General introduction 1.1 Introduction

General introduction 1.1 Introduction

Humans have always envisioned swimming like a fish. Throughout history,

having enviously watched the fishes swimming in water and breathing through

their gills, humans have always longed for a device that functions as gills.

In the past century, several underwater swimming and diving equipments

were developed. One of these equipments was an oxygen-supplying device that

supplies oxygen from the atmosphere to an underwater diver through a hose.

This air-pumping hose limits the diver’s area of free movement, and in most

cases, it entangles, thereby resulting in several accidents.

In recent years, scuba-diving equipment bearing tanks of compressed air or

oxygen was developed. This device is referred to as an “aqualung” and is widely

used for recreational purposes since it eliminates the entangling of air pipes and

provides complete freedom of movement. However, after exhaustion of the

compressed air or oxygen in the tanks, the diver must return to the surface.

These previously developed equipments have not attempted and succeeded

in providing any equivalent to fish gills, whereby dissolved oxygen is extracted

from the water and whereby carbon dioxide is disposed of by passing it to the

water. Humans, hence, tried to develop the device that takes up oxygen from

water like a fish gill. The device, which is called “artificial gill”, has been

studied by several researchers, and several artificial gills were developed.

However, these artificial gills have not yet practical, because the oxygen transfer

rate form water is not adequate, and the oxygen partial pressure provided in the

air is too low for human respiration.

In the present thesis, novel artificial gills that efficiently transfer oxygen

from water to air were developed on the basis of methodologies in chemical and

2

Chapter 1

biomedical engineering. These gills enhanced the oxygen transfer from water to

air and provided high oxygen partial pressure in air, which was suitable for

human respiration. This thesis would be a step toward the realization of artificial

gills and the fulfillment of the dream of swimming under water.

3

General introduction

1.2 Conditions for designing an artificial gill

The artificial gill is a device that transfers oxygen from water to underwater

divers. Hence, the artificial gill is designed based on human respiration and

oxygen concentration in seawater. The oxygen consumption rate in humans

determines the required oxygen transfer rate from water to air, and the oxygen

concentration in seawater determines the required flow rate of seawater and the

driving force for oxygen transfer. The conditions for designing the artificial gill

are described in this section.

1.2.1 Supply of oxygen and removal of carbon dioxide

The most important function of an artificial gill is to supply oxygen. The

amounts of oxygen consumption and carbon dioxide production in human

respiration are 250-300 cm3/min and 200 cm3/min, respectively [1,2]. These

values increase more than 10 times during physical exercise. The minimum

required oxygen partial pressure during inspiration is 13.3 kPa; however, for

stable breathing, a pressure greater than 17.3 kPa is desired. It is known that a

very small concentration of carbon dioxide is required during inspiration. Since

the central nervous system is sensitive to carbon dioxide, a carbon dioxide

concentration higher than 0.1% could pose serious problems [1].

4

Chapter 1

1.2.2 Oxygen concentration in seawater

For designing an artificial gill, knowledge regarding the oxygen

concentration in seawater is important because the required flow rate of

seawater and driving force of oxygen uptake vary with a change in the oxygen

concentration (oxygen partial pressure). Seawater contains several gases such as

nitrogen, oxygen, carbon dioxide, etc. As shown in Fig. 1.1, the concentration of

oxygen and carbon dioxide in seawater vary with water depth. Oxygen is

absorbed from the atmosphere and spreads throughout seawater by convection.

In addition, photosynthesis of seaweeds also contributes to the oxygen content in

seawater. Oxygen concentration is constant at approximately 5-6 cm3/m3 (STP)

at a depth of up to 100 m. In the depth zone, oxygen concentration decreases

with increasing water depth because oxygen is consumed during respiration by

sea animals and seaweeds. Carbon dioxide concentration is also constant at 46

cm3/m3 (STP) at a depth of up to 100 m, and it increases with water depth

greater than 100 m [1,3].

Fig. 1.1 Oxygen (a)

(a)

and carbon dioxide (b) con

5

(b)

centrations in seawater


1.3 Previously developed artificial gills

Several artificial gills have been developed by researchers in the field of

chemical engineering and medical science. First, a prototype of the artificial

gills was developed using a gas permeable membrane. Next, novel artificial gills

were developed using an oxygen adsorbent and an oxygen carrier solution.

These artificial gills possess certain characteristics for transporting oxygen from

water to air. The characteristics of these artificial gills are described in this

section.

