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These experiments suggest that a common CYP11B ancestor gene that possessed both 11b-hydroxylase and aldosterone synthase activity under-went a gene duplication event before or shortly a

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Analyses of the CYP11B gene family in the guinea pig suggest

activity

Hannes E Bu¨low1,* and Rita Bernhardt2

1

Max-Delbru¨ck-Centrum fu¨r Molekulare Medizin, Berlin-Buch, Germany;2Universita¨t des Saarlandes, FR Biochemie, Saarbru¨cken, Germany

In this study we describe the isolation of three genes of the

CYP11Bfamily of the guinea pig CYP11B1 codes for the

previously described 11b-hydroxylase [Bu¨low, H.E., Mo¨bius,

K., Ba¨hr, V & Bernhardt, R (1996) Biochem Biophys Res

Commun 221, 304–312] while CYP11B2 represents the

aldosterone synthase gene As no expression for CYP11B3

was detected this gene might represent a pseudogene

Transient transfection assays show higher substrate

speci-ficity for its proper substrate for CYP11B1 as compared to

CYP11B2, which could account for the zone-specific

syn-thesis of mineralocorticoids and glucocorticoids,

respec-tively Thus, CYP11B2 displayed a fourfold higher ability to

perform 11b-hydroxylation of androstenedione than

CYP11B1, while this difference is diminished with the size of

the C17 substituent of the substrate Furthermore, analyses

with the electron transfer protein adrenodoxin indicate

dif-ferential sensitivity of CYP11B1 and CYP11B2 as well as the

three hydroxylation steps catalysed by CYP11B2 to the availability of reducing equivalents Together, both mecha-nisms point to novel protein intrinsic modalities to achieve tissue-specific production of mineralocorticoids and gluco-corticoids in the guinea pig In addition, we conducted phylogenetic analyses These experiments suggest that a common CYP11B ancestor gene that possessed both 11b-hydroxylase and aldosterone synthase activity under-went a gene duplication event before or shortly after the mammalian radiation with subsequent independent evolu-tion of the system in different lines Thus, a differential mineralocorticoid and glucocorticoid synthesis might be an exclusive achievement of mammals

Keywords: guinea pig; 11b-hydroxylase; aldosterone synth-ase; phylogeny

Higher vertebrates regulate vital processes like volume/

electrolyte homeostasis and glucose/lipid metabolism by

means of steroid hormones, namely mineralocorticoids and

glucocorticoids The biosynthesis of these steroids occurs

primarily in the adrenal cortex within morphologically and

functionally distinct zones Accordingly, mineralocorticoids

are produced by the outer zona glomerulosa while

gluco-corticoids are formed in the two inner layers of the cortex,

the zonae fasciculata/reticularis Originating from

cholester-ol they are synthesized by a number of consecutive

oxidations and dehydrogenations where all oxidative

reac-tions are catalysed by enzymes of the cytochrome P450

superfamily [2] The first and rate-limiting step is the

conversion of cholesterol to pregnenolone by the

mitochon-drial cytochrome P450 side-chain cleavage enzyme (P450scc,

CYP11A1) Subsequently, pregnenolone is

dehydroge-nated and oxidized in position 17 and/or 21 to yield

11-deoxycortisol or 11-deoxycorticosterone, respectively

Both compounds in turn are substrates for the cytochrome P450 enzymes of the CYP11B subfamiliy, namely the 11b-hydroxylase (CYP11B1) and the aldosterone synthase (CYP11B2) While CYP11B1 hydroxylates 11-deoxycorti-sol in position 11 to give corti11-deoxycorti-sol as the major glucocorti-coid, the closely related aldosterone synthase forms aldosterone as the major mineralocorticoid by means of

an 11b-hydroxylation and an 18-hydroxylation/oxidation of 11-deoxycorticosterone Thus, the proteins of the CYP11B subfamily catalysing the last biosynthetic steps are the key enzymes for the synthesis of both mineralocorticoids and glucocorticoids

From molecular cloning of the corresponding genes and analyses of the cDNAs it became obvious that the encoded isoenzymes share a very high degree of similarity ranging up to 95% on the amino acid level for human CYP11B1 and CYP11B2 [3] There are, however, a number of significant species differences For example, humans [3], mice [4], rats [5], and hamsters [6,7], possess at least two functionally different genes with the encoded proteins exhibiting different enzymatic activities While one protein modifies the steroid entity predominantly in position 11, the other one is able to hydroxylate and oxidize position 18 as well In contrast, cows [8], pigs [9], sheep [10], and frogs [11] apparently possess only one type

of a bipotent enzyme that is capable of catalysing the reactions at both positions 11 and 18 Nonetheless, the production of mineralocorticoids and glucocorticoids is strictly zone specific in all species It is, however, unknown

Correspondence to R Bernhardt, Universita¨t des Saarlandes, FR

Biochemie, PO Box 15 11 50, D-66041 Saarbru¨cken, Germany.

