AND - NASA Technical Reports Server (NTRS)
63
a m (ACCESSION NUMBER) J "p (NASA CR OR TMX OR AD NUMBER) iCArEEORY) THERMODYNAMICS AND APPLICATIONS OF BEOELECTROCHEMICAL d ~ Hard copy (HC) Microfiche (MF) .AT ff 653 July65 L 0 Y 3 NATIONAL "4ERONALJlCS AND SPACE ADMINISTRATION / / WASHHN@T3N0 D, C,
Transcript of AND - NASA Technical Reports Server (NTRS)
a m
(ACCESSION NUMBER)
J "p (NASA CR OR TMX OR AD NUMBER) iCArEEORY)
THERMODYNAMICS AND APPLICATIONS OF BEOELECTROCHEMICAL d
~
Hard copy (HC)
Microfiche (MF) .AT ff 653 July65
L
0 Y
3 NATIONAL "4ERONALJlCS A N D SPACE ADMINISTRATION
/ / WASHHN@T3N0 D, C ,
TABLE O F CONTENT
2 A . Change i n F r e e Energy and E l e c t r i c a l P o t e n t i a l --- - B. Genera t ion of E l e c t r i c a l P o t e n t i a l s i n B i o l o g i c a l
c < - Oxidation-Reduction Reac t ions ....................
( a ) Glucose-Glucose Oxidase System ----------- 9
(c] Urea-vrease System ....................... / v
(b9 Amino Acid-D-Amino Acid Oxidase System --- I !
C. B i o l o g i c a l Genera t ion of F u e l s f o r E l e c t r i c a l Energy
111, Appl i ca t ions of B ioe lec t rochemica l Conversion --------
/Y B . Sources of Power o r Energy ....................... 1, Requirement.s fo r 1-10 M i l l i w a t t s ------------- / f 2 . Requirements fo r 2-5 Wat t s ------------------- 20 3 . Requirements for 20 Watts .................... 2s 4. Requirements g r e a t e r t h a n 20 Wat t s ----------- J 3
( a ] U r i n a r y Waste a s a Source of Energy ------ 3-7’ Qb) V e g e t a t i v e Sources of Energy ------------- jC 7
C. D e t e c t i o n and Genera t ion of Cont ro l S i g n a l s ------St
L R
,
F i g u r e
F igu re
F igu re
F i g u r e
F i g u r e
F igure
F i g u r e
F i g u r e
F i g u r e
F i g u r e
T a b l e
T a b l e
LIST O F FIGUNS AND TABLES
1 -- B i o l o g i c a l E l e c t r o n T r a n s p o r t
2 -- P o l a r i z a t i o n of a Glucose Bioanode
3 -- R e l a t i o n of C e l l Cur ren t t o E x t e n t of Urea Hydrolysis
4 -- Labora to ry Magnesium S u l f a t e B i o C e l l s
5 -- Y e a r l y World Energy - Country D i s t r i b u t i o n
Page 6
1 0
1 3
21
25
6 -- Y e a r l y World Energy - Popu la t ion D i s t r i b u t i o n 2 6
'7 -- Anodic P o l a r i z a t i o n of p l a t i n u m i n Ur ine 28
8 -- Current-Voltage of V e g e t a t i v e Bio-Fuels 30
9 -- Current-Voltage of B i o l o g i c a l l y Ca ta lyzed V e g e t a t i v e Bio-Fuels 31
10 -- Appl i cab le Power Levels fo r B ioe lec t rochemica l Conversion 34
1 -- E l e c t r o d e P o t e n t i a l s of Biochemical Reac t ion 8
11 -- Biochemical Generat ion of F u e l s 16
T a b l e 1x1 -- 'Yearly World Energy D i s t r i b u t i o n 2 4
I. I n t r o d u c t i o n
B i c e l e c t r o c h e m i c a l energy convers ion ( i e e a , c o n v e r t i n g
chemical f ree energy Of b i o l o g i c a l l y c a t a l y z e d r e a c t i o n s
t o e l e c t r i c a l energy) is n c t a newly d i s c o v e r e d phenomenon.
As l o n g ago a s 1786 Galvan i observed t h a t a f r o g muscle
tw i t ched when tcluched w i t h copper-zinc c o u p l e s i n t h i s
e a r l y i n s i g h t i n t o t h e e lec t r ica l c h a r a c t e r i s t i c s of bio-
l o g i c a l systems.
Over 50 y e a r s ago $1912) P o t t e r demonst ra ted t h a t a
" b a c t e r i a l c u l t u r e d u r i n g t h e p r o c e s s of ene rgy conve r s ion
i s i n a sense, therefore, a p r i m a r y e l e c t r i c a l h a l f c e l l
and a s such should conce ivab ly be a b l e t o per form work."
Cohen, i n 1930, o b t a i n e d 1,25 mil l i amps f r o m s i x
y e a s t c e l l s b i o c h e m i c a l l y c o n v e r t i n g g l u c o s e i n s o l u t i o n .
Through t h i s p r o c e s s he l a t e r b u i l t a b a t t e r y a b l e t o
f u r n i s h 2 mi l l i amps a t about 35 volts.
During the p a s t 10 y e a r s i n t e r e s t i n b iochemica l
ene rgy h a s i n c r e a s e d f a n t a s t i c a l l y , r e a c h i n g e x p o n e n t i a l
p r o p o r t i o n s w i t h i n t h e l a s t f i v e . P a r t i c u l a r a t t e n t i o n i n
t h e p a s t t w o y e a r s h a s been d i r e c t e d t o app ly ing t h e re-
s u l t s of r e s e a r c h and development t o t h i s t y p e o f ene rgy
-1-
conver s ion . T h i s p a p e r w i l l c o n s i d e r t h s e s a p p l i c a t i o n s i n
a s t a t e - o f - t h e - a r t review and w i l l p r e s e n t a s y n o p s i s of
sugges t ed a p p l i c a t i o n s r ang ing f r o m the use of b i o e l e c t r i c
c u r r e n t s t o i d e n t i f y t o x i c m a t e r i a l s and power human
implanted c a r d i a c pace makers t o the g e n e r a t i o n of e lectr ic
power i n remote a r e a s of the w o r l d ,
Research i n b iochemica l energy conve r s ion -- l i m i t e d t o
t h e l a b o r a t o r y -- is i n its in fancy , A v a i l a b l e d a t a a r e
inadequa te t o form a sound b a s i s f o r d e f i n i n g s p e c i f i c
e n g i n e e r i n g and economic c r i t e r i a t h a t might p o i n t the way
toward s e l e c t i n g p a r t i c u l a r technology f o r development and
l a t e r a p p l i c a t i o n s , S i n c e c r i t e r i a fo r b i o e l e c t r o c h e m i c a l
sys tems canno t now be d e f i n e d , it i s s t r o n g l y sugges t ed
t h a t p r e s e n t and e x t r a p o l a t e d c h a r a c t e r i s t i c s of such
systems should n o t be compared w i t h t h o s e of o t h e r energy
c o n v e r t e r s i n u s e o r b e i n g developed. Such a p r a c t i c e
c o u l d be d i scouraged and might r e s u l t i n f a i l u r e t o r e a l i z e
the f u l l p o t e n t i a l o f b i o e l e c t r o c h e m i c a l conve r s ion .
-2-
*
11. Fundamental P r i n c i p l e s
The fundamental p r i n c i p l e s of b i o e l e c t r o c h e m i s t r y
shou ld be c o n s i d e r e d i n order t o f u l l y r e a l i z e t h e
p o t e n t i a l i t i e s o f t h i s f i e l d . Some i n s i g h t i n t o t h e
e l e c t r i c a l p o t e n t i a l s a s s o c i a t e d w i t h b i o e l e c t r i c a l -
chemica l sys tems may be d e r i v e d f r o m the Second Law of
Thermodynamics. T h i s law de te rmines t h e r e l a t i o n
be tween f ree energy changes and the s t a n d a r d o x i d a t i o n
p o t e n t i a l of r e a c t i o n s o c c u r r i n g i n b i o l o g i c a l systems.
A. Chanqe i n Free Enerqy and E l e c t r i c a l P o t e n t i a l s
A s is w e l l known, the f ree ene rgy F, of t h e
r e a c t a n t s and p r o d u c t s i n t h e b iochemica l sys tem
aA+bB cC+dD+ --- may be expres sed i n t e r m s of the
chemica l p o t e n t i a l s a s
(2) = c / u C + d//D + ----_-------------_________ 'prod
A t c o n s t a n t t empera tu re and p r e s s u r e , t h e f r e e energy
change of the r e a c t i o n i s g iven by
A F T p = c/C + d/UD i- --- ( 3 I
- a p A - b/UB - --- The chemica l p o t e n t i a l p i s given i n t h e s t a n d a r d s t a t e
/ u o
(4) ,Q =/o+ RT I n 21
-3-
C
where 3 is the a c t i v i t y of t h e s p e c i e s i n q u e s t i o n under
d e f i n e d c o n d i t i o n s . S u b s t i t u t i o n of (4) and ( 3 ) , and
c o l l e c t i n g t e r m s ,
O F = A P ~ + RT I n - c D a b TP T
(59 .- - -
a o a A B
When the r e a c t a n t s a r e inco rpora t ed i n an e l e c t r o c h e m i c a l
conve r s ion system,
where F is the Faraday c o n s t a n t , E the e l e c t r o d e p o t e n t i a l
and n i s the number of e l e c t r o n s a s s o c i a t e d w i t h the
r e a c t i o n . Equat ion ( 6 ) i s of g r e a t importance s i n c e it
permits the c a l c u l a t i o n of s t anda rd electrode p o t e n t i a l s
Eo ( s t a n d a r d c o n d i t i o n s and u n i t a c t i v i t y ) f r o m f ree energy
d a t a , S u b s t i t u t i n g -nFE f o r A F and nFEo f o r A F O and
s u b s t i t u t i n g c o n c e n t r a t i o n (C) for a c t i v i t i e s (a l though an
approximation9.
Equat ion 5 becomes c d
E = Eo - - RT In '@ "@C nF a b
'A "'B
f r o m the s t a n d a r d o x i d a t i o n - r e d u c t i o n r e a c t i o n
X reduced - X o x i d i z e d + e- T
(7 9
- 4-
E = E, - $ I n - xox X r e d
(9)
B. Gene ra t ion o f E l e c t r i c a l P o t e n t i a l s i n B i o l o g i c a l
Ox i d a t ion-- Reduc t ion R e a c t i on s
Energy t r a n s f e r r e a c t i o n s i n b i o l o g i c a l sys tems a r e
of the o x i d a t i o n - r e d u c t i o n type . Equat ion (9) p e r m i t s
t h e c a l c u l a t i o n o f t h e e l ec t r i ca l p o t e n t i a l of t h e s e sys tems
f o r v a r i o u s d e g r e e s o f o x i d a t i o n .
I n g e n e r a l there a r e t w o main schemes f o r t h e
b i o l o g i c a l o x i d a t i o n o f o r g a n i c m a t e r i a l s . The f i rs t
( f i g . 1) i s based on an i n i t i a l hydrogen removal from
t h e reduced ( o r f u e l ) molecule , followed by a s u c c e s s i v e
series o f hydrogen atom and e l e c t r o n t r a n s f e r s a long a
c h a i n o f redox c o u p l e s r e s u l t i n g i n e l e c t r o n t r a n s f e r t o
oxygen. The e n t i r e p r o c e s s i s c a t a l y z e d by b i o l o g i c a l
c a t a l y s t s (enzymes)
The second i n v o l v e s t h e d i r e c t a c t i v a t i o n of
molecu la r oxygen b y t h e ox idase enzymes. Three t y p e s
of o x i d a s e s a r e those which c a t a l y z e : (1) d i r e c t oxygen
a d d i t i o n t o a molecule , (2) r e c u c t i o n o f one oxygen atom
+ A
m 0
-6-
( i n 02) b y e l e c - r o n r a n s f e r and d i rec t a d d i t i o n of t h e
other t o a r e a c t i n g molecule , and ( 3 ) r e d u c t i o n of oxygen
t o H202 or H20.