1.3.1 Membrane-type artificial gill

In one of the earliest studies on artificial gills, Ayres developed artificial

gills using a flat silicone membrane that only permeated gas and not water [4].

The expired air came in contact with water through the membrane, and the

oxygen dissolved in water was transferred to the expired air through the

membrane. This transfer was driven by the oxygen partial pressure difference

between water and expired air. Carbon dioxide was also transferred from expired

air to water, as shown in Fig. 1.2. This type of artificial gill is termed

“membrane-type artificial gill.” Bodell reported a gas permeable apparatus with

coils of capillary tubes made of silicone rubber with a length of 600 m, as shown

in Fig. 1.3; this apparatus could keep a rat alive for 25 h [5,6]. Paganelli et al.

reported artificial gills developed using a porous membrane. At an oxygen

partial pressure of 13.3 kPa in air, the required membrane surface areas were 8

m2 at rest and 80 m2 during exercise [7]. Yang and Cussler [8] developed an

6

Chapter 1

artificial gill using hollow fiber membranes composed of porous polypropylene.

They successfully kept a dog alive by using this artificial gill. Matsuda and

Sakai designed an artificial gill module consisting of a hollow fiber membrane

by computer analysis [9].

Over the years, gas permeability of the membrane has been greatly

improved. Thus, a greater portion of oxygen transfer resistance of the

membrane-type artificial gills is located on the waterside of the laminar film.

Hollow fiber arrangement and module structure were improved by disrupting the

water flow to decrease the laminar film resistance [7-9].

However, the oxygen transfer rate from water to air obtained using either

the hollow fiber arrangement or module structure is not sufficient for human

respiration because of the small driving force involved in oxygen transfer, which

is the oxygen partial pressure difference between water and air. Furthermore, the

oxygen partial pressure provided in air is significantly lower than that in

seawater [7]. Therefore, a large membrane surface area and device volume were

required to apply these models to humans.

Fig. 1.2 Partial pressure profiles of oxygen andcarbon dioxide in membrane-type artificial gills

Fig. 1.3 Artificial gills using capillary tubes composed of silicone rubber [5]

7


1.3.2 Adsorbent-type artificial gill

Bonaventura et al. developed an artificial gill using an oxygen adsorbent,

which was made by immobilizing hemoglobin in porous polyurethane (Fig.

1.4), and they increased the oxygen transfer rate from water to air [10]. The

oxygen adsorbent was termed “hemo-sponge.” Oxygen was adsorbed by the

contact of water with the hemo-sponge and released by changing the pH. It was

possible to supply highly concentrated oxygen with this artificial gill. Shimada

et al. developed the same system using a photo bridge formation matrix and

hemoglobin [11]. Oxygen was released into the air by the oxidation of

hemoglobin. The oxygen adsorbent has a film structure, which results in rapid

oxygen adsorption as compared to that on hemo-sponge. On the other hand, an

artificial gill was developed by circulating nitrogen gas and using an adsorbent

[12-17]. Oxygen was transferred to nitrogen gas through a membrane with large

oxygen partial pressure difference (driving force) and was concentrated using an

adsorbent. However, these artificial gills were not portable because a large and

complicated apparatus was required to dissociate oxygen from the oxygen

adsorbent.

8

Chapter 1

Fig. 1.4 Adsorbent-type artificial gill [10]

Fig. 1.5 Adsorbent-type artificial gill fabricated with a gas permeable membrane and by circulating nitrogen gas [12-17]

9


1.3.3 Oxygen carrier solution type artificial gill

Haramoto et al. developed an artificial gill using two hollow fiber

membrane modules and an oxygen carrier solution [18,19].

Perfluorooctylbromide (PFOB), one of the perfluorocarbons, was used as the

oxygen carrier solution. Oxygen was absorbed from water into the oxygen

carrier solution through one module and released into expired air through the

other module (Fig. 1.6). The oxygen solubility of PFOB is approximately twenty

times larger than that of water. Therefore, the oxygen carrier solution served as

an oxygen storage tank during oxygen shortage in seawater.

Matsuda et al. developed an artificial gill using red blood cell suspension as

a thermoresponsive oxygen carrier solution [20,21]. Fig. 1.7 shows the artificial

gill with the circulation of an RBC suspension. During oxygen uptake from

water to the oxygen carrier solution, the oxygen carrier solution was cooled to

293 K. This enhanced oxygen uptake because the oxygen affinity of red blood

cells was increased due to cooling. During the release of oxygen into the expired

air, the oxygen carrier solution was heated to 310 K. In this case, the oxygen

release was enhanced because the oxygen affinity of red blood cells decreased

with heating.