Fax: + 49 681302 4739, Tel.: + 49 681302 3005,

E-mail: ritabern@mx.uni-saarland.de

*Present address, Columbia University, College of Physicians &

Surgeons, New York, NY 10032, USA.

Note: a website is available at

http://www.uni-saarland.de/fak8/bernhardt.

(Received 12 April 2002, revised 11 June 2002, accepted 26 June 2002)

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which factors convey this specificity and how these similar

but distinct systems evolved

To investigate the zone-specific synthesis of

mineralocor-ticoids and glucocormineralocor-ticoids and the evolution of the

hormonal system in more detail we chose the guinea pig

as a model The guinea pig is an interesting species because

its taxonomical position remains controversial [12,13]

These features should provide new insight into the evolution

and function of the hormonal system We first cloned the

genes of the CYP11B family of the guinea pig The

11b-hydroxylase of the guinea pig showed higher substrate

specificity than the aldosterone synthase In addition, the

aldosterone synthase exhibited unique properties in that

18-hydroxylase activity was strongly dependent on the

presence of high levels of reducing equivalents whereas basic

levels were sufficient for high 11b-hydroxylase activity of

this enzyme This suggests a new regulatory level in

aldosterone synthesis that together with the higher substrate

specificity of the 11b-hydroxylase could be crucial for the

tissue-specific synthesis of steroid hormones Phylogenetic

analyses indicate a gene duplication event of a bipotent

CYP11B ancestor gene before the mammalian radiation

with subsequent distinct evolution in different clades This

indicates that a differential glucocorticoid and

mineralocor-ticoid synthesis is an exclusive property of mammals

E X P E R I M E N T A L P R O C E D U R E S

General procedures

Molecular biology procedures were carried out according to

standard protocols [14] unless stated otherwise Chemicals

and enzymes were purchased from the highest quality

sources commercially available

Screening of a guinea pig genomic library

A total of 1· 106clones of a guinea pig genomic library

(Stratagene, #946110) were screened under low stringency

conditions as described for Southern blots using a guinea

pig CYP11B1 full-length probe (1618 bp XbaI fragment

of pHBL5 [1] Positive clones were purified to

homoge-neity and analysed by Southern blotting using various

restriction endonucleases Appropriate genomic fragments

were subcloned into pBluescript SK(–) (Stratagene) and

sequenced using gene-specific primers Furthermore, to

sequence parts not represented by genomic phage clones

genomic fragments were amplified by PCR and sequenced

directly

RNA preparation

Tissue was homogenized in 6M guandinium thiocyanate

and subsequently RNA was purified by centrifugation

through a CsCl gradient [14] PolyA+RNA was isolated by

three rounds of affinity purification on oligodT cellulose

(Stratagene)

RNAse protection analyses

RNAse protection analyses were carried out using a

HybSpeedTM RPA Kit (Ambion) according to the

manufacturer’s recommendations Briefly, specific 32P labelled RNA antisense transcripts (corresponding to nucleotides 1491–1700 in the CYP11B1 cDNA [1] and nucleotides 1511–1750 in the CYP11B2 cDNA; Fig 2) were hybridized with total RNA from different tissues After digestion of the reaction mixture with RNAse A/H protected fragments were separated by PAGE and visual-ized by autoradiography

RACE The cDNA for CYP11B2 of the guinea pig was amplified and cloned using a Marathon cDNA Amplification Kit (Clontech) following the supplier’s recommendations In brief, after reverse transcription of 1 lg of polyA+RNA and second-strand synthesis an adapter comprising the T7 promoter sequence combined with a NotI and a SmaI site was ligated to both ends of the cDNA pool Using a combination of a primer complementary to the adapter (adapter primer: 5¢-CCATCCTAATACGACTCACTA TAGGGC-3¢) and a gene-specific sense primer (5¢-GCCG CTCGAGTTTGAGTTAGCCAGAAACTCC-3¢, XhoI site underlined) or antisense primer (5¢-ATACGGGCCC GACAGTGGTGTGCCTGGGAAC-3¢, Bsp120I site underlined), respectively, a PCR reaction was carried out with KlenTaqTM(Clontech) under the following conditions:

94C 2 min initial denaturation, 94 C 45 s denaturation,

72C 1 min annealing (annealing temperature reduced at 1.4C per cycle), 72 C 3 min polymerization; 10 cycles, followed by 25 cycles at 94C 45 s, 58 C 1 min and 72 C