I n t h e work r e p o r t e d t o d a t e on a p p l i c a t i o n of
t h e f o r e g o i n g p r i n c i p l e s t o b i o e l e c t r o c h e m i c a l ce l l s
t h e p rocedure h a s been t o b r e a k the o x i d a t i o n sequence
so t h a t t h e e n t i r e enzyme system is i n one or t h e other
of the e l e c t r o d e compartments. Systems such a s t h o s e
shown i n f i g u r e 1 a r e d i v i d e d i n t o an oxygen e l e c t r o d e
and an o r g a n i c fuel-enzyme system s e p a r a t e d b y a s u i t a b l e
i o n i c conduc to r . O f p a r t i c u l a r s i g n i f i c a n c e is the s t e p
i n the o x i d a t i o n sequence a t which e l ec t r c jn t r a n s f e r t o
an i n e r t e l e c t r o d e can occur.
1, Bioanodes
Tab le 1 l i s t s a number of p o t e n t i a l b i o -
e l e c t r o c h e m i c a l o x i d a t i o n - r e d u c t i o n c o u p l e s which a r e
anod ic t o oxygen a t t h e more normal b i o l o g i c a l pH of
7. The p o t e n t i a l s i n Tab le I i n d i c a t e t h a t w i t h t h e
a p p r o p r i a t e enzyme c a t a l y s t s , s u b s t a n c e s found i n
n a t u r a l s o u r c e s such a s ace t a ldehyde , x a n t h i n e , g l u c o s e ,
and c y s t e i n e may be f e a s i b l e a s f u e l electrodes w i t h an
-7 -
TABLE I
ELECTRODE POTENTIALS OF BIOCHEMICAL REACTIONS
Electrode Couple Enzyme
Aceta t e/Acet a ldehyde Xanthine Oxidase
Latic Acid/Xanthine Xanthine Oxidase
Gluconolactone/Glucose Glucose oxidase
Cyst in e/Cys t e ine
Acetaldehyde/Ethanol Alcohol dehydrogenase
Pyruvate/Lactate Lactic dehydrogenase
Oxaloacetate/Malate Malic dehydrogenase
Furnara te/Succ in a te
Dehydroascorbate Ascorbate Ascorbic oxidase
Ferricytochrome c/Ferrocytochrome c
Oxidized cyt . oxidase/Cytochrome oxidase 02 + 4 ~ + + 4e
None
Succinic dehydrogenase
2 ~ 2 0
- E"m7
-0.58
-0.39
-0 .36
-0.33
-0 .20
-0.18
-0.16
+o. 02
+O. 06
+O. 27
+0.29
+O. 82
*Em7 is the potential at pH 7 in the presence of equal
concentrations of oxidized and reduced forms of reactants.
- 8-
.
oxygen ( a i r ) ca thode . The energy d e n s i t y of these m a t e r i a l s
is on t h e o r d e r of 5 pounds p e r k i lowa t t -hour . S e v e r a l
enzymes c a t a l y z e d and whole organism-catalyzed redox
c o u p l e s have been s t u d i e d under l a b o r a t o r y c o n d i t i o n s . The
r e s u l t s a r e d i s c u s s e d b e l o w :
( a ) Glucose - Glucose Oxidase System
The e l e c t r o d e mechanism h a s n o t been
c r i t i c a l l y d e s c r i b e d for t h i s system. S e v e r a l mechanisms
a r e sugges t ed . I n a d i r e c t mechanism g l u c o s e and t h e
enzyme g l u c o s e o x i d a s e r e a c t t o f o r m a complex i n t e r -
med ia t e . The i n t e r m e d i a t e is o x i d i z e d a t t h e anode t o
g l u c o n o l a c t o n e and t h e enzyme is l i b e r a t e d . (Equat ions
10 and 11).
Glucose Oxidase (Glucose . Enzyme) ‘gH1206
(Glucose-Enzyme) m o d e C,HLo06 + 2H+ + 2e- (11)
Anodic p o l a r i z a t i o n d a t a f o r t h e g lucose-
g l u c o s e o x i d a s e bio-anodes i s shown a s f i g u r e 2. I n these
s t u d i e s , t h e enzyme g l u c o s e ox idase is i n c o r p o r a t e d i n t h e
p t - b l a c k electrode s u r f a c e and g l u c o s e ( reduced form is
added t o t h e c e l l ) . As shown i n f i g u r e 2, the e l e c t r o c h e m i c a l
-9-
9 4,
f
' I
o x i d a t i o n of g l u c o s e on p l a t inum is markedly enhanced by
the i n c o r p o r a t i o n of the g lucose o x i d a s e a s a c a t a l y s t .
(b) Amino A c i d - D - Amino A c i d Oxidase
System
The normal a e r o b i c r e a c t i o n p r o d u c t s
of the amino a c i d D - amino ac id o x i d a s e (DAO) system ill-
c l u d e the p y r u v i c a c i d d e r i v a t i v e o f the amino a c i d , hydrogen
p e r o x i d e and ammonia.
Experiments have been conducted on
the b i o e l e c t r o c h e m i c a l behavior of the three amino a c i d s
Tryptophane, t y r o s i n e and pheny la l an ine and their r e s p e c t i v e
D-amino a c i d o x i d a s e r e a c t i o n p r o d u c t s indole-3-pyruvic a c i d ,
para-hydroxy phenyl p y r u v i c a c i d , and phenyl p y r u v i c a c i d .
R e s u l t s t o d a t e on p l a t i n u m e l e c t r o d e s show t h a t observed
c u r r e n t s a r e d e r i v e d f r o m the e l e c t r o c h e m i c a l o x i d a t i o n of
the a romat i c p y r u v i c r e a c t i o n p roduc t s . Ammonia n o t p e r o x i d e
c o n t r i b u t e d a p p r e c i a b l y t o the e l e c t r i c a l c u r r e n t s . C u r r e n t s
of the o r d e r of 350 / fA/cm2 a t 200 mv have been d e r i v e d
w i t h indole-3-pyruvic a c i d .
C u r r e n t s on the order of 45/u A/cm2
a t 200 mv have been d e r i v e d f rom ce l l s i n which i n d o l e
p y r u v i c a c i d i s g e n e r a t e d enzymat i ca l ly f r o m Tryptophane.
-11-
.
These s t u d i e s i n d i c a t e t h a t : (1) t h e c u r r e n t l i m i t a t i o n i s
enzymat ic , ( 2 ) t h e r e a c t i v e s p e c i e s is t h e e n o l form of t h e
k e t o a c i d d e r i v a t i v e of the n a t u r a l l y o c c u r r i n g amino a c i d s
( a b s o r p t i o n s p e c t r a d a t a ) , and ( 3 ) f u r t h e r s t u d i e s a r e
needed t o de te rmine o p t i m a l c o n d i t i o n f o r enzyme and electro-
chemica l a c t i v i t y i n o r d e r t h a t t h e p o t e n t i a l of u t i l i t i z i n g
complex n a t u r a l o c c u r r i n g m a t e r i a l s a s e l e c t r o d e r e a c t a n t s may
be e x p l o i t e d .
(c) The Urea-Urease System
T h e o r e t i c a l l y it would be expec ted t h a t
i n t h i s ce l l t h e enzyme u r e a s e would g e n e r a t e ammonia from
u r e a and t h e ammonia e l e c t r o c h e m i c a l l y o x i d i z e d :
CO (NH2)2 + H20 Urease r 2 "3+CO2 (12 1
2 NH + 6 OH- N2 + 6 H20 + 6s ( 1 3 1 3
I n s t u d i e s t o d a t e t h e Urea-Urease System h a s p r e s e n t e d a
r a t h e r c o n s i s t a n t dilemma. I n ce l l s wich b r i g h t p l a t i n u m
e l e c t r o d e s i n 0.25 m ammonium n i t r a t e i n t r is b u f f e r (tris-
hydroxymethyl amino methand) a t pH of 6.5 - 9.0 ammonia
was r e p o r t e d l y n o t o x i d i z e d . I n t h e same ce l l , n e v e r t h e l e s s ,
t h e a c t i o n of u r e a s e r e s u l t e d i n t h e augmentat ion of the
c e l l c u r r e n t and t h e enzymatic h y d r o l y s i s of u r e a p a r e l l e l s
t h e c e l l c u r r e n t , ( f i g . 3 ) . Other s t u d i e s have shown t h a t
-12-
a
c.3
3 LA
.
g, k n
-13-
a t pH 6 i n a K C1 - c i t r a t e b u f f e r u s i n g p l a t i n u m impregnated
carbon electrodes i n c o r p o r a t i n g the u r e a s e enzyme, short
2 c i r c u i t c u r r e n t s of 1-3 ma/cm w e r e d e r i v e d on a d d i t i o n o f
u r e a , F u r t h e r s t u d i e s on t h i s system a r e b e i n g conducted .
2 . S u l f a t e Bioca thode
P o t e n t i a l s a s s o c i a t e d w i t h b i o l o g i c a l l y
c a t a l y z e d r e d u c t i o n s have a l s o been i n v e s t i g a t e d . The
r e d u c t i o n of s u l f a t e t o hydrogen s u l f i d e by the organism
D e s u l f o v i b r i o d e s u l f u r i c a n s , a t t a c h e d t o po rous i r o n elec-
t r o d e s , h a s been e x t e n s i v e l y s t u d i e d . However, the
mechanism for t h i s e l e c t r o d e h a s n o t been completely
e s t a b l i s h e d . It is t h o u g h t t h a t t h e r e a c t i o n $ f o r the
b i o e l e c t r o c h e m i c a l r e d u c t i o n of s u l f a t e may be a s fo l lows :
2W20 + 2e- Ca thode , - H2+20H- (14)
S04=+4H2- S= + 4H20 (15 1
S0,=+4H20 + 8e" S= + 80H- (16)
C, B i o l o q i c a l Genera t ion of F u e l s f o r E l e c t r i c a l
Enerqy
B i o l o g i c a l ene rgy s o u r c e s may a l s o i n d i r e c t l y
g e n e r a t e e l ec t r i c i ty . Biochemical a g e n t s may g e n e r a t e chemi-
c a l species s p e c i f i c a l l y t a i l o r e d t o a b i o l o g i c a l e n e r g y
-14-
c o n v e r s i o n sys tem op t imized t o the r e q u i r e m e n t s and con-
s i s t e n t w i t h a v a i l a b l e f u e l . Examples i n c l u d e t h e g e n e r a t i o n
of hydrogen, ammonia, or methanol from h i g h e r molecu la r
we igh t m a t e r i a l s (such a s s u g a r s , p r o t e i n s , f a t s , s t a r c h e s ,
u r e a ) by means of whole l i v i n g ce l l s o r ce l l free e x t r a c t s
o r c r y s t a l i z e d enzymes.
Samples of b iochemica l sys tems f o r the g e n e r a t i o n
of p r imary f u e l s from complex m a t e r i a l s a r e p r e s e n t e d as
T a b l e 11. The l i t e r a t u r e h a s been reviewed and o v e r 200
r e f e r e n c e s a r e inc luded i n t h e b i b l i o g r a p h y under
"Genera t ion of B ioe lec t rochemica l Fue ls . "
A p p l i c a t i o n s o f b i o e l e c t r o c h e m i c a l c o n v e r s i o n a r e
d i s c u s s e d i n t h e f o l l o w i n g paragraphs .
-15-
. .
m ,& A.
-16-
111. A p p l i c a t i o n s of B ioe lec t rochemica l Convers ion
A. General
Research and development l o o k i n g toward t h e
a p p l i c a t i o n s o f b i o e l e c t r o c h e m i c a l conve r s ion is i n
i t s e a r l y phases . However, a t p r e s e n t f o u r g e n e r a l
a r e a s f o r p o t e n t i a l f u t u r e a p p l i c a t i o n s appear t o be
emerging.
These inc lude :
Power sciurces for supp ly ing r e l a t i v e l y
sma l l amounts of e l e c t r i c a l ene rgy i n
s p e c i a l i z e d a p p l i c a t i o n s anl! l o c a t i o n s .