This artificial gill system significantly enhanced oxygen transfer from water

to air. The oxygen transfer performance of these artificial gills depends on the

oxygen carrier solution. Hence, these artificial gills require a novel oxygen

carrier solution that provides high oxygen carrying performance for an optimal

operating condition.

In this thesis, the novel oxygen carrier solutions were developed, and an

optimal operating condition was determined to transfer oxygen more efficiently.

10

Chapter 1

Fig. 1.6 PFOB circulating type artificial gill [18]

Fig. 1.7 Artificial gill with the circulation of an RBC suspension [20]

11


1.3.4 Clarification of the fish gill mechanism and its application to artificial gill

A fish can exchange gases effectively by the indirect contact of blood with

water in its gills. A comparison of respiration in fishes and humans is shown in

Table 1.1. For example, water contains a small amount of oxygen as compared

to air, and the oxygen diffusion rate in water is smaller than that in air. It would

be useful to elucidate the mechanism of a fish gill for developing an efficient

artificial gill.

Table 1.1 Comparison of respiration in fishes and humans [22] Fishes Humans

Structure of respiratory organs Gill filament Alveoli

Ventilation Single pass Tidal movement Circulation Counter current flow Complex mixed flow

Respiratory medium Water Air Body temperature Variable Constant

O2 pressure of inspired medium 1-200 mmHg 80-100 mmHg CO2 pressure of inspired medium 0-3 mmHg 40-45 mmHg

O2 diffusion rate Low (in water) High (in air) O2 capacity of the medium Low High

Density of the medium High Low

Hazelhoff and Evenhuts [23] reported the importance of water flow

direction in fish gills. Water was made to flow in the same as well as opposite

directions to blood flow in the fish gill. Further, oxygen utilization in water was

obtained by measuring the oxygen concentration at the inlet and outlet of the

fish gill. The utilization in the opposite direction was found to be larger than that

in the same direction. This suggested that water and blood flow are in opposite

directions in fish gills. This countercurrent system is important for effective

12

Chapter 1

oxygen uptake in fish gills.

Mizoguchi et al. [24] observed fish gills with a fiberscope and measured

water flow velocity in the vicinity of the gill filament. The linear velocity of

water in the vicinity of the gill filament was 5 cm/s. The water flow in the

buccal cavity was in one particular direction; however, it was disturbed in the

vicinity of the gill filament. They suggested that the turbulent flow in the

vicinity of the gill filament disrupts the waterside film resistance and enhances

oxygen uptake from water.

Matsuda and Sakai [9,21] evaluated the secondary lamella of fish gills by

computer simulation analysis. They established a secondary lamella model, as

shown in Fig. 1.8. They found that waterside and blood side film resistances

were small because the water and blood paths were remarkably narrow, and the

oxygen transfer across the biological membrane is a rate-determining step for

oxygen transfer through the secondary lamella.

Fig. 1.8 Secondary lamella model established by Matsuda and Sakai [9,21]

13


1.3.5 Controlled Ecological Life Support System with artificial gill

The Controlled Ecological Life Support System (CELSS) has been studied

for its application to space exploration. It is an ecological system in which

several creatures coexist in a closed system such as a space station. An artificial

gill system was used to exchange respiratory gases between the algae cultivation

tank and animal habitation space. As shown in Fig. 1.9, oxygen is produced by

photosynthesis in cultivated algae and is supplied to the animal habitation space

through an artificial gill module. In contrast, the expired carbon dioxide from an

animal is transferred to the algae cultivation tank, and carbon dioxide is used in

photosynthesis by the algae.

Bowman and Thomae [25,26] were successful in sustaining a mouse for 66

days in a closed chamber. Oxygen that was produced due to photosynthesis in

the algae was supplied from the algae cultivation chamber through a gas

permeable membrane. Mastumoto et al. designed a water-water CELSS in order

to culture fish [26-28]. They demonstrated that it was possible to exchange

dissolved oxygen and carbon dioxide between the aqueous phases in algae

cultivation and fish habitation tanks in opposite directions by the contact of

these phases in an artificial gill module.