3 min with a final extension step for 8 min at 72C The 5¢-RACE product was cloned directly into a TA Cloning vector pCR2.1 (Invitrogen) yielding pCR2.1/HG17 while 3¢-RACE products were inserted by using the XhoI and NotI sites into pBluescript SK(–) (Stratagene) giving pBSSK/3¢RACE HG17

DNA sequencing DNA sequencing was carried out using a Thermo Sequen-aseTMCycle Sequencing Kit (Amersham/USB) in combi-nation with [a-35S]dCTP followed by autoradiography with HyperfilmTMMP (Amersham)

Southern blotting Genomic DNA was digested with the appropriate enzymes, extracted twice with phenol/chloroform and precipitated using EtOHand sodium acetate After extensive washing the DNA was redissolved in Tris/EDTA, pH8.0 and sep-arated on a 1· Tris/borate/EDTA, 0.9% agarose gel After capillary transfer to HybondTMnylon membranes (Amer-sham) nucleic acids were UV cross-linked (0.24 JÆcm)2) Prehybridization was performed in 5· NaCl/Cit, 5 · Den-hardt’s, 0.5% SDS and 50 lgÆmL)1sonicated salmon sperm DNA for 2 h at 65C [a-32P]dCTP labelled DNA probes ( 1 · 106c.p.m.ÆmL)1) were hybridized in the same solu-tion for 16 h For low stringency hybridizasolu-tion the blot was washed twice at room temperature in 2· NaCl/Cit, 0.1% SDS for 10 min followed by two 30 min washes at 50C in

1· NaCl/Cit, 0.1% SDS Autoradiography was carried out with HyperfilmTMMP (Amersham)

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Construction of expression plasmids

For the construction of pCMV/11B2, pRc/CMV was

digested with Bsp120I, trimmed with Pfu polymerase

(Stratagene) and subsequently digested with NotI Likewise,

pCR2.1/HG17 was digested with SpeI, trimmed with Pfu

polymerase and digested with NotI to release a fragment

comprising the ORF of the guinea pig CYP11B2 This

fragment was ligated using NotI/blunt into the eukaryotic

expression vector

Hydroxylation assays

COS-1 cells were maintained as described previously [15]

Transfections were carried out using LipofectAMINETM

(Gibco/BRL) according to the manufacturer’s

recommen-dations One mL of transfection mix contained 2 lg of the

respective expression construct together with 1 lg pBAdx4

(bovine adrenodoxin; gift of M R Waterman, Vanderbilt

University, Nashville, TN, USA) and 6 lL

LipofectAMINETM unless stated otherwise Twenty-four

h after transfection cells were incubated with appropriate

substrates for 48 h using [1,2-3H]cortisol, [14

C]11-deoxy-corticosterone or [1,2–3H]androstenedione, respectively, as

tracers Media were extracted and analysed by high

performance TLC as described previously [16]

Phylogenetic analyses

Phylogenetic analyses were conducted using the PHYLIP

package (Version 3.5c, 1993) [17]

The sequences have been submitted to GenBank under

the accession numbers AF191278, AF191279 (for

CYP11B1), AF191281, AF191280 (for CYP11B2), and

AF191282 (for CYP11B3)

R E S U L T S

In a previous study we isolated an 11b-hydroxylase of the

guinea pig [1] by screening an adrenal cDNA library with a

PCR amplified orthologous probe Upon expression, the

isolated cDNA turned out to be a pure 11b-hydroxylase

with no detectable 18-hydroxylation activity suggesting the

existence of additional isoenzymes of the CYP11B

subfam-ily in the guinea pig To investigate this notion, a Southern

blot was performed utilizing an exon-1-specific probe of

CYP11B1under low stringency conditions and digesting the

genomic DNA with various restriction endonucleases that

did not cut within exon 1 The result (Fig 1) strongly

suggested the existence of at least three different genes as

judged from the appearance of three bands if the DNA was,

e.g digested with EcoRI/EcoRV, XbaI, or XbaI/HindIII

Although guinea pigs had been sodium depleted to

stimulate the expression of a putative aldosterone synthase

as much as possible [18], repeated screening of the cDNA

library did not result in the identification of any cDNA

other than CYP11B1 (data not shown) Thus, we devised

another strategy for the identification of additional genes of

the CYP11B subfamily in the guinea pig To this end, a

genomic library was screened under low stringency (see

Experimental procedures) utilizing a full-length guinea pig

CYP11B1 cDNA as a probe As opposed to a cDNA

library, screening of a genomic library should yield clones in

relation to their abundance in the genome rather than their relative abundance due to differential expression Indeed, this approach lead to the isolation of eight genomic clones that were classified into three subgroups based on restriction digests and hybridization experiments (data not shown) One clone termed kHG13 turned out to represent the CYP11B1 gene while kHG17 and kHG15 represented closely related genes of the CYP11B family demonstrated

by similarities of > 75% at the nucleotide level They were tentatively named CYP11B2 and CYP11B3, respectively