D e t e c t o r s f o r s p e c i f i c con taminan t s i n l o w
c o n c e n t r a t i o n s .
Senso r s f o r g e n e r a t i o n of con t ro l s i g n a l s .
C a t a l y s t s f o r t h e g e n e r a t i o n of electro-
chemica l r e a c t a n t s from complex n a t u r a l l y
o c c u r r i n g m a t e r i a l s and f r o m was te m a t e r i a l s .
Ava il a b l e in fo rma t ion i n d i c a t e s t h a t b ioelectro-
chemica l power g e n e r a t i o n w i l l most l i k e l y be l i m i t e d t o
s p e c i a l i z e d a p p l i c a t i o n s . Competit ion w i t h major power
g e n e r a t i o n methods is u n l i k e l y . B i o e l e c t r o c h e m i c a l power
-17-
g e n e r a t i o n w i l l p robab ly supply l i m i t e d emergency power,
serve remote and una t tended power s u p p l i e s , and supplement
e x i s t i n g n a t u r a l f u e l s ( such as v e g e t a t i o n ) when t r a n s -
p o r t a t i o n costs f o r a d d i t i o n a l f u e l s a r e e x c e s s i v e .
B. Sources of Enerqy or Power
AS power s o u r c e s b i o e l e c t r o c h e m i c a l c o n v e r t e r s
may be a r b i t r a r i l y c l a s s i f i e d i n terms of power l e v e l s for
sugges t ed a p p l i c a t i o n s .
1. Requirement for 1-10 m i l l i w a t t s
Low power level i m p l a n t a b l e t r a n s d u c e r s ,
s t i m u l a t o r s , and o t h e r e l e c k r o n i c d e v i c e s a r e needed
t o r e g u l a t e p h y s i o l o g i c a l and b i o l o g i c a l f u n c t i o n s .
For example, the present day peacemaker used i n t h e r e g u l a -
t i o n of t h e e l e c t r i c a l p r o f i l e of the human h e a r t r e q u i r e s
e l e c t r i c a l energy a t about 2 . 4 vo l t s w i t h c u r r e n t p u l s e s
2 m i l l i s e c o n d s i n d u r a t i o n a t a f requency of one t o two /
second. The ave rage c u r r e n t and power a r e abou t 2 5 A
amperes and 1 0 0 ~ w a t t s , r e s p e c t i v e l y . T h i s ene rgy is
norma l ly s u p p l i e d by f i v e pr imary cel ls , c a l c u l a t e d t o
l a s t fo r t w o t o t h r e e y e a r s , which a r e made p a r t of t h e
i m p l a n t a b l e package. Surgery is r e q u i r e d t o r e p l a c e the
-18-
dead b a t t e r i e s . The o p e r a t i n g l i f e o f b a t t e r i e s for other
i m p l a n t a b l e d e v i c e s may be much less.
The development of i m p l a n t a b l e ene rgy con-
ver tors w h i c h d e r i v e t h e i r energy on a con t inuous o r
periodic b a s i s from p h y s i o l o g i c a l f l u i d s may be q u i t e
advantageous. Consequent ly , t h e development of an i m -
p l a n t a b l e f u e l c e l l w i t h o u t p u t of 2 0 0 A w a t t s a t a v o l t a g e
leve l i n the v i c i n i t y of 1 v o l t may be a v e r y wor thwhi le
objective.
The l i t e r a t u r e a v a i l a b l e on the measurement
of o x i d a t i o n - r e d u c t i o n p o t e n t i a l s of mammalian b lood is
e x t e n s i v e . Electrode p o t e n t i a l s r a n g i n g from 0.5 t o 4 . 3
a r e r e l a t i v e l y common i n qammalian body f l u i d s . W i t h a f u e l
c e l l of 0.5 v o l t a t a c u r r e n t d e n s i t y of 1 0 N a m p e r e s per
s q u a r e c e n t i m e t e r , the power o u t p u t would be 5 A w a t t s per
c m 2 of e l e c t r o d e s u r f a c e a r e a . Even a t such l o w c u r r e n t
d e n s i t i e s the peacmaker power r equ i r emen t s cou ld e a s i l y
be s a t i s f i e d w i t h electrode s u r f a c e a r e a s of the o r d e r of
2 100 c m . I n an exper imenta l ana log of the c o n d i t i o n s
found i n the blood s t r e a m the open c i r c u i t v o l t a g e was
-19-
approximate ly 0.1 v o l t when p la t inum b l a c k e l e c t r o d e s w e r e
used.
s q u a r e c e n t i m e t e r w e r e found t o be l i n e a r w i t h the p o l a r i -
z a t i o n v o l t a g e s hav ing a s l o p e o f n e a r l y 2 1/2 m i l l i v o l t s
C u r r e n t d e n s i t i e s ranging f r o m 10 t o 50 ,Uamps per
per P a m p e r e per s q u a r e c e n t i m e t e r .
2. Requirements for 2-5 w a t t s
A t t e n t i o n h a s been g iven t o the a p p l i c a t i o n
of d i r ec t b i o e l e c t r o c h e m i c a l c o n v e r t e r s f o r l o n g d u r a t i o n
una t t ended power g e n e r a t i o n . U s e of these c o n v e r t e r sys tems
t o s u p p l y 2-5 w a t t s o f power i n the ocean h a s been b r o a d l y
explored. S u l f a t e , a v a i l a b l e i n t h e ocean , h a s been s t u d i e d
e x t e n s i v e l y a s the c a t h o d i c r e a c t a n t of such a power s o u r c e
device. I n t h i s d e v i c e b a c t e r i a ( D e s u l f o v i b r i o d e s u l f u r i c a n s )
a r e a p p l i e d t o t he ca thode where t h e y consume hydrogen and
r educe s u l f a t e ion t o s u l f i d e ion . The anodic p r o c e s s is
the o x i d a t i o n of magnesium. L i m i t i n g c u r r e n t d e n s i t i e s a s
high a s 3 ma/cm2 a t -0.8V vs SCE have been r e p o r t e d under
optimum c o n d i t i o n s . C e l l de s ign h a s n o t been op t imized h u t
power d e n s i t i e s i n t he r a n g e of 5-20 W / f t 3 dnd ene rgy d e n s i -
t i es of approx ima te ly 30 K" / f t3 may be e s t i m a t e d for a ce l l
t o o p e r a t e two y e a r s w i t h o u t a t t e n t i o n . A l a b o r a t o r y f u e l
c e l l is shown i n f i g u r e 4.
-20-
t
3 . Requirements f o x 20 w a t t s
The a v d i l a b i l i t y of used oxygen and the enzyme
u r e a s e h a s sugges ted t h e i r u s e i n an open-cycle power
g e n e r a t o r . S e v e r a l i n v e s t i g a t t u n s have been conducted
of the e l e c t r o c h e m i c a l performance of a u r e a z e u r e a
oxygen ( a i r ) b a t t e r y . I n t he f u t u r e t h i s t y p e of b a t t e r y
might be used t c produce r e l a t i v e l y low power (below 20
w a t t s ) f o r shor t p e r i o d s o f t i m e ( 2 weeks, fo r example) .
As anode m a t e r i a l s p l a t inum b l a c k electro-
d e p o s i t e d p l a t i n u m , p l a t i n u m impregnated cd rbon , a c t i v e
impregnated carbofi , a c t i v a t e d c a r b o n , R a n e y s i l v e r , and
e l e c t r o d e p o s i t e d n i c k e l have been i n v e s t i g a t e d .
C r y s t a l l i n e enzyme c a t a l y s t s would be i n c o r p o r a t e d i n the
e l e c t r o d e s ; monel s c r e e n s and pa rous carbon blocks used
3s c u r r e n t c o l l e c t o r s . A 3 M KC1, c i t r a t e b u f f e r a t
p H 6 , r e s u l t e d i n maximum l i m i t i n g c u r r e n t 6 e n s i t i e s . The
a i r ca thode i s a porous p l a t i n i z e d carbon electrcde.
These f u e l c e l l s hdve achieved an open c i r c u i t vol tage
of abou t 0.8V and a s h o r t c i r c u i t d e n s i t y of 3 .6
anip/ft2 f G r s h o r t p e r i o d s cf t i m e .
4. Power Requirements G r e a t e r t h a n 2 0 w a t t s
S e v e r a l f a c t o r s need t o be ana lyzed when
c o n s i d e r i n g b i o e l e c t r o c h e m i c a l c o n v e r t o r s f o r power
a p p l i c a t i o n s i n e x c e s s of 20 w a t t s . Worldwide energy
demand and f u e l l o g i s t i c s a r e t w o of these i m p o r t a n t con-
s i d e r a t i o n s . A d i s t r i b u t i o n of t h e w o f l d ' s y e a r l y e l e c t r i c a l
ene rgy consumption is shown a s t a b l e 111, d i s t r i b u t i o n
by c o u n t r y a s f i g u r e 5, and d i s t r i b u t i o n on t h e b a s i s of
wor ld p o p u l a t i o n a s f i g u r e 6. These d a t a show t h a t a b o u t
2 4 p e r c e n t of t h w world's c o u n t r i e s , w i t h 37 p e r c e n t of i t s
p o p u l a t i o n , have an ave rage y e a r l y e l e c t r i c a l ene rgy con-
sumption of only 2 0 k i l o w a t t hour s p e r c a p i t a . It is
e v i d e n t f r o m t h i s f a c t t h a t s p e c i a l remote l o c a t i o n s
th roughou t the w o r l d may w e l l be provided w i t h a minimal
power s o u r c e a t minimal c o s t s b y u s i n g b i o l o g i c a l sLurces
of energy .
B i o l o g i c a l sou rces of energy c o u l d be used
f o r the g e n e r a t i o n o f e l e c t r i c a l power d i r e c t l y by bio-
e l e C t r L C h e m i C d 1 energy convers ion o r i n d i r e c t l y b y
b i o c a t a l y t i c g e n e r a t i o n of s imple f u e l s from complex
-23-
Group Range KWH per c a p i t a
A 1,000-10,346
B 500-1,000
C 200-500
D 100-200
50-100 E
F 0-50
TABLE I11
Average KWH per c a p i t a
2,964
6 81
331
129
70
20
P e r c e n t C o u n t r i e s
24.2
11.3
16.1
10.5
13.7
24.2
P e r c e n t Popu la t ion
28.9
4.3
6.9
4.4
18.3
3 7 . 2
-24-
' . l
L . -
I I I
. ' I
al d' (1
7 1
H- H
w
Q I
§l
j *
! !I
.--
I
-26-
n a t u r a l l y o c c u r r i n g m a t e r i a l s . O f p a r t i c u l a r s i g n i f i c a n c e
i s t h e u t i l i z a t i o n o f b i o l o g i c a l ene rgy s o u r c e s i n t h e i r
n a t u r a l f o r m .
( a ) Ur ina ry Waste a s a Source o f Energy
T h e o r e t i c a l l y , b i o e l e c t r o c h e m i c a l con-
v e r s i o n o f u rea i n human u r i n a r y w a s t e s cou ld supp ly on
t h e o r d e r o f 18 KWH p e r c a p i t a y e a r l y based on a con-
v e r s i o n e f f i c i e n c y of 50 p e r c e n t .
Work h a s a l r e a d y been conducted on t h e
e l e c t r o c h e m i c a l b e h a v i o r o f systems f u e l e d by raw u r i n e
and c a t a l y z e d by growing b a c t e r i a . T h e b a c t e r i a B a c i l l u s
p a s t e u r i i h a s been s t u d i e d i n a sys tem because of i t s
e s t a b l i s h e d u r e o l y t i c a c t i v i t y . P r e l i m i n a r y d a t a ( f i g . 7 )
i n d i c a t e t h a t a p r e l i m i n a r y 18-hour i n c u b a t i o n of raw
u r i n g w i t h t h i s b a c t e r i a p r o v i d e s i n c r e a s e d c u r r e n t . A t
170 mV, f o r example, the c u r r e n t c a r r y i n g c a p a c i t y of the
electrode f u e l e d by p re incuba ted m a t e r i a l w a s g r e a t e r by
d f a c t o r of 15 t h a n the unincubated m a t e r i a l .