Fig. 1.9 Schematic of a Controlled Ecological Life Support System (CELSS)

14

Chapter 1

1.4 Relevant study for artificial gill

Several relevant studies provide hints on further improvement of the

artificial gill, such as the study on the blood oxygenator, hollow fiber module,

blood substitute, oxygen carrier complex, gas separation, etc. For example, a

blood oxygentor possesses the ability to enhance oxygen transfer to venous

blood, and a blood substitute can carry oxygen to tissues. These characteristics

are useful for developing a more efficient artificial gill.

1.4.1 Blood oxygenator and hollow fiber module

The blood oxygenator, referred to as “artificial lung,” is a device that

supplies oxygen to venous blood. It replaces the pulmonary function during

cardiac surgical procedures that require cardiopulmonary bypass. In the past,

several cardiac surgeons used a bubble oxygenator [30] and a film oxygenator

[31], which enable direct contact of venous blood with oxygen (Fig. 1.10).

These oxygenators cause significant blood damage because of exposure to

oxygen gas. Hence, a membrane oxygenator, which transfers oxygen to venous

blood through a hollow fiber membrane, is widely used at present because of its

excellent blood compatibility [32-34]. These membrane oxygenators use hollow

fiber membranes, such as porous polypropylene, having high gas permeability

[35-46]. The rate-determining step of oxygen transfer is located at the blood side

boundary layer because the membrane and oxygen gas-side resistances are

negligibly small as compared to the blood side resistance [35,47].

15


Thus, various hollo

resistance. A blood

1.11) [47-56] and fo

was developed to

researchers demons

are perpendicular

[72-77]. Currently,

arrangement. In an

solution, flowing o

oxygen transfer to

blood oxygenator m

artificial gill.
Fig. 1.10 Film and bubble oxygenators [30,31]
w fiber modules were designed to disrupt the blood side

oxygenator for blood flowing into coiled hollow fibers (Fig.

r blood flowing outside the hollow fibers (Fig. 1.12) [57-71]

enhance the oxygen transfer. After several attempts, some

trated that a hollow fiber module in which the hollow fibers

to blood flow exhibit a high gas exchange performance

almost all membrane oxygenators use this hollow fiber

artificial gill, a fluid, such as seawater or oxygen carrier

utside and perpendicular to the hollow fibers may enhance

or from the outer hollow fibers. The theory of designing a

ay be useful to optimize the hollow fiber arrangement in the

16

Chapter 1

Fig. 1.11 Blood oxygenator for blood flowing into coiled hollow fibers [49]

Fig. 1.12 Blood oxygenator for blood flowing outside hollow fibers [47]

On the other hand, the hollow fiber modules for other purposes, such as

absorption, separation, and pervaporation, have been extensively studied for

their high mass transfer performance and low cost [79-86]. These modules were

designed to enhance mass transfer and reduce the operating energy. The

methodology of designing such modules would also be useful to design the gas

exchange module in the artificial gill.

17


1.4.2 Blood substitute

Several researchers have extensively studied the blood substitutes, such as

the artificial red cell (hemoglobin vesicles) [87-99], modified hemoglobin

[100,101], recombinant hemoglobin [102-104], and perfluorocarbon emulsions

[105-112] (Fig. 1.13). They were developed to transfuse blood to a patient

during the lack of availability of donated blood. Hence, these blood substitutes

are capable of transporting sufficient oxygen to peripheral tissues. The

methodology for developing these oxygen carriers would be helpful to develop a

more efficient artificial gill.

Blood substitutes are broadly divided into two categories: one is a

hemoglobin-based oxygen carrier, such as encapsulated hemoglobin, and the

other is a chemical substance that has high oxygen solubility, such as a

perfluorocarbon (PFC).

Among the hemoglobin-based oxygen carriers, the hemoglobin vesicles

(encapsulated hemoglobin) have been extensively studied because of their

excellent biocompatibility. Furthermore, the oxygen affinity of hemoglobin is

adequately regulated and methemoglobin formation is restrained because both

allosteric effectors and enzymatic methemoglobin reduction systems are

included in the vesicles. The excessive oxygen affinity and short lifetime are

issues that require consideration to improve the efficiency of an artificial gill

fabricated using RBCs. The methodology for preparing hemoglobin vesicles

would be helpful for developing a new oxygen carrier solution.

18

Chapter 1

19

Hemoglobin vesicle

Modifiedhemoglobin

Fig. 1.13 Blood

On the other hand, PFCs have at

oxygen-dissolving capacity after Clark

breathe in PFCs, as shown in Fig. 1.1

compounds that are chemically and biolo

in oxygen and other respiratory gases [1

the emulsified PFC as a blood substitute

have several advantages such as low cos

no risk of infection. However, the oxy

compared to other blood substitutes suc

Fig. 1.15.