To clone the corresponding cDNAs, the RACE tech-nique was used PolyA+RNA was converted into a double-stranded cDNA pool and adapters comprising the promoter sequence of the T7 bacteriophage were ligated to both ends The sequences of the T7 promoter are extremely rare in eukaryotic genomes and thus convey a high degree of specificity in subsequent PCR reactions Using a primer combination of an adapter primer and gene-specific sense or antisense primers, respectively, we were able to amplify two overlapping fragments in case of kHG17 Upon sequencing

of these cDNA fragments the complete sequence of the cDNA of CYP11B2 could be deduced It comprised

2611 bp and an ORF of 1503 bp coding for a putative mitochondrial preprotein of 501 amino acids with a calculated molecular weight of 57.7 kDa (Fig 2) After Leu24 a cleavage site for the matrix-associated protease was predicted resulting in a mature mitochondrial protein of

55 kDa The deduced amino acid sequence showed 81% similarity to the guinea pig CYP11B1 and 80% similarity to the human CYP11B2, respectively (see below) The 3¢-UTR comprised 1079 bp with a canonical polyadenylation site

16 bp upstream of the polyA tail with no indications for the existence of alternative poly adenylation sites (Fig 2)

We next investigated the expression of the CYP11B genes A Northern blot probed with a CYP11B2-specific probe showed a single band of 2.9 kb (data not shown) which is consistent with the length of the isolated cDNA for CYP11B2 assuming a polyA tail of  200–300 adenine residues To see where the CYP11B genes were expressed

Fig 1 Southern blot analyses with a CYP11B1 exon 1-specific probe Fifteen micrograms of guinea pig genomic DNA was digested with the indicated endonucleases After transfer, membranes were probed under low stringency conditions with an exon 1-specific probe of CYP11B1 (nucleotides 1–141; see Experimental procedures for details) Sizes of fragments are indicated on the right.

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and whether they played a role during postnatal

develop-ment we used a highly sensitive RNAse protection assay

with RNAs from different tissues and developmental stages

As shown in Fig 3, expression of both the 11b-hydroxylase

and the aldosterone synthase was exclusively in the adrenal

gland Moreover, there was no difference in expression

between postnatal day 1 and the adult stages suggesting that

the genes were not differentially regulated during postnatal

development With respect to kHG15 we were not able to

demonstrate expression of the gene in adult tissues using

RT/PCR with various gene-specific primer combinations

(data not shown) Thus, this clone might represent a

pseudogene of the CYP11B family or a gene that is not

expressed in adult tissues

To compare the enzymatic activities of CYP11B2 and

CYP11B1, the cDNAs were cloned under the control of a

viral promoter and transiently transfected into COS-1 cells

Transfected cells were incubated with different substrates

and the resulting metabolites were analysed using TLC As seen in Fig 4A, CYP11B2 converted 11-deoxycorticoster-one to corticoster11-deoxycorticoster-one and both 18(OH)-corticoster11-deoxycorticoster-one and aldosterone These results clearly demonstrate that CYP11B2 is the aldosterone synthase of the guinea pig as

it is capable of modifying position 11 and 18 of the steroid ring In contrast, CYP11B1 produced only corticosterone and traces of 18/19(OH)-deoxycorticosterone, confirming earlier results [1] Furthermore, CYP11B2 transfected cells efficiently converted 11-deoxycortisol to cortisol and fur-ther to 18(OH)-cortisol (Fig 4B) As 11b(OH)-androsten-edione is the major C19 steroid in the guinea pig, we also used androstenedione as a substrate Under the experi-mental conditions large amounts of 11b(OH)-androstendi-one were synthesized by CYP11B2 in comparison with CYP11B1 (Fig 4C) It is noteworthy, that CYP11B2 displayed a higher enzymatic activity than CYP11B1 based

on 11b-hydroxylase activity These differences were highest

Fig 2 Sequence of the CYP11B2 cDNAof the guinea pig The nucleotide sequence and the deduced amino acid sequence are both shown The ORF (putative start and stop codon underlined) encodes a mitochondrial preprotein with a calculated molecular mass of 57.7 kDa An arrowhead indicates the presumptive cleavage site for the mitochondrial matrix associated protease Numbers on the left denote amino acids, those on the right indicate nucleotides A canonical polyadylation site is shown boldface.