(b) Vege ta t ive Sources o f Energy
S e v e r a l o t h e r systems us ing n a t u r a l m a t e r i a l s
a s f u e l s have been s t u d i e d . Labora to ry s t u d i e s have shown
-27-
a -a=
0
-28-
t h a t some power g a i n s may be r e a l i z e d b y t h e b i o l o g i c a l
c a t a l y z a t i o n of e l e c t r o c h e m i c a l systems u s i n g n a t u r a l
m a t e r i a l s such a s f r e s h mushrooms, t o a d s t o o l s , s u c r o s e ,
and a l g a e a s f u e l s and oxygen ( a i r ) ca thodes .
Chemical d i g e s t i o n of n a t u r a l m a t e r i a l s
w i t h s u l f u r i c a c i d and potdssium hydrox ide r e s u l t s i n
the g e n e r a t i o n of e l e c t r o c h e m i c a l l y a c t i v e o r g a n i c and
i n o r g a n i c m a t e r i a l and an o v e r - a l l n e t r e a c t i o n may be
w r i t t e n :
1 / 2 CH2O + 1 / 2 0 2 --a 1 / 2 C02 + 1/2 H 2 0 (17) ( B i o l o g i c a l fuel)
Some l a b a r s t o r y r e s u l t s f L r t h e non-
b i o l o g i c a l l y c a t a l y z e d systems a r e p r e s e n t e d a s f i g u r e 8.
The b i o l o g i c a l c a t a l y z e d o x i d a t i o n o f
n a t u r a l f u e l s w i t h s u l f u r i c a c i d u s i n g t h e b a c t e r i a
D e s u l f l o v i b r i o may be used a s anodic r e a c t a n t s i n a system
w i t h an oxygen ( a i r ) ca thode . The o v e r - a l l n e t r e a c t i c n
may be g iven a s fo l lows :
2 CH20 + H 2 S 0 4 + 1/2 02 --> C 0 2 + 3H20i-S (18)
LaLoratory r e s u l t s f o r s e v e r a l systems
s t u d i e d a r e p r e s e n t e d a s f i g u r e 9. A cbmparison of
-29-
Le
d mm
m
>. .- ...
-30-
\
w
B m
4
3 c
N
f i g u r e s 8 and 9 i n d i c a t e s a g r e a t e r t h a n 4 f u e l i n c r e a s e
i n c u r r e n t d e n s i t i e s may be r e a l i z e d by b i o l o g i c a l
c a t a l y s t s i n systems u s i n g complex n a t u r a l f u e l s . These
s t u d i e s have been conducted under l a b o r a t o r y c o n d i t i o n s
i n o r d e r t o e l u c i d a t e t h e pa rame te r s e f f e c t i n g b i o -
e l e c t r o c h e m i c a l a c t i v i t y . Much work remains t o be done
b e f o r e the f e a s i b i l i t y is e s t a b l i s h e d of u t i l i z i n g such
phenomena a s p r a c t i c a l a p p l i c a n t s where complex n a t u r a l
m a t e r i a l s a r e r e a d i l y a v a i l a b l e .
C. D e t e c t i o n and Genera t ion of C o n t r o l S i g n a l s
Another a r e a o f a p p l i c a t i o n s f o r b i o e l e c t r o c h e m i c a l
conve r s ion i s i n (1) t h e d e t e c t i o n of s imple and complex
chemica l s p e c i e s i n ex t remely low c o n c e n t r a t i o n s , and ( 2 )
i n the use o f e lec t r ic s i g n a l s a s s o c i a t e d w i t h b iochemica l
systems f o r c o n t r o l . I l l u s t r a t i v e work t o d a t e i n c l u d e s
the t o x i c g a s d e t e c t o r and m y o e l e c t r i c s e r v e b o o s t system.
The i n f l u e n c e o f v a r i o u s chemica l s on the a c t i v i t y
of n a t u r a l l y o c c u r r i n g microorganisms h a s been u t i l i z e d
i n t he d e t e c t i o n o f t o x i c agen t s .
The a c t i v i t y o f i h e microorganism h a s been found
t o be p r o p o r f i o n a l t o the c o n c e n t r a t i o n of v a r i o u s agenc t .
-3 2-
S p e c i f i c b i o l o g i c a l a g e n t s have been p r e s e l e c t e d which
w i l l p r o v i d e d e t e c t i o n of t r a c e m a t e r i a l s a t concen t r a -
t i o n s of p a r t s p e r b i l l i o n .
The f e a s i b i l i t y h a s been demonst ra ted of u s i n g
e l e c t r i c a l s i g n a l s a s s o c i a t e d w i t h c o n t r a c t i o n o f
musc les t o c o n t r o l a s e r v o b o o s t sys tem which would
e n a b l e an i n d i v i d u a l t o remotely h a n d l e adve r se t a s k s .
I n t h i s a p p l i c a t i o n s i lver f o i l e l e c t r o d e s a r e a t t a c h e d
e x t e r n a l l y t o a s u b j e c t and a p o t e n t i a l o f 1-3 mi l l i vo l t s
peak t o peak a t 3-1000 cyc les / second a r e p icked off and
used t o d i rec t an e x t e r n a l c o n t r o l l o g i c .
F i n a l l y , i n the b r o a d e s t s e n s e , b i o e l e c t r o -
chemica l energy conve r s ion may show numerous and v a r i e d
a p p l i c a t i o n s . Such a p p l i c a t i o n s a r e a r b i t r a r i l y o rgan ized
I a cco rd ing t o the l e v e l o f a s s o c i a t e d power a s f i g u r e 10.
T h e a p p l i c a t i o n s i l l u s t r a t e d do n o t r e p r e s e n t a complete
su rvey , s i n c e the e n t i r e a rea i s r e l a t i v e l y new and a
comple te p i c t u r e h a s n o t been developed.
However, it i s hoped t h a t the above d i s c u s s i o n
w i l l serve t o s t i m u l a t e t h i n k i n g i n t h i s a r e a .
-33-
Y W
0 I
-3 4-
REFERENCES
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CHUNG, K. L. (1954). On as tochas t ic Approximation Method [ 2 ] Ann. Math. S ta t i s t . 25 463-483. -
[3] CRAMER, H. (1946). Mathematical Methods of S ta t i s t ics ,
Pr ince ton Univ. P r e s s , Pr ince ton ~ 6 7 .
DAVENPORT, W . and ROOT, W . (19 58). Random Signals
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[5] GARDNER, L . (May 1964) P r i v a t e communication.
[ 6 ] HELSTROM, C. R . (1960). S ta t i s t ica l Theory of Signal
Detection, Pe rgamon , Oxford, Chap. 11.
[7] HELSTROM, C. R . op. ci t , 312-315.
[8] KIEFER, J . and WOLFOWITZ, J . (1952). Stochastic Esti-
mat ion of the Maximum of a Regres s ion Function.
Math. S ta t i s t . 23 462-466.
Ann.
-- [ 9 ] PRICE, R . (1956). Optimum Detection of Random Signals in
Noise with Application t o Sca t te r - Multipath Communication
T r a n s . I . R . E . IT-2 , N o . 4 , 125. ---- [lo] ROBBINS, H. and MUNRO, S. (1951). A Stochastic Approxi-
mat ion Method. Ann. Math. S ta t i s t . 22 400-407. -- [ll] SACKS, J . (1958). Asymptotic Distribution of Stochastic
Approximation P rocedures . Ann. Math. Stat is t . 29 373-405. - [12] ZADEH, L. and RAGAZZINI, J. (1950). An Extension of
Wieners Theory of Predict ion, J . Appl. Phys . 21 645-655. ...-
-35-
I
The fo l lowing b ib l iog raphy on bioelectroehemical energy
conversion and r e l a t e d subjects h a s been compiled f r o m
r e fe renced works i n the a r e a of b ioe lec t rochemis t ry , The
l i s t i n g i s not complete, It is in tended t o establish a
r e p r e s e n t a t i v e compi la t ion of r e f e r e n c e s needed by an in-
v e s t i g a t o r to embark upon r e sea rch i n t h i s a r e a . The
fo l lowing a b b r e v i a t i o n s were used i n t h e b ib l iog raphy t o
a s s i s t i n the l o c a t i o n of reports and documents.
N numbers refer t o S c i e n t i f i c and Technica l Aerospace Reports (STAR)
A numbers refer t o I n t e r n a t i o n a l Aerospace A b s t r a c t s
AD numbers refer t o Armed Se rv ices Technica l Information Agency { M T I A ) cow c a l l e d D e f e n s e Documentat ion Center (BDC)
BIBLIOGRAPHY OF BIOELECTROCHEMICAL PROCESSES
TABLE OF CONTENTS
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2.
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4.
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7.
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10.
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5
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Role of Metal Ions in Enzyme Systems - 12
BIBLIOGRAPHY OF BIOELECTROCHEMICAL PROCESSES
TABLE OF CONTENTS
(CONTINUED)
A.
B.
Fundamental I n v e s t i g a t i o n s -------------- 1, E l e c t r o d e S t u d i e s -_----------------- 2. B i o e l e c t r i c A c t i v i t y ---------------- 3 . O r g a n i c Me&ranes ------------------- B i o e l e c t r o c h e m i c a l F u e l C e l l s -----------
P a g e
12
12
12
16
18
20
A BIBLIOGRAPHY OF BlOELECTROCHEMlCAL PROCESSES
I . GENERAL
3 t Anonymous, Standard Methods f o r the Examinat ion o f Water and Wastewater, p u b l i s h e d j o i n t l y by the American P u b l l c Hea l th Assn., American Water Works Assn., and Water P o l l u t l o n Cont ro l Federa t ion (1961)
9~ L l o y d L. Ingraham, Biochemical Mechanisms, John Wi ley and Sons, I nc . , p 77 (1962)
>k Spector, W. S . , Handbook o f B i o l o g i c a l Data, WADC Technica l Re- p o r t 56-273, A S T l A Document No. AD 110 501 (1956)
1 1 . SOURCES AND GENERATION OF BlOELECTROCHEMlCAL REACTANTS
I I A L I V I N G ORGANISMS
I I A l SEWAGE D I G E S T I O N
Bogen, R. H . and D . 0. Chapman, Deve M ic rob io logy , 3, 45, Plenum Press, N
9, Br isou, B., B u l l . SOC. Pa tho l . Exot.