PFCemulsion

Recombinant hemoglobin

substitutes [87,102]

tracted considerable attention for their

and Gollan demonstrated that mice can

4. PFCs are highly fluorinated organic

gically inert and display high solubility

06]. Several researchers have developed

because it is immiscible in water. They

t of production, long shelf stability, and

gen transport capacity is inadequate as

h as hemoglobin vesicles, as shown in


Fig. 1.14 Liquid ventilation in oxygen-saturated perfluorocarbon [106]

Fig. 1.15 Oxyhemoglobin dissociation curve of RBC and PFC [110]

In the previously developed artificial gill using an oxygen carrier solution,

perfluorooctylbromide (PFOB), which is one of the PFCs, was used as an

oxygen carrier solution. It showed a high oxygen uptake rate from water and a

very low oxygen release rate into expired air. However, the details of its oxygen

transfer characteristics were not revealed in this attempt because the low oxygen

permeability of the hollow fiber membranes, which was used in this artificial

gill, significantly decreased the oxygen release into air. Thus, the PFCs have the

potential to become efficient oxygen carrier solutions for the artificial gill.

1.4.3 Oxygen carriers for gas separation membrane

The separation of gaseous mixtures is a major operation in the chemical

industry with the separation of oxygen or nitrogen being one of the main

applications [112], such as combustion of natural gas, coal gasfication, and

production of peroxide. Over the years, a gas separation process using gas

separation membranes, such as selective permeability membrane [113], liquid

membrane [114-116], and carrier-fixed membrane [117-118] (Fig.1.16), for the

20

Chapter 1

production of oxygen-enriched air has been developed. In particular, a solid

membrane process using the concept of facilitated transport mediated with a

fixed carrier has been considered to be an energy-saving process. Novel artificial

oxygen carriers have been synthesized with the development of several

oxygen-enriching membranes.

First, a membrane that contains cobalt Schiff base complexes as oxygen

carriers had been developed [117-121]. Cobalt Schiff base oxygen carrier is the

oldest and simplest example of oxygen-carrying chelates [122-128] (Fig. 1.17)

that have been used as oxygen absorbents [12-17]. Tsuchida and Nishide

demonstrated that a CoSalen (CoS)-fixed membrane (Fig. 1.18) (CoS is one of

the cobalt Schiff base oxygen carriers) shows oxygen enriching characteristics

[12-131]. At an oxygen partial pressure of 10 mmHg in upstream, the

permeability ratio P(O2)/P(N2), which represents the ratio of partial pressure of

oxygen to that of nitrogen, was 15. The permeability ratio was dependent on the

fixed oxygen carrier concentration.

(c) (b) (a)

Fig. 1.16 Concept of gas separation membranes: (a) Selective permeability membrane, (b) Liquid membrane, and (c) Carrier-fixed membrane

21


Fig. fixed[131

N

bindi

Nish

comp

to an

rever

perm

P(O2

perm

spect

oxyg

oxyg

T

used

provi

artifi

Fig. 1.17 Cobalt Schiff bass oxygen carrier [129]

Fig. 1.19 Cobalt porphyrin complex as a fixed carrier in an oxygen enriching membrane [141]

1.18 Cobalt Schiff bass oxygen carrier as a carrier in an oxygen enriching membrane ]

ext, metal porphyrins, which have a structure similar to that of the oxygen

ng site of hemoglobin, were used as fixed oxygen carriers (Fig. 1.19).

ide et al. have performed a detailed study on fixed cobalt porphyrin

lex carriers [131-142]. They reported that oxygen sorption and desorption

d from the fixed carrier complexes in their membranes are very rapid and

sible resembling the form of the Langmuir isotherm. The oxygen

eability was enhanced by a decrease in the upstream oxygen pressure,

), and the oxygen transport was analyzed by dual mode transport. The

selectivity P(O2)/P(N2) reported was greater than 10. Using in situ UV-VIS

roscopy, they showed that in order to enhance the facilitated transport of

en in the membrane, the complexes formed should posses both strong

en-binding affinity and fast oxygen dissociation kinetics.

hese oxygen carriers are also useful oxygen absorbents. In fact, CoS was

as an oxygen absorbent for the artificial gill and CELSS. These studies

de a hint to develop a more efficient oxygen carrier solution for the

cial gill.

22

Chapter 1

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Chapter 1

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26

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37

Documents

General introduction 1.1 Introduction