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for androstenedione (fourfold) and lowest for

11-deoxy-cortisol (Fig 4) This shows a higher substrate specifity of

CYP11B1 which could be due to differences in the active

centre and/or the entry channel Moreover, it could be

important for tissue-specific synthesis of glucocorticoids

given the differences in expression levels of the two

enzymes

We next asked whether other accessory proteins might

contribute to the zone-specific synthesis of steroid

hor-mones A good candidate is adrenodoxin, an iron sulfur

containing electron donor protein that is required for the

function of mitochondrial cytochrome P450 proteins [19]

and has been shown to interact directly with the

cyto-chromes To test its significance we carried out an

experi-ment where adrenodoxin was either cotransfected or

omitted After transfection, cells were incubated with

11-deoxycorticosterone as a substrate As shown in Fig 5,

the omission of Adx leads to a sharp decrease in the activity

for the 11b-hydroxylase, CYP11B1 Intriguingly, however,

the 11b-hydroxylase activity of the aldosterone synthase

CYP11B2 was basically unaffected whereas the

18-hydroxy-lation and oxidation potential were abrogated almost

completely These results indicate clear structural differences

on the surface of these proteins involved either in

glucocor-ticoid or in mineralocorglucocor-ticoid biosynthesis despite a high

degree of similarity between the two isoenzymes More

importantly, these results indicate a new level of regulation for tissue-specific aldosterone synthesis depending on the availability of reducing equivalents

One intriguing question is how and when animals developed a hormonal system that differentially regulated the control of both electrolyte/volume homeostasis and glucose metabolism Knowing when and how differential synthetic pathways for mineralocorticoids and glucocorti-coids developed would lead to deeper understanding of these important evolutionary processes Because the guinea pig’s taxonomical classification is controversial [12,13], this species is extremely interesting in terms of vertebrate evolution and might provide insight into some aspects of the evolution of the hormonal system

Fig 4 Enzymatic acivities of CYP11B2 COS-1 cells were transfected with pBAdx4 (bovine adrenodoxin) and the expression plasmid pCMV5 [1] (CYP11B1), pRc/CYP11B2 (CYP11B2), or pRC/CMV (mock), respectively Twenty-four h after transfection cells were incubated for 48 h with 5 l M 11-deoxycorticosterone (DOC) includ-ing 4 nCiÆmL)1 [ 14 C]DOC (A), 5 l M androstendione including 0.5 lCiÆmL)1 [ 3 H]androstendione (B), or 2.5 l M 11-deoxycortisol including 0.5 lCiÆmL [3H]11-deoxycorticosterone (C) Subsequently, steroids were extracted and separated by TLC [16] In culture medium incubated substrates served as an additional control (substrate) Positions of cold standards are denoted on the left On the right percentage of total radioactivity or relative activity is given ± SD; data are from at least two different experiments performed in triplicate.

Fig 3 Tissue and age-specific RNAse protection assays Different

amounts of total RNA from different tissues and stages as indicated

were hybridized in solution with CYP11B1 and CYP11B2-specific

probes Both probes were chosen from the 3¢ untranslated regions of

the genes where sequence divergence was maximal between the two

isoenzymes Following RNAse digestion the probes protected a 210

nucleotide fragment of CYP11B1 (corresponding to nucleotides 1491–

1700 [1]) or a 240 nucleotide fragment for CYP11B2 (corresponding to

nucleotide 1511–1750; Fig 2), respectively A control lane without

RNAse (–RNAse) shows the corresponding undigested riboprobes of

242 nucleotides (for CYP11B1) and 272 nucleotides (for CYP11B2) A

molecular size marker is given on the left Different developmental

stages are denoted on the right: P1, postnatal day 1; adult.

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To answer the question how these genes might have

evolved we determined the complete genomic structure of

both genes As shown in Fig 6, both genes exhibit the

typical organization of the family, characterized by nine

exons and eight introns supporting the idea of a gene

duplication event It is, however, noteworthy that the exons

are grouped into three clusters comprising exons 1 and 2,

exons 3–5 and exons 6–9, respectively These clusters are

separated by intron 2 and intron 5, which are not only

larger than any other intron but also show considerable

differences in sequence similarity For example, an

align-ment [20] of intron sequences requires the introduction of 11

and 14 gaps for intron 2 and 5, respectively, as compared to

1 (intron 7) to 7 (intron 6) for the remaining introns Finally,

the 3¢ UTRs of the guinea pig CYP11B genes show only

42% similarity whereas the 3¢UTR of the guinea pig

CYP11B2 gene shares up to 72% identity with the

corresponding human homologue indicative of a close

relationship of CYP11B2 sequences between species

Comparing the protein sequences of the CYP11B family (Table 1) we were surprised to find that both CYP11B1 and CYP11B2 of the guinea pig are always more closely related (or equal) to the CYP11B2 sequences of other species Moreover, the guinea pig CYP11B2 is always more similar

to CYP11B proteins of other species than CYP11B1 of the guinea pig (compare lines A and B) Together these results suggest that the CYP11B2 genes are the primordial genes and that a common ancestor containing both enzymatic activities was duplicated The resulting two genes subse-quently evolved to give both different regio-specificities and differential regulatory circuits