opments i n I n d u s t r i a l Y. (1962)
54, 746 (1961)
Jc Buck, T. C . , C . E. Keefer and ti. Hatch, Sew. and Ind. Wastes, 25, 993, (1953)
Jf Buck, T. C . , C . E. Keefer and H. Hatch, Sew. end Ind . Wastes, 26, I64 (1954)
* Buck, T . C . and C . E. K w f e r , Sew. and Ind . Wastes, 31, 1267 ( 1959)
* Buswell, A. M., S p e t i c Tank t o C o n t r o l l e d Dlgestlon, I n 810- l o g i c a l Treatment o f Sewage and l n d u s t r l a l Wastes, Vol .2 , Eds, J, McCaba rnd W.W. Eckenfelder, J r . , Rs inho ld Pub. Corp., N . Y . (1958) , 3-8
* Buthsux, R. and 0 , A . A . Mossel, J. Appl . B a c t e r l o l . , 24, 353 (1961)
* B u t t e r f i e l d , C . Publ. Hea l th Repts., 50, 571 (1935)
- 1 -
7': Chapman, D. D . , Proceedings o f t h e I n s t i t u t e o f Environmental Sciences, p . 283, (1960)
:t Col lee, L . G . , J . A. Knowlden, and B . C . Hobbs, J. Appl . B a c t e r i o l . , 24, 326(1961)
;': Consolazio, D . F. , Johnson, R . E . , and Pecora, L . J., Physio? l o g i c a l Measurements o f Metabol ic Funct ions o f Man, McGraw- H i l l Book Company, New York (1963)
;': Eckenfe lder , W. W. J r . , and O'Connor, D . J., Anaerobic Bio- l o g i c a l Treatment Processes, i n B i o l o g i c a l Waste Treatment, Pergamon Press, New York (1961), 248-269
;t G a l l , L . S . , Fenzer, D . B . , and Helvey, W . M . , Bio-Ecology o f D iges t ion , i n B i o l o g i s t i c s f o r Space Systems Symposium (May 1962), Technical Documentary Report No. AMRL-TDR-62-116 (October 1962), 382-390
;': G a r r e t t , J r . , M. T . , Sew. and Ind. Waste, 30, 253 (1958)
;': G o l d b l i t h , S . A . , and Wick, E. L . , Ana lys is o f Human Fecal Components and Study of Methods f o r T h e i r Recovery i n Space Systems, ASD Technica l Report 61-419, Wr igh t -Pat te rson A i r Force Base, Ohio (1961)
;': G o l d b l i t h , S . A. and E. L. Wick, Contract AF 33(616)-6136, ASO-TR-61-419 ( 1 961 )
7': G o l d b l i t h , S . A. and E. L. Wick, Ana lys is o f Human Fecal Components and Study o f Methods f o r The i r Recovery i n Space Systems, U. S.A. F. Aeronaut Systems D i v . Tech. Report 61-419, 1-57, (1961)
9; Golueke, C. G . , W. J. Oswald and F . ii. McGanky, Sew. and Ind . Waste, 31, 1125 (1959)
;k Hawkes, H. A-, Ecology o f Ac t iva ted Sludge and Bac te r ia Beds, i n Waste Treatment, Ed., P.C.G. Issac, Pergamon Press, Oxford, ( 1 9601, 52-98
;t Hogan, R . H., Chapman, D . D. , and Er icsson, L. H . , Aerobic B i o l o g i c a l Degradat ion o f Human Waste i n Closed Systems, Advances i n As t ronau t i ca l Sciences, 6 (1961) 390-398
f; Ingram, W . T . , TDR #AMRL-TDR-62-126, Contract AF 33(616)-7827, ( 1 962)
- 2-
;k Kaplovsky, A . J . , Appl . M ic rob io l . , 5, I75 (1957)
I
;k Kountz, R . R . and C . Forney, Jr., Sew. and ind . Waste, 31, 819 (1959)
5; Lackey, J. B . , Hendrickson, E . R . , Biochemical Bases o f Anaerobic D iges t ion , i n B i o l o g i c a l Treatment o f Sewage and I n d u s t r i a l Wastes, Volume 2, EDS. J. McCabe, and W. W. Ecken- f e l d e r , J r . , Reinhold Pub1 i sh ing Corporat ion, New York (1958) 9- 24
5; Leone, D. E . , Contract NASw-95, U413-63-041, General Dynamics, E l e c t r i c Boat D i v i s i o n , Groton, Conn. (1963)
;': McKinney, R . E . , M ic rob io logy f o r San i ta ry Engineers, McGraw- H i l l Book Co., Inc . , New York, 1962
McKinney, R. E . , and R. G . Weichlein, Appl . M i c r o b i o l . 1 , 259 ( 1 953)
7': Melek, I . , Development and Fur ther Perspec t ive o f the Continu- ous C u l t i v a t i o n o f Microorganisms, p . 3-20, I n Continuous Cu l tu re o f Microorganisms, Society o f Chemical i ndus t r y , Lon- don, 1961
;': Moser, H. , The Dynamics o f B a c t e r i a l Populat ions Mainta ined i n the Chemostat, Carnegie I n s t i t u t e o f Washington, Washington, D . C . , 1958
Moyer, J. E . , Aerobic Waste Disposal Systems, i n B i o l o g i s t i c s f o r Space Systems Symposium (May 1962), Technica l Documentary Report No. AMRL-TDR-62-116 (October 1962), 281-289
Moyer, J. E . , TDR No. AMRL-TDR-62-116, Aerospace Medical Div- i s i o n , A i r Force Systems Command, Wr ight -Pat terson A i r Force Base, Ohio, p . 281 (1962)
7': Piper , W. O . , and-Quon, J . E., Growth o f C h l o r e l l a on Prod- uc ts f rom t h e i n c i n e r a t i o n of Human Wastes, i n B i o l o g i s t i c s f o r Space Systems Symposium (May 1962), Technica l Documentary Report No. AMRL-TDR-62-116 (October 1962), 315-327
Pote, H. L . , Waste Conversion by Anaerobic Thermophi l ic Methods, i n B i o l o g i s t i c s f o r Space Systems Symposium (May 1962), Tech- n i c a l Documentary Report No. AMRL-TDR-62-116 (October 1962), 290- 294
-3-
;k Pote, H. L . , Gaf ford, R . D. Waste Processing f o r Closed A s t r o n a u t i c a l Sciences, 6 (
;t Rogovskaza, Ts. I . and M. F ( 1 959)
and Richardson, D. E . , Anaerobic Ecolog ica l Systems, Advances i n 9611, 339-403
Lazareva, M i k r o b i o l o g i c a , 28,
i, Rosebury, T , , Yicroorganisrns indigenous t o Man, McGraw-Hi 1 Book Co., i n c . , New York, 1962, p . 435
9: Ruckhoft, C . C . , J . G . K a l l a s and G . P. Edwards, J . Bacter 19, 269 (19303
9; Smith, H. W . and W . E . Crabb, J. P a t h o l . B a c t e r i o l ., 82, 53 (1961)
565
o l . ,
Miss iss. ipp i S t a t e U . , S t a t e College, Biochemical Study o f Mixed C u l t u r e Pro to type i n a Closed Eco log ica l System, NASA
A+ Progress Report No. Ui, Dec. 1 , 1962 - J u l y 1 , 1963, T ischer , R . G., I963 34p 10 r e f s /NASA Grant NSC-80-60/ /NASA CR-50860/ OTS- $3.60 FH, $ I .22 MF N63-20248
4 Juhrman, R . E . , T r e a t i n g Waste Waters f o r C i t i e s and i n d u s t r i e s p . 647, i n Water, The Yearbook o f A g r i c u l t u r e , U . S . Dept. o f A g r i c u l t u r e (1955).
7: Z e f f , 9. D., Barnbenek, R . A. , Development o f a U n i t f o r Re- covery o f Water and Disposal o r Storage o f S o l i d s f rom Human Wastes, P a r t I The Study Phase, Wr ight A i r Development Center Technical Report 58-562 (1959)
! l A 2 PRODUCTION OF AMMQNJA AND HYDROGEN
k Alexander, M . , I n t r o d u c t i o n t o S o i l M ic rob io logy , p . 259, John Wi ley and Sons, inc. , N . Y . (196,)
;': Cohen, .J. S . and Busr is , 1955, A Method f o r t h e C u l t u r e o f Hydrogen Bacter ia , 3 . B a c t e r i o l . , 69, 316-319
$: Cooke, d . 'd. and H. R . Ke i th , J . B a c t e r i o l . , 13, 315 (1927)
9~ Cowles, P . B . ar,d L . F. Ret tger , J . B a c t e r i o l . , 21, 167 (1931)
,- F u l l e r , W . E. and A . G. Norman, J. B a c t e r i o l . , 46, 273 (1943)
-,'c F u l l e r , W . H. and A. G . Norman, J . B a c t e r i o l . , 46, 281 (1943)
A F u l l e r , W . H . and A . G , Norman, 3 . B a c t e r i o l . , 46, 291 (1943)
- 4-
k Gest, H., B a c t e r i o l . Revs., 18, 43 (1954)
9; Gibbons, R. J. and R. N. Doetsch, J. B a c t e r i o l . , 77, 417 (1959)
;t Hermann, E . R., J. SOC. Engineer ing D i v i s i o n Proc. American SOC. C i v i l Engineers, 88, SA 5, 1 , (1962)
9; Hungate, R. E . , Bact. Revs., 14, 1 (1950)
9; Khouvine, Y . , Ann. de I ' I n s t . Pas t . , 37, 711 (1923)
Melpar Corp., Contract DA 36-039 SC-90878, Second Q u a r t e r l y Progress Report, 1 Oct. - 31 Dec. 1962 (1963)
N a g l i s k i , J,, J. W, White, Jr., S. R. Hoover and J . J . Wi l lamin , J. B a c t e r i o l . , 49, 563(1945)
Nisman, R . , M. Raynard, and G . N. Cohen, Arch. Biochem., 16, 473 (1948)
J o i n t P u b l i c a t i o n s Research Service, Washington, D. C . , New ;k Developments i n Biochemistry. S . Sever in. June 15, 1962. 12p
T rans l . f r o m Pravda/Moscow/, Sept. 16, 1961. p. 6. /JPRS-14129/ D i s t r i b u t e d by OTS. N62-13101
;k St i ck land , L . H. , Bioch. J., 28, 1746 (1934)
;? Wheaton, R . B . , J. J . Symons, N. G . Roth and H. H. M o r r i s , TDR No. AMRL-TDR-62-116, Aerospace Medical D i v i s i o n , A i r Force Systems Command, Wright-Patterson A i r Force Base, Ohio, p . 295 (1962)
9; Wiley, W. H. and J. R . Stokes, J. B a c t e r i o l . , 84, 730 (1962)
Zobe l l , C . E . , M i c r o b i a l Transformat ion o f Molecular Hydrogen i n Marine Sediments w i t h P a r t i c u l a r Reference t o Petroleum, Am. Assoc. Petroleum Geol. 31, 1709 (1947)
;k Zobe l l , C . E., A s s i m i l a t i o n o f Hydrocarbons by Microorganisms, Advances i n Enzymology 10, 443 (1950)
I I B ENZYMES
I 131 CELLULASES
;k Basu and Whitaker, Arch. Biochem. Biophys., 42, 12 (1953)
;k Duncan, Manners and Ross, Biochem. J., 63, 44 (1956)
-5 -
i'c Studies i n Cel
Enebo e t . a l . , ;'c Festens te in , B
u lose Decomposition, Enebo, Stockholm (1954)
J. o f the I n s t . o f Brew., 59, 207 (1953)
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9: B i o l o g i c a l Degradation o f Ce M. M. Casoigne, But te rwor ths
;'c G r e e n f i e l d and Lane, J. B io l
Holo and S z i l a g y i , Ind. ag r . ( 1 957)
lu lose , J. A . Gascoigne and London , Eng 1 and ( 1 960)
Chem. , 204, 669(1953)
e t . a l imen t . (Par is ) 74, 131
tt Hungate, B io l . B u l l . , 83, 303(1942)
;'c Husemann and L o t t e r l e , Makromol. Chem., 4, 278 (1950)
Jermyn, Aust. J. Sc i . Res., 8 5 , 409 (1952)
;'c K a r r e r and I1 1 ing, Kol l o idzsch r . , 36, 91 (1925)
