proton gradients to damaged tissue areas. These damaged surfaces are devoid of hydrophilic biohydrogel layers because of increased roughness, aberrant contact angle hysteresis, and decreased wettability2; consequently, the biologic exclusion 2 Often characterized as fibrillation due to its collagen content, exposed damaged interstitial matrices serve as an impediment to reestablishing surface barrier mechanisms because the roughened surface distorts adhesive and friction forces thereby creating altered hydrophobic matrix configurations (which itself can further discharge interfacial energy of adjacent normal surface-confined assemblies during treatment). This matrix failure leads to altered wettability that creates biohydrogel phase boundary motion described by widely aberrant contact angle hysteresis. At such

313 zone proton gradient veneer cannot form appropriately upon the exposed hydrophobic interstitial matrices [2]. In these locations, the inverse mass ratio battery energy is consumed through the fixed negative charge density of the exposed interstitial matrix as a protonating force effecting electrostatic and hydration energies. Since both the irrigant and interfacial batteries are based upon proton gradients in water that demonstrates fast intermolecular bond oscillation rates, trait-targeting energy has been modeled as a direct current supercircuit represented by instantaneous voltage energy transfers [2]. As designed for the physiochemical scalpel, the inverse mass ratio battery energy capacity is customized to achieve nanometer resection precision through a guest chemical denaturization process below the isoelectric point of exposed damaged interstitial tissue matrices in order to create a healthy lesion site by decreasing roughness and increasing wettability of damaged surfaces to allow restoration of surface-confined assemblies during wound healing that enable more normal tissue-specific responses (Fig. 4). This therapeutic process was adapted from a biologic treatment hint offered by polymorphonuclear neutrophil granulocytes; wherein, their respiratory burst myeloperoxidase system produces low stability protonating agents involved in exothermic tissue homeostasis and repair mechanisms through disproportionation redox reactions [22–25]. Because of high proton motilities in water, stoichiometric protonation3 ðbHn Þ is a very rapid charge redistribution process that leads to biopolymer disaggregation through molecular cleavage planes accessible due to normal tissue surface barrier losses and degenerate matrix properties characteristic of damage tissue sites [4,29]. Previous irrigant proton recruitment and pressure force biophysical design modeling for a commonly deployed 25 W alternating current input demonstrated the movement of 5.3  1011 protons per 1.3 ms half period yielding 2.8 mmHg [3]. This protic solvent pressure force is similar in magnitude to the transcapillary net filtration gradient required to generate normal net capillary filtration [30] and facilitates preferential irrigant access into damaged interstitial matrices at an energy level sufficient to chemically denature diseased collagen–proteoglycan matrices and bring about nanometer level resection precision [4,29] at the (footnote continued) normal-to-damage transitions, the biohydrogel becomes structured as membrane-like coalesced pores due to varied oligolamellar advancing and receding edges that are associated with fluctuating interfacial energy. As a further manifestation of this surfaceconfined assembly dysfunction during treatment, once surface roughness asperity heights, even when controlled for elasticity, surpasses the ability to maintain a fluid film of appropriate thickness, elastohydrodynamic film formation becomes ineffective at mitigating perturbation, leading to functional disturbances in other complementary lubrication regimes designed to modulate tissue-specific perturbation. This disease process is associated with chemomechanotransductive alterations in cellular phenotype that further impair differentiated wound healing. 3 bHn is the cumulative protonation constant for the addition of the nth proton for the formation of HnP from nH + and P, where P is an interstitial matrix protein or polymer complex. The energy transduction processes of protonation coupled conformational dynamics relative to accompanying thermal contributions is a rapidly expanding biotechnology discipline [26–28].

314

W.K. Auge II

Figure 4 Artistic illustration of biologic trait-targeting through capacitive balancing for a geographically contained tissue surface lesion. Typical dimensional estimations [11,15,17–19]: proton gradient charge barrier 0.5–3 mm; biologic water exclusion zone 10–300 mm; biohydrogel 100–450 nm; matrix without cellular structures 4–8 mm; superficial zone 100–200 mm. The lower right insert depicts increased surface asperities associated with damaged tissue against a background of a biohydrogel; the center insert depicts the self-assembly formation mechanism of biohydrogel lamina [18]. Note that electrode-to-tissue distance (i.e. 0.5 mm) maintained by the plenum does not physically encroach upon or deliver alternating current directly to any tissue charge barrier; that the electrode height (i.e. 2.59 mm) allows the molecular energy conversion loop to occur within the region of the biologic water exclusion zone’s generated proton gradient charge barrier acting as a protonating source reaction catalyst when used with electrolyte cations with lower electrode potential than H + ; and that the model applies to any normal-abnormal tissue surface border characterized by widely aberrant contact angle hysteresis edge effect at the transition to a macroscopic rough surface at which the biohydrogel edge is structured much like a membrane pore. Because of these dimensions and structural properties, the physiochemical scalpel can facilitate electrowetting (lowered contact angles) at biohydrogel damage margins [20] and protective electromagnetic induction coupling (with or without resonance tuning to increase battery charging transmission range) [21] at normal biologic water exclusion zone surfaces. The image depicts a static conceptualization of interrelated interfacial surfaceconfined assembly regimes present during treatment conditions, including aspects of complementary elastohydrodynamic film formation and boundary lubrication mechanisms that participate during various transitive perturbation conditions.

wound bed with its periphery protected from the protonation potential by the normal interstitial matrix negative charge density magnitude. Because resection precision guards against volumetric and functional over-resection that can

contribute to disease burden [2,4,9,10,29], the foundation of charged species movement in alternating current redox magnetohydrodynamics [31] remains a basis for tissue rescue procedural development [1,2,4,9,10,29,32,33] supportive of

Inverse mass ratio batteries the preserved subadjacent tissue by increasing cell/matrix enrichment ratios through local extracellular matrix contraction [29] and accessing biosynthetic tissue assembly genomic control mechanisms [32,33].

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Wayne K. Auge II is a Diplomat of The American Board of Orthopaedic Surgery and Fellow of the American Academy of Orthopaedic Surgeons specializing in knee and shoulder care. He obtained his Doctorate of Medicine from Northwestern University Medical School and Bachelor of Science Cum Laude from Loyola University of Chicago focusing upon molecular genetics, chemistry, and philosophy. Dr. Auge is internationally recognized through his research, novel surgical techniques, and medical inventions being used today by many surgeons in many countries. He is currently serving as Chief Clinical Officer for NuOrtho Surgical, Inc. to advance the science of tissue preservation in order to reduce human disease burden.