We next asked when the aforementioned gene duplication event might have occurred To this end we conducted phylogenetic analyses with all known sequences of the CYP11B family of proteins Including the sequences of the guinea pig with its highly controversial taxonomical posi-tion into this highly homologous family of proteins could possibly give new insights into both its taxonomical classification and the evolutionary relationships within this protein family Also, these analyses might indicate when the gene duplication event occurred that subsequently led to isoenzymes harbouring different enzymatic activities like, for example, those in humans or to an exclusively differen-tial regulation like seen in cattle Amino acid sequences of 16 CYP11B proteins were subjected to phylogenetic analyses using two fundamentally different methods The use of various methods should provide an estimate of methodical errors On the one hand, two distance matrix methods, the UPGMA (unweighted pairgroup method using arithmetic mean) and the neighbor joining method (reviewed in [21]), were used The distance matrices for the calculation of phylogenetic trees were produced with three different algorithms for amino acid exchanges, namely the Dayhoff model [22], Kimura’s model [23] and the categories model developed by Felsenstein [24] On the other hand, the maximum parsimony method as a single character state algorithm was used to evaluate the phylogenetic relation-ships between these proteins This approach assumes the most probable phylogeny to be the one that requires the fewest nucleotide exchanges [17] The frog was used as an outgroup in all applications and the reliability of a given topology was assessed using the bootstrapping procedure [25]

The results are depicted in Fig 7 No matter which algorithm was used, the guinea pig sequences were grouped together with bootstrapping probabilities of at least 98% The maximum parsimony method placed the guinea pig into one group with rodents requiring 1349 nucleotide exchanges thus supporting monophyly of the rodents Within the rodents the branching consistently grouped the orthologues of rat and mouse together demonstrating the close relationship between these species In contrast, both distance matrix methods showed the guinea pig together

Fig 5 Influence of bovine adrenodoxin on enzymatic activities COS-1

cells were transfected with pBAdx4 (bovine adrenodoxin) and the

expression plasmids pCMV5 [1] (CYP11B1), pRc/CYP11B2

(CYP11B2), or pRC/CMV (mock), respectively Twenty-four hours

after transfection, cells were incubated for 48 h with 5 l M

11-deoxy-corticosterone (DOC) including 4 nCiÆmL)1[ 14 C]DOC Metabolites

were analysed by TLC Enzymatic activity is given as relative

radio-activity White bars represent cotransfection with adrenodoxin (¼ 100)

and black bars represent no cotransfection expressed in relation to

100 ± SD; n ¼ 9 for each data point.

Fig 6 Genomic structure of CYP11B1 and CYP11B2 of the guinea pig.

Shown is the complete genomic structure of CYP11B1 and CYP11B2.

Exon and intron boundaries are indicated Scale bar represents 1000

nucleotides.

Table 1 Pair-wise sequence similarities of CYP11B proteins Similarities for the CYP11B proteins were determined pair-wise using the PALIGN

program (PcGENE, Intelligenetics) for the proteins from human (HS), mouse (MM), rat (RN) hamster (MA), guinea pig (CP), sheep (OA), cow (BT), pig (SS) and frog (RC).

H S B1 H S B2 MM B1 MM B2 RN B1 RN B2 MA B1 MA B2 CP B1 CP B2 OA B0 BT B0 SS B0 RC B0

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with artiodactyls and primates, i.e supported the paraphyly

of the order rodentia The bootstrapping probabilities were

however, comparatively low (Fig 7D) using the neighbor

joining approach with 49, 52 or 68% for the categories

model, the Dayhoff model or Kimura’s model, respectively

Using UPGMA the probabilities were slightly higher;