;+ Koviman, Enzymologia, 18, 22 (1957)
M is ra and Ranganathan, Proc. l nd . Acad. Sc i . , 398, 100 (1954)
;': Nisizawa, J Biochem. (Japan) 42, 825-827 (1955)
;': Okamoto and Asai , J. A g r i c , Chem. SOC. (Japan), 26 (1952)
;'c Reese, G i l l gan and Norkraus, P h y s i o l . P lan t , 5, 379 (1952)
Saunders, S i r e and Genest, J. B i o l . Chem., 174, 697 (1948)
i? S e i l l e r e , C . R . , SOC. Bio. (Pa r i s ) , 61, 205 (1906)
S e i l l e r e , C . R . , SOC. Bio. (Pa r i s ) , 63, 151 (1907)
;': S e i l l e r e , C. R . , SOC. Bio . ( P a r i s ) , 68, I O 7 (1910)
Sison, Schubert and Nord, Arch. Biochem. Biophys., 75, 260 ( 1 958)
+c Stone, Ph.D. Thesis, U n i v e r s i t y o f London (1954)
9: Stone, Biochem. J.,6G, 1 (1957)
7': Toyama, J. Ferment. Technol. (Japan), 34, 281 (1956)
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;'i Whitaker, Arch. Biochem. Biophys., 43, 253 (1953)
;k Whitaker, Science, 116, 90 (1952)
I I82 PECTl NESTERASES
Advances i n Enzymology, Vol 20, H. Deuel and E . Stu tz , l n t e r s c i e n c e Publ ishers, I nc . , N . Y . e d i t e d by F. F. Nord, (1958)
;'i Holden, M., Biochem, J . , 40, I03 (1946)
;': Lineweaver, H., and G. A . Ballow, Arch. Biochem., 6, 373 (1945)
;': Advances i n Enzymology, Vol . I I , H. Lineweaver and E . F. Jansen, l n t e r s c i e n c e Publ ishers, Inc. , N. Y . , e d i t e d by F. F. Nord (1951)
it MacDonnell, L . R . , E. F. Jansen and H. Lineweaver, Arch. B io- chem., 6, 389 ,( 1945)
;$ McColloch, R . J., J. C. Moyer and Z. I . Kertesz, Arch. B io - chem., 10, 479 (1946)
;'c McColloch, R. J . , Z . I . Kertesz, Arch. Biochem., 13, 217 (1947)
;k M i l l s , C. B . , Biochem. J . , 44, 302 (1949)
5: Owens, H. S . , R . M. McCready and W. D . Maclay, Ind. Eng. Chem. 36, 936 (1944)
;': P i thawala, R . R. , C . R . Savur and A, Screenivasan, Arch. B io- chem., 17, 235 (1948)
:'; Schul tz , T. H., H. Lotzkar , H. S . Owens and W . D . Maclay, J . Phys. Chem., 49, 554 (1945)
l J B 3 POLYGALACTURASES
5; Deuel, H., and F. Weber, Helv. Chim. Acta, 29, 1872 (1946)
;k Jansen, E. F., L . R . MacDonnell and R . Jang, Arch. Biochem. 8, 1 1 3 (1945)
:': Jansen, E. F., R . Jang, L. R . MacDonnell, Arch. Biochem. 15, 415 (1947)
;? Koch, J . , F ruch tsa f t - l nd . , 1 , 66 (1956$
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-7-
:? Ozawa, J., Ber. Ohara I n s t . l andw i r t sch . Forsch. K u r a s k i k i Japan, 9, 431 (1951)
;'c Pallman, H. and H. Deuel, H. Chimia, 1 , 27 ,(1947)
9: Schubert, E., Biochem. J. , 78, 323 (1952)
fc Schubert, E . , M e l l i a n d T e x t i l b e r , 8, (1954)
I 18.4 L I PASES
Bay l i ss , M., D . G l i c k and R. A . Siem, J . B a c t e r i o l . , 55, 307 ( 1 948)
fc Biochemical Problems o f L i p i d s , B. Borgstromm, G. Popjak and E. LeBreton, eds., Bu t te rwor ths , London, England (1956), 179
fc Methods i n Enzymology, Vol . I , e d i t e d by Sidney Colowick and Nathan Kaplan, Academic Press Inc . , New York (1955)
;': Connstein, W . , E. Hoyer and H. von Wartenberg, Ber. 35, 3988 ( 1 902)
fc Constant in, M. J . , L . Pasero and P. Desnuelle, Biochem. a t . Biophys. Acta, 43, 103 (1960)
;? The Enzymes o f L i p i d Metabolism, e d i t e d by P . Desnuelle, Pergamon Press, London, England (1961)
fc F io re , J. V . and F. F. Nord, Arch. Biochem., 26, 382 (1950)
;? G o l d b l i t h , S . and E. Wicks, ASD Technical Report 61-419, ASTlA 266882 (1961)
;': Gorbach, G . and H. Guntner, S i t z b e r . Akad. W i s s . Wein. Mathnaturw, K I , Ab t . I I b , 141, 415 (1932)
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:k Marchis-Monrew, G . , L . Sarda and P . Desnuelle, Biochem. e t . Biophys. Acta, 41, 358 (1960)
;': Savory, P . and P. Desnuelle, Biochem. e t . Biophys. Acta, 21, 349 (1956)
7': Schonheyder, F. and K. Volqvartz, Enzymologia, I I , 178 (1944)
i? Schonheyder, F. and K . Volquartz, Acta P h y s i o l . Scand., 10, 62 (1945); 1 1 , 349 (1946)
-8-
it S t a r r , M. P . and W. H. Burkholder, Phytopathology, 32, 598(1942)
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:; W i l l s , E. D., Biochem. Biophys. Acta, 40, 487 (1950)
7'; W i l l s , E. D., Biochem. J., 57, 109 (1954)
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I l B 5 PAPAINS
9; Anson, M. L., J. Gen. Phys io l . 22, 79 (1938)
;> B a l l , A . K . and H. Lineweaver, J . B i o l . Chem., 130, 669 (1939)
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+; Hwang, K. and A. C . Evy, Ann. New York Acad. Sc i . , 54, 161 (1951)
k I r v i n g , G . W . J r . , J . S . Fru ton and M. Bergmann, J. B i o l . Chem., 138, 231 (1941)
:> K inne l , J. R . and E. L . Smith, J . B i o l . Chem., 207, 515 (1954)
;> Kun i tzy , M., J. Gen. Phys io l . , 30, 311 (1947)
;': Lineweaver, H. and S. Schwimmer, Enzymologia, 10, 81 (1941)
l l B 6 UREASES
2'; Methods i n Enzymology, Vol . 2, e d i t e d by Sidney P . Colowick and Nathan 0. Kaplan, Academic Press, I nc . , New York (1955)
Dounce, A. L . , J . B i o l . Chem., 140, 307 (1941)
9~ Fosman, G . D . and C. Niemann, J . Am. Chem. S O C . , 7 3 , 1646 (1951)
9; Gorin, e t a l . , Biochemistry, 1 , 911 (1962)
,k Hellerman, L, , F. B. Chinard and U. R . Die tz , J . B i o l . Chem., 147, 443 (1943)
-9-
;': K is t iakowsky , C . 8. and R. Lumry, J . Am. Chern. SOC. , 71, 2006 (1949)
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;k Larson, A. D. and R . E. K a l l i o , J. B a c t e r i o l . , 68, 67 (1954)
5: Shaw, W. H. R. and C . B. K is t iakowsky, J. Am. Chem. SOC., 72, 2817 (1950)
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Sumner, J. B. and L . 0. Poland, Proc. SOC. E x p t l . B i o l . Med., 30, 553 (1933)
3': Wa l l , M. C . and K . J. L a i d l e r , ABB, 43, 307 (1953)
;'; Wal l , M. C . and K. J. L a i d l e r , ABB, 43, 299 (1953)
l l B 7 SULFATE REDUCTASES
i': A l l e n , L. A. , The E f f e c t of Nitro-Compounds and Some Other Substances on Produc t ion o f Hydrogen Sulphide by Sulphate- reduc ing B a c t e r i a i n Sewage, Proc. SOC. Appl . B a c t e r i a l . 20, 26-28 (1949)
;k Booth, G. H. and T i l l e r , 1960, P o l a r i z a t i o n Studies o f M i l d S tee l i n Cu l tu res o f Sulphate-reducing B a c t e r i a , . T r a n s . Faraday SOC. , 56, 1689-1696
B u t l i n , K. R . , Adarns, and Thomas, 1949, The I s o l a t i o n and C u l t i v a t i o n o f Sulphate-reducing Bac ter ia , J . Gen. M i c r o b i o l . , 3, 46-59
Gregory, J. D. and P. W. Robbins, Metabol ism o f S u l f u r Com- pounds ( S u l f a t e Metabol ism), Ann. Rev. Biochem. 29, 347-3614 ( 1 960)
5: L a z z a r i n i , R . A. , The Reduct ion o f N i t r i t e by Enzymes o f Escher ich ia C o l i , Ph. D. Thesis, U n i v e r s i t y o f C a l i f o r n i a , (Los Angel es) , (June 1960)
;k M i l l e r , L . P . , 1950, Tolerance o f Su l fa te - reduc ing B a c t e r i a t o Hydrogen S u l f i d e , Cont r ib . Boyce Thompson I n s t . , 16, 73-83
4 M i l l e r , L . P . , 1949, S t i m u l a t i o n o f Hydrogen S u l f i d e Produc t ion by Su l fa te - reduc ing Bac ter ia , C o n t r i b . Boyce Thompson I n s t . , 15, 467-474
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;f Postgate, J . R. , S u l f a t e Reduct ion by B a c t e r i a , Annual Rev. M i c r o b i o l o g y 13, 505 (1959)
+: H. R . Schre iner and A. P . R i n f r e t , E f f e c t o f Water-Soluble Polymers on N i t r a t e Reductase A c t i v i t y , Nature 190, 1110-1112 (1961)
it: S i s l e r , F. D . and ZoBe l l , 1951, N i t r o g e n F i x a t i o n reducing B a c t e r i a I n d i c a t e d by N i t r o g e d a r g o n Rat 113, 511-512
;': Starkey, R. L . Su l fa te - reduc ing B a c t e r i a - Physio P r a c t i c a l S i g n i f i c a n c e , U . o f Md., Dept. o f M i c r o B u l l e t i n , 1960
by S u l f a t e - os, Science,
ogy and i o l o g y
;f Zobel 1 , C . E . , R i t tenberg , S. C . , Sul f a t e - r e d u c i ng B a c t e r i a i n Mar ine Sediments, J . Marine Research (Sears Foundat ion 7, 602 (1948)
;': ZoBe l l , C . E . , 1958, Ecology o f S u l f a t e - r e d u c i n g B a c t e r i a , Producers Monthly, 22, 12-29
I l B 8 HYDROGENASES
7': Adams, M. E . , B u t l i n , Hol lands and Postgate, 1951, The Role o f Hydrogenase i n t h e Autot rophy o f Desu lphov ib r io , Research, 4, 245-246
;k Kresna, A. I ., E. R i k l i s , and D. R i t tenberg , The P u r i f i c a t i o n and P r o p e r t i e s o f t h e Hydrogenase o f D e s u l f o v i b r i o d e s u l f u r i c a n s J . B i o l . Chem. 235, 2717-2720, (1960)
;': M a r s h a l l , C. E. and Bergman, W . E. J . Am Chem. SOC. 63, 1911 1941
;f Marsha l l , C . E. and K r i n b i l , C . A . , J . Am. Chem. SOC. 64, 1814, 1942
;? Mechalas, B. J . and S. C . R i t tenberg , Energy Coupl ing i n Desul- f o v i b r i o d e s u l f u r i c a n s , B a c t e r i o l . Proc., A b s t r . P53, 164, (1960)
:': Ormerod, J . G . , and H. Gest, Hydrogen Photosynthes is and A l t e r - n a t i v e M e t a b o l i c Pathways i n Photosynthe t ic B a c t e r i a , B a c t e r i o l . Rev. 26, 51-66 (1962)
+: R i c k l i s , E. and R i t tenberg , 1961, Some Observat ions on t h e Enzyme, Hydrogenase, J . B i o l . Chem, 236, 2526-2529
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Sadana, J. C . and A. V. Morey, The P u r i f i c a t i o n o f Hydrogenase o f D e s u l f o v i b r i o desu l fu r i cans , Biochem. Biophys. Acta. 32, 592-593, (1959)
;k B. L . V a l l e e and F. L . Hock, Yeast Alcohol Dehydrogenase, Z inc Metalloenzyme, J. Am. Chem. SOC., 77, 821 (1955)
F. H. Westheimer, H. F. F The Enzymatic T rans fe r o f Chem. SOC., 73, 2403 ( I95
I l B 9 CATALASES
sher, E. E. Coon, and B . Vennes Hydrogen from Alcohol t o DPN, J 1
A
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7 ' ~ 8 . Chance, D . S. Greenstein, and F. J. W. Roughton, The Mechanism o f Catalase Ac t i on . 1 . Steady-State Ana lys i s . Arch. Biochem. Biophys. 37, 301 (1952)
l l B l O ROLE OF METAL IONS I N ENZYME SYSTEMS
;': Lehninger, A. L., Role of Metal Ions i n Enzyme Systems, Phys- i o l og i ca 1 Revi ew, 30, 393-483 ( 1 950) 225 Reference
:': H. Kubo and M. Iwatsubo, A Spectrometr ic Study o f Meta ls i n Some Oxidases, Bunko Kenkyu I , No. 4, p 15-21 (1949)
I l l BIOELECTROCHEMICAL CONVERTERS AND RELATED STUDIES
l l l A FUNDAMENTAL INVESTIGATIONS
I l l A l ELECTRODE STUDIES
;'i Elec t rode K i n e t i c s and Fuel C e l l s . L. G. A u s t i n /Pennsylvania S t a t e U n i v e r s i t y , Dept. o f Fuel Technology, U n i v e r s i t y Park, Pa./ IEEE, Proceedings, Vol . 51, May 1963, P. 820-837. 15 Refs. A63- 16775
;': Booth, G. H., and T i l l e r , A . K . , Faraday Society, 1960, 56, I689
;k Booth, G. H., and Wormwell, F., F i r s t I n t e r n a t i o n a l Congress on M e t a l l i c Corrosion, 1961, p . 341
Aeronautronic, Newport Beach, C a l i f . Study o f Basic B io -E lec t ro - chemistry Q u a r t e r l y Engineering Progress Report, 19 Mar. - 19 June 1963, M. H. Boyer, R. C. Bean, Y . H. Inami, E. R . Walwick, and R. E. Kay J u l y 19, 1963 41p 12 r e f s /NASA Contrac NASW- 655/ /NASA C R - 5 1 1 1 3 , u-22081 OTS $4.60 PH, $1.43 MF, ~63-21729
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Aeronaut ic , Newport Beach, C a l i f . Study o f Basic B io -E lec t ro - Chemistry Q u a r t e r l y Engineer ing Progress Report, 20 June. - 19 Sept. 1963, M. H. Boyer, R. C. Bean, Y . H. Inami, and W . C. Shep- herd 19 Oct. 1963 69p /NASA Contract N A S W - 6 5 9 /NASA CR-52607, U-2332/ OTS- $6.60 PH, $2.27 MF, N64-11103
Magna Corp., Anaheim, C a l i f . Research and Development Div . B io - chemical Fuel C e l l s Four th Q u a r t e r l y Progress Report, Apr. 1 -
i'c June 30, 1963, J . M. Brake, W . R. Momyer, and H. P. Si lverman 1963 3Op 1 1 r e f s . , /Contract DA 36-039-SC-90866/ N63-23418
Magna Corp., Anaheim, Cat i f . Research and Development D iv . B io - chemical Fuel Ce l l s , F i f t h Q u a r t e r l y Progress Report, 1 J u l . - 1963 38p re fs . , /Contract DA-36-03g-SC-90866/ /AD-426937/ N64- 13968
;k 30 Sept. 1963, J. M. Brake, W. R. Momyer, and H. P. Si lverman
Magna Corp., Anahelm, C a l i f . Research and Development D iv . , Research on App l ied B ioe lec t rochemis t ry , Q u a r t e r l y progress
;k Report No. 2, J u l . 1 - Sep. 30, 1963, James H. Canf ie ld , Oct. I963 46p r e f s /NASA Contract NAS!J-623/ /NASA CR-52606, 339/7014/ T6, 714-772-1261/ OTS- $4.60 PY, $1.58 MF, N64-11323
;'c. Carr , C. W . Gregor, H. P., and So l l ne r , K . J. Gen. Phys io l . 28, 179, 1945
;k Clark , W . M . , Oxidat ion-Reduct ion P o t e n t i a l s o f Organic Systems, Wi l l iams & Wi l k ins , Bal t imore, 1960
7'; Cohen, B., The B a c t e r i a l Cu l tu re as an E l e c t r i c a l H a l f - C e l l , Jour . o f Bac ter io logy , Vo l . 21, p . 18 (1931)
5: Cohen, Barnet t , 1931, The B a c t e r i a l Cu l tu re as an E l e c t r i c a l Ha l f -Ce l l , J. B a c t e r i o l . 21, 18-19
+; Do l i n , M. I . , Survey o f M ic rob ia l E l e c t r o n Transpor t Mechanisms Chapter 6 o f The Bac te r ia Vol . I I , e d i t e d by I . C . Gunsalus and R. Y. Stan ier , Academic Press 196
;k Gatty , O. , and Spooner, E. C . R., o f Corroding Meta ls i n Aqueous So X .
;k Gregor, H . P. and So l l ne r , K . , J .
Elec t rode P o t e n t i a l Behavior u t i o n s , Oxford, 1938, Chapter
Phys. Chem. 58, 409, 1954
The A c t i o n o f Magnetic F i e l d on the Sodium Transpor t Across the
Mi lan, I n s t i t u t e o f Human and General Phys io logy, Mi lan , I t a l y / i'c C e l l Membrane, T. G u a l t i e r o t t i and V . Capraro / U n i v e r s i t y o f
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. .'
Cospar, I n t e r n a t i o n a l Space Science Symposium, 4 th , Warsaw Poland, June 3-11, 1963, Paper. 8p A63-18961
Hadley, R . F . , 1943, The In f l uence o f Sporov ib r i o desu l fu r i cans on the Current and P o t e n t i a l Behavior o f Corroding I ron , Bu. Stand., S o i l Corros ion Conf., S t . Louis , pp76
Kedrov, K . P. , The C h a r a c t e r i s t i c s o f t h e Oxidat ion-Reduct ion Processes i n t h e I n t e s t i n e s , Biochem. , J . (Ukraine) 1 1 , 243 ( 1 938)
Union Carbide Corp., Parma, Ohio, Th in Fuel Ce l l E lect rodes 9: Q u a r t e r l y Report No. 1 , 1 June - 1 Sep. 1963, K . V . Kordesch
F o r t Monmouth, N.J. Army E lec t ron . Res. and Develop. Lab. 1963 167p Refs. , /Contract DA-36-039-AMC-O2314/E// /AD-425031/ N64- 1 2058
J o i n t P u b l i c a t i o n s Research Serv ice, Washington, D . C . , B io- geochemistry o f S u l f u r , s. I . Kuznetsov 9 Jan. 1964 20p Refs. , T rans l . i n t o Eng l i sh o f an A r t i c l e f rom I z v . Akad. Nauk SSSR Ser. B i o l . /Moscow/, No. 5, 1963 p 668-680, /JPRS-22672, OTS- 64-21 249/ OTS- $0.50 , N64- 13007
Lemaire, R . , On the Oxidat ion-Reduct ion P o t e n t i a l o f A r t e r i a l Blood i n Vivo, SOC. de B io log ie , Pa r i s , Comptes Rend. 141, 775, (1947)
i'c L i t t l ewood , D . and Postgate, 1957, On the Osmotic Behaviour o f Desu lphov ib r io desulphur icans, J . Gen. M i c r o b i o l . , 17, 596- 60 3
Magna Products, Inc. , B io -E lec t rode Ocean B a t t e r Research and Development Program, Tech. Rpt. , J u l y 1961, 9
;'i Mechalas, B. and R i t tenberg , 1960, Energy Coupl ing i n Desul- f o v i b r i o desu l fu r i cans , J. B a c t e r i o l . , 80, 501-507
i'c Nagamatsu, M. , Seiyania, T . , and Sakai, W . , J . Electrochem. SOC. Japan 21, 270-4, 1953
Postgate, J . , Progress i n I n d u s t r i a l M ic rob io logy , Vol . 2, l n t e r s c i e n c e Pub1 i she rs , Inc . , New York (1960)
5; P o t t e r , M. C . , E l e c t r i c a l E f f e c t s Accompanying the Decomposi- t i o n o f Organic Compounds Proc. Roy. SOC. (London) Ser ies B Vol . 84 (1911)
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Magna Corp. Research and Development Labs., Anaheim, C a l i f .
J. H. Can f ie ld i n Army Signal Research and Development Lab. E l e c t r o n i c Components Dept., Sources Conf., F o r t Monmouth, N.J . May 22-24, 1962 p18-21 , /See N63-14123 09-06/ /Cont rac ts NOBS- 78659, NOBS-84243 , and NOBS-84622/ N63- 141 30
;? Biochemical Fuel Ce l l s , G. H. Rohrback, W. R . Sco t t , and
ROSS, S . , Markar ian, M . , and Schroeder, W . , U. S . Patent 2, 648, 717
;': Sawada, T., Oshima, T . , Suzuki, I . , Oxidat ion-Reduct ion Po- t e n t i a l s i n R e l a t i o n t o t h e C u l t i v a t i o n o f Entamoeba H is to - l y t i c a and t o t h e Establ ishment o f Amoebic I n f e c t i o n . Guma J . o f Med. Sciences (Japan) 2, 127-35 (1953)
;? S i s l e r , F. D . and Zobe l l , C . E . , J. Bact. , 60, 1950, 747
f: So l lne r , K . and Gregor, H. P . , J. Phys. Chern. 51, 299, 1947
fc So l lne r , K . J . Electrochem. SOC. 97, 139C, 1950
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4 S o l l n e r , K . and Gregor, H. P . , J . C o l l . S c i . 6, 557, I951
f; S o l l n e r , K . and Gregor, H. P . , J. C o l l . S c i . 7, 37, 1952
9: T i l l e r , A . K . , and Booth, G . H., Trans. Faraday Soc ie ty , Pa r t I I , 1962, 58, 110
fc T r i v e d i , A . K . M. and D iva t i a , A. S . , Proc. I nd ian Acad. Sc i . 37A 33-37, 1953
General Dynamics/Fort Worth, Tex. I n v e s t i g a t i o n o f E l e c t r o - Chemical P roper t i es o f L i q u i d and Frozen E l e c t r o l y t e s a t Low
fc Temperatures, H. J. Weltman, 4 Nov. 1963 65p Refs., /Cont rac t AF 33/657/-11214/ /FGT-2917, AD-423614/, N64-12318
J o i n t P u b l i c a t i o n s Research Service, Washington, D . C . , Studies
T rans l . i n t o Eng l i sh o f Three A r t i c l e s f rom Vopr. Med. Khim. ;k i n Biochemistry, N. I . Yelkina e t a l 2 J u l . 1963 25p Refs.,
/MOSCOW/, V . 9 , NO. 2, 1963 p 154-160, 180-188 /JPRS-19995 OTS-63-31185/ OTS- $0.75, N64-12570
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l l l A 2 BIOELECTRIC ACTIVITY
* Abrams, I . and S o l l n e r , K.,J. Gen. P h y s i o l . 26, 369, I943
* Bennett, M . V . L . and Wurzel, M. and Grundfest, H., The E l e c t r o - phys io logy o f E l e c t r i c Organs o f Marine E l e c t r i c Fishes I, J. Gen. Phys io l . , 44, 757 (1961)
* Bennett, M . V . L . and Grundfest, H., The E l e c t r o p h y s l o E l e c t r i c Organs o f Marine E l e c t r i c Fishes 1 1 , J. Gen 44, 805 (1961)
09Y of P h y s i o l .