between 70 and 82% Moreover, the hamster proteins were

now assigned to their rat and mouse paralogues

Interest-ingly, Kimura’s model consistently produced the highest

bootstrapping probabilities for a given topology

D I S C U S S I O N

In this paper, we describe the isolation and characterization

of the CYP11B genes of the guinea pig In an earlier study

[1] we isolated a single cDNA using an orthologous probe

that had been obtained using degenerated primers to screen

a guinea pig adrenal cDNA library This cDNA proved to

code for the abundantly expressed 11b-hydroxylase,

CYP11B1, of the guinea pig which exhibited exclusive

11b-hydroxylase activity [1] Although cloning strategies

using PCR-based approaches with degenerated primers

have often been successful this is sometimes hampered by

large differences in expression levels Thus, we were unable

to isolate more than one cDNA of the CYP11B family of

the guinea pig either by PCR-based approaches or by

repeated screening of the library under low stringency

conditions, even under conditions in which sodium was

depleted to achieve induction of the aldosterone synthase

gene The enzymatic activity of the cloned protein, however,

strongly suggested the existence of additional isoenzymes

with different enzymatic activities To test this hypothesis,

we performed a Southern blot analysis using an exon

1-spe-cific probe of CYP11B1 This experiment indicated the

existence of at least two additional genes of this family in the guinea pig To clone these genes we screened a genomic library which should circumvent difficulties associated with largely differing expression levels This led to the isolation of two additional genes, tentatively named CYP11B2 and CYP11B3 For CYP11B2, we were able to isolate a cDNA with a complete ORF In contrast, no specific transcripts could be detected for CYP11B3 in sensitive RT-PCR experiments with RNA from adult animals Thus, this gene might be a pseudogene that evolved as a consequence of a secondary gene duplication event (see below) Similar observations have also been made in cows that have five genes of the CYP11B family only two of which are functional [8] Alternatively, CYP11B3 might be a developmentally regulated gene as in rats, in which it is expressed solely during

a few specific days of postnatal development [26]

However, no differential expression was observed for either CYP11B1 or CYP11B2 during postnatal develop-ment of the guinea pig using RNAse protection assays Instead, we saw exclusive adrenal expression of both genes This does, however, not rule out expression in other tissues

at lower levels For example, expression of CYP11B genes in the rat has been demonstrated in brain [27] and in the heart [28] using very sensitive RT-PCR and in situ hybridization techniques The physiological significance of this low level expression remains unclear

To compare the catalytic activities of the guinea pig CYP11B isoenzymes we cloned the cDNAs downstream of

a cytomegalovirus promoter to drive expression in COS-1 cells This system has been proven suitable for the characterization of enzymes of the steroidogenic pathway [15] These analyses demonstrated a potent 18-hydroxyla-tion and 18-oxida18-hydroxyla-tion activity of CYP11B2 using various substrates thus showing it to be the aldosterone synthase

of the guinea pig It was interesting to note that CYP11B2

of the guinea pig had a considerably higher enzymatic activity in terms of 11b-hydroxylated product formed than the guinea pig CYP11B1 These results are in contrast with findings in other species For example, the human CYP11B1 has a 20-fold higher activity towards 11-deoxy-cortisol than CYP11B2 [29] Moreover, the activity of the guinea pig CYP11B2 compared to CYP11B1 could be correlated to the size of the C17 substituent of the substrate Thus, the differences were most pronounced with androstenedione and least with 11-deoxycortisol as a substrate These results might indicate steric hindrance in the entry channel of the cytochrome P450 enzymes with CYP11B1 being more selective for its proper substrate This would contribute to the zone-specific synthesis of glucocorticoids given the vast differences in expression level

of the two genes

In a second set of experiments, we investigated the significance of adrenodoxin, an iron sulfur protein that is essential for electron transfer from adrenodoxin reductase

to mitochondrial cytochrome P450 enzymes [19] Adreno-doxin has been shown to significantly increase enzymatic activities of steroidogenic enzymes in transfection experi-ments [15] If this cotransfection was omitted, the two guinea pig enzymes showed differential properties The 11b-hydroxylase activity of CYP11B1 was strongly reduced (Fig 5), whereas that of the aldosterone synthase was basically unaffected, while the 18-hydroxlase and oxidase activity was also greatly diminished These differences can

Fig 7 Phylogenetic analyses Shown are the phylogenetic trees

obtained by the maximum parsimony method (A), the UPGMA

method (categories model) (B), and the neighbour joining method

(categories model) (C) Numbers represent bootstrapping probabilities

of 1000 replicates The Table in D gives the bootstrapping probabilities

for monophyly and paraphyly of the order rodentia in detail Pr,

primates; Ar, artiodactyls; My, myomorphs; Cp, guinea pig.