* Bennett, M.V.L. and Grundfest, H., The E l e c t r o p h y s l o ogy o f E l e c t r i c Organs o f Marine E l e c t r i c Fishes I l l , J. Gen. Phys io l . 44, 819 (1961)
* Bennett, M . V . L . and Grundfest, H, and Keynes, R. D., The D l s - charge Mechanisms o f t h e E l e c t r i c C a t f i s h , J. P h y s i o l . , 143, 52 ( 1 958)
* Bennett, M . V . L . and Grundfest, H., E l e c t r o p h y s i o l o g y o f E l e c t r i c Organ I n Gymnotus Carpo, J. Gen. P h y s i o l . , 42, 1067 (1959)
* Carr, C. W. and S o l l n e r , K. J. Gen. P h y s l o l . 28, 119, 1944
Jf Chance, B r i t t o n , Free Radicals I n B i o l o g i c a l Systems, Academic Press, New York (1961)
* Cox, R. T. , Coates, C. W. and Brown, M. V., E l e c t r i c a l Charac- t e r i s t i c s o f E l e c t r i c Tlssue, Ann. N . Y . Acad. Sc l . 487-500(1946)
Naval R a d l o l o g l c a l Defense Lab., San Franc isco, C a l i f . Sodium * Dependence o f B l o e l e c t r l c Outputs i n R a t Stomach, 3. T. Cummins and B . E. Vaughn, Jan, 14, 1963 l o p 9 Refs /USNRDL-TR-608/ N63- 13573
C a l i f o r n i a U., Berke ley. Lawrence R a d i a t i o n Lab. B i o e l e c t r i c S e n s i t i v i t y t o I r r a d i a t i o n o f t h e Ret ina and V isua l Pathways, * C. T. Gaf fey and A. K. Ke l ley , 9 Sep. 1963, 41p r e f s . , /Contract W-7405-ENG-48/ /UCRL- 1 IOOS/ OTS- $ 1 . O O , N64- 1 1097
JC Grundfest , H., E l e c t r i c l n e x c i t a b i l i t y o f Synapses and Some Consequences I n t h e Central Nervous System, P h y s i o l . Rev., 37, 337 (1957)
* Gunsalus and S t a n i e r , The B a c t e r l a , Vo l . I : S t r u c t u r e , Academic Press, New York (1960)
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Electroencephalographic I n v e s t i g a t i o n o f t h e Func t iona l S t a t e of t he Human Central Nervous System Under Cond i t ions o f Prolong- ed I s o l a t i o n , Elektroentsefalograficheskoe l s s ledovan ie Funktsional7':Nogo S o s t o i a n i i a T s e n t r a l n Noi Nervnoi Sistemy Cheloveka, Nakhodiashchegosia V U s l o v i i a k h Dlite1:;Nogo Odino-
7': chestva, G. V . lzosimov and V . I . Miasn ikov . lskusstvennye Spu tn i k i Zemli, No. 15, 1963, p . 120-123. I n Russian. A63-18209
;k Johnels, A. F., On t h e O r i g i n o f t h e E l e c t r i c Organ i n Malapterurus E l e c t r i c u s , Quart. J. M ic ro . Sci. ,97, 455-64(1956)
3'; Kel lenberger, K . , M i c r o b i a l Genetics, Cambridge Univ. Press, London ( 1 960)
:': Keynes, R. D . , E l e c t r i c Organs i n t h e Phys io logy o f Fishes, Vol . I I , M.E. Brown, ed., Academic Press, Inc . , New York (1957) pages 323-43
J o i n t P u b l i c a t i o n s Research Service, Washington, D. C. Respira- +: t i o n and Conversion o f Energy i n t h e L i v i n g C e l l , Kotel$cNikova
I n i t s S tud ies i n Biophys. 23 Apr. 1963 p 21-33 /See N64-10795 OTS- $1.00, N64-10797
;': Langmuir, I . and Waugh, D. F . , J . Gen. Phys io l . , 21, 745-55 ( 1 938)
;': Lessman, H. W . , On t h e Func t ion and E v o l u t i o n o f E l e c t r Organs i n Fish, J. Exp. B i o l . , 35, 156 (1958)
;: Machin, K . E. and Lessman, H. W . , The Mode o f Operat ion E l e c t r i c Receptors i n Gymnarchus N i t o t i c u s , J. Exp. B io 801-81 1 (1960)
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o f t h e ' Y 39,
M ichae l i s , L . and Weech, A . W . , J . Gen. Phys io l . 1 1 , 147, 1927
:: Nachmansohn, D . e t a l , J. B i o l . Chem. 165, 223 (1946)
J o i n t Pub1 i c a t i o n s Research Service, Washington, D . C . , Ther- modynamics o f I r r e v e r s i b l e Processes and t h e Problems o f B io - genesis /Termodinamika Neobratimykh Protsessov I Problemy
:': Biogeneza/. L . A. Nikolaev. Apr. 2, 1962, 20p. 12 r e f s . , /JPRS- 13286/ T r a n s l . f rom Zhur. F i z . Khim,/Moscow/ V . 36, No. 1 , 1962 p . 3-14. D i s t r i b u t e d by OTS. N62-12261
+: Robertson, J. David, Progress i n B iophys ics , Vol . 10, Per- gamon Press, New York (1960)
i': Scho f fen ie l s , E . , Les Bases Physiques e t Chimiques des P o t e n t i a l s B i o e l e c t r i q u e s chez Electrophorus E l e c t r i c u s L . , Arch. I n t e r n a t .
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Phys io l . Biochem., 68, 1-151
i': Schwan, H . , Advances i n B i o l o g i c a l and Medical Physics, Vol . 5, Academic Press, New York (1957)
D i e 1 e k t r i c h es ka i a P r o n i t sa emos tyc B i o 1 og i c h es k i kh ObcE k t o v D i - e l e c t r i c Pe rmeab i l i t y o f B i o l o g i c a l Ob jec ts . B . I . Sedunov and
Apr. 1963, p . 617-639. 86 Refs. I n Russian. A63-16889 ;': D. A. Frank-Kamenetski i . Uspekhi F i z i c h e s k i k h Nauk, Vol . 79,
;k D i e l e c t r i c Constants o f B i o l o g i c a l Ob jec ts . B . I . Sedunov and D. A . Frank-Kamenetski i . /Uspekhi F i z i c h e s k i k h Nauk, Vol 79, Apr. 1963, p . 617-639./ Soviet Physics - Uspekhi, Vol. 6, Sept. Oct. 1963, p . 279-293. 86 Refs. T r a n s l a t i o n . f o r Abs t rac t see Accession no. A63-16889 13-16. A63-25129
Electrophytogram o f Response Rhythms o f P lan ts t o Pulsed- ;? L i g h t S t i m u l a t i o n . Aleksandra D . Semenenko, M. A. Khvedelidze,
and Agnessa D. Semenenko/Academy o f Sciences, I n s t i t u t e o f Cybernet ics, T b i l i s i , Georgian SSR/. /Adademiia Nauk SSSR, Doklady, Vol. 147, Nov. 1962, p . 727-730./ Sov ie t Physics - Doklady, Vol. 7, May 1963, p . 1061-1063. T r a n s l a t i o n . A63-17930
So l l ne r , K . , Dray, S . , G r i m , E . , and Neihof, R . , E lec t rochemica l S tud ies w i t h Model Membranes, i n J. T. Clarke, I on Transpor t . '
Across Membranes, Academic Press, New York, (1954), Page 144
i': Suck1 ing, E. E . , B i o e l e c t r i c i t y , McGraw-Hi 1 1 , 1961
Naval Rad io log i ca l Defense Lab., San Francisco, C a l i f . Radio- s e n s i t i v i t y o f B i o e l e c t r i c Funct ions o f R a t Stomach and Caecum
;': B . E. Vaughan and A. K . Davis Jan. 8, I963 28p 24refs, /USNRDL- TR-611/ N63- 13079
i': von Wolzogen Zuhr, C . A. H. and Van der V lug t , L . S . , Water (The Hague), 1934, 16, I47
Aerospace Medical D iv . School o f Aerospace Medicine, Brooks AFB Tex. E f f e c t s o f Calcium De f i c iency and Excess on Transmembrane
Aug . 1962 1 2p Refs . , /SAM-TDR-62- l o o / N63-85914 i'c P o t e n t i a l s i n Frog Heart Technical Documentary Report F. Ware,
I l l A 3 ORGANIC MEMBRANES
fc Bodamer, G . W . , U .S. Patents 2, 681,319, and 2, 681,320 (June 15, 1954
;': Clarke, J . T., Marinsky, J . A., Juda, W . , Rosenberg, N. W . , and Alexander, S . , J. Phys. Chem. 56, 100, 1952
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f: G o t t l i e b , M. H . , Neihof, R . , and S o l l n e r , K . , J. Phys. Chem. 61, 154-159, 1957
;k Graydon, W. F. and Stewart, R . J . , . J. Phys. Chem. 59, 86, 1955
Gregor, H. P . , and Wetstone, D . M., J. Phys. Chem. 61, 147-151, 1957
+: Gregor, H . P. Jacobson, H. Shai r , R. C . , and Wetstone, D. M . , J. Phys. Chem. 61, 191-197, 1957
7': H i l l s , G . , K i tchener , J., Ovenden, P . , Trans. Faraday SOC. 51, 719-728, 1955
;': Juda, W . , Rosenberg, N . W. Marinsky, J. A . , and Kasper, A. A . , J. Am. Chem. SOC. 74, 3736, 1952
8 Juda, W . and McRae, W. A . , J . Am. Chem. SOC. 72, 1044, 1950
;': Kosaka, Y . and Tajirna, A . J. Chern. SOC. Japan, Ind. Chem. Sect. 56, 279-281, 1953
Kressman, T. R . E . , Nature 165, 568, 1950
9: Krishnaswamy, N. , J . Sc i . Ind. Research I n d i a 138, 722-726, 1954
;t Neihof, R . , J. Phys. Chem. 58, 916, 1954
;': Peterson, M . and Gregor, H. P . , J . Electrochem. SOC. 106, 1051-1061, 1959
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I I I B BIOELECTROCHEMICAL FUEL CELLS
Harvard U. Graduate School o f Business Admin i s t ra t i on ,
Adams, e t a1 Fuel C e l l s Res. ASSOC., Cambridge, Mass., Oct. 1960 60p. Refs. Fuel Cel 1 Res. Assoc. , Cambridge- $18.75, N63-81905
7'; Cambridge, Mass. Fuel C e l l s -Power f o r t h e Future, David R.
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7': Bagotsk iy and A. N. Frumkin. Sept. 13, 1962. 34p. 19 Refs. , T r a n s l . o f A r t i c l e f rom Vestn ik Akad. Nauk SSSR/Moscow/, V. 32. no. 7, 1962. p . 19-32. /JPRS-15257/ OTS- $3.60. N62- 1 558 1
P h i l l i p s Petroleum Co., Atomic Energy D iv . , Idaho F a l l s , Idaho, The Design o f a P o t e n t i o s t a t f o r E lec t rochemica l Research R. H. Brown, AEC Na t iona l Reactor T e s t i n g S t a t i o n , May 1963 40p. 8 Refs., /Cont rac t at/10-1/-205/ /lD0-16852/ OTS- $1.00 N63- 1761 8
9; Fuel C e l l s - Progress, Programs, and Problems. Erns t M. Cohn, /NASA, E 1 ec t rochemi ca 1 Techno 1 ogy P r o j ec t s , Wash i ng ton, D. C . In - 12 th I n t e r n a t i o n a l A s t r o n a u t i c a l Congress, Proceedings, Vo l . 1 . Washington, D. C . , Oct. 1-7, 1961. New York and Lon- don, Academic Press, Inc. , 1963, p. 438-445. A63-21265
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Marquardt Corp., Van Nuys, C a l i f . Study o f B ioc emical Fuel C e l l s Second Q u a r t e r l y Progress Report, 1 Aug. 1963 - 31 Oct.
9: 1963. George E. E l 1 i s and Edward E. Sweeney 1963 47P /NASA Cont rac t NASW-654/ /NASA CR-5281 3, Rept. 25105/ OTS- $4.60 PH. $1.61 MF, N64-11299
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* ' - Marquardt Corp., Van Nuys, C a l i f . Biochemical Fuel Cel Is F i r s t Q u a r t e r l y Progress Report, Mar. 22 J u l y 31, 1963
9; George E. E l l i s and Edward E . Sweeney Aug. 10, 1963 59p 38 /NASA Contract NASW-654/ /NASA CR-51565, Mr-25093/ OTS- $5 PH, $1.97 MF, N63-22894
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AFMTC-TN-59-4, AD-260721 / N63-84327
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Naval Research Lab., Washington, D. C . , D i r e c t Energy Conversion L i t e r a t u r e Abs t rac ts J u l y 1963 183p 1077 Refs. , OTS- $3.00 N63-23603
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