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be explained by a lower binding affinity of CYP11B1 to

adrenodoxin when compared with CYP11B2 CYP11B1

has a tryptophan at position 366 while all other proteins of

the CYP11B family including CYP11B2 of the guinea pig

have a basic residue (arginine or lysine, respectively) at the

corresponding position These two basic residues have been

shown in site-directed mutagenesis experiments to be of

significance to the electrostatic interaction of bovine

CYP11A1 (cytochrome P450SCC), a closely related

mito-chondrial protein with adrenodoxin [30] Accordingly, the

11b-hydroxylase activity of CYP11B2 was hardly affected

by omission of cotransfected adrenodoxin However, the

subsequent enzymatic reactions involving the

18-hydroxy-lation and oxidation were severely impaired This could

indicate altered binding affinities for adrenodoxin after

the 11b-hydroxylation In this regard it is interesting to

note that in vitro experiments with purified bovine

CYP11B0 indicate a conformational change of the protein

due to rearrangement of the substrate after the first

hydroxylation step [31] This might account for an altered

binding site for adrenodoxin or modified binding

affini-ties Also, experiments in a reconstituted system with

bovine CYP11B0 using mutant forms of adrenodoxin that

have increased electron transfer capabilities showed a shift

in the spectrum of products formed towards compounds

modified at position 18 [32] Interestingly, studies with the

microsomal cytochrome P450 enzyme 17a-hydroxylase/

17,20-lyase demonstrated a dependence of the more electron

consuming lyase reaction on the presence of high

concen-trations of the electron donor protein [33] Taken together,

our results with the guinea pig suggest a new regulatory level

of aldosterone synthesis by the availability of reducing

equivalents In the light of results with the bovine and

human enzymes [32] this might be a more commonly used

mechanism which could be crucial for the zone-specific

biosynthesis of mineralocorticoids In this respect it would

be interesting to see whether expression of adrenodoxin is

differentially regulated

To investigate the evolution of the CYP11B genes, we

compared protein sequences of the CYP11B family These

analyses showed that CYP11B2 proteins are more closely

related to each other than CYP11B1 proteins across species

Furthermore, the 3¢ UTR of the guinea pig CYP11B2

shows considerable similarity to its human counterpart

while exhibiting only low resemblance to its paralogue in the

guinea pig On a functional level the CYP11B1 proteins also

show greater differences across species For example, the

hamster CYP11B1 produces  50% of 19-hydroxylated

product besides the 11b-hydroxylated steroid [7] Moreover,

as mentioned above, human CYP11B1 is a very potent

11b-hydroxylase as compared with CYP11B2 while in the

guinea pig this situation is reversed These findings suggest

that CYP11B2 genes, i.e those encoding bipotent enzymes,

are the primordial genes that underwent a subsequent

duplication and, as a consequence, the CYP11B1 genes

evolved independently in different species within the limits

of functional constraints

To see how this evolution might have occurred, we

determined the complete genomic structure of the two

functional guinea pig genes Interestingly, we observed the

greatest differences between these closely related genes within

intron 2 and intron 5 This could indicate frequent

recom-bination between the genes for which close association has

been shown in mice [4] and humans [34] Indeed, in humans

an unequal crossover between CYP11B genes, fusing the CYP11B2gene under control of the CYP11B1 promoter and vice versa, has been demonstrated to cause glucocorticoid remediable aldosteronism, an autosomal dominant disorder leading to severe hypertension [34], or congenital adrenal hyperplasia [35] In this context it is interesting to note that the crucial determinants for regio-specificity have been shown to reside in exon 5 [29] Moreover, analysis of breakpoints in patients suffering from glucocorticoid reme-diable aldosteronism indicate that important regulatory elements are contained within intron 2 [36] Thus, a scenario

is conceivable where recombination between the two genes in intron 2 and intron 5 eventually lead to both distinct regio-specificities and/or differential regulation

We next sought to determine when this gene duplication event might have occurred To this end, we conducted phylogenetic analyses with 16 sequences of the CYP11B family of proteins To assess possible methodical problems

we used different algorithms, namely the maximum parsimony and two distance matrix methods The maxi-mum parsimony method consistently grouped the guinea pig with a bootstrapping probability of 98% into one clade with rodents thus favouring monophyly of the order rodentia This is in contrast with the findings of Graur and colleagues [12] who postulated paraphyly of the order Our results are however, in accordance with the results of Hasegawa et al [13] who questioned the paraphyly of the order rodentia using the same data as Graur In contrast, the distance matrix algorithms again placed the guinea pig together with artiodactyls and primates, thus supporting paraphyly albeit only with bootstrapping probabilities between 49 and 82% Interestingly, the highest values were obtained when Kimura’s model [23] was used to calculate the matrices This might reflect the fact that this model assumes conservative and nonconservative changes to be equally likely which could lead to an overestimation of conservative changes

According to Frye et al [37] the ambiguity of the phylogeny as seen in our analyses with respect to the guinea pig can be interpreted as insufficient methodology For example, the data and the algorithms might not be adequate

to assign a statistically unambiguous topology if the radia-tion of species has occurred in a sufficiently small time frame Thus, the guinea pig presumably branched off at a very early time point within the mammalian radiation irrespective of the branching order Intriguingly, however, the guinea pig possesses already two functional CYP11B genes as have all other mammals investigated so far Theoretically it is possible that the gene duplication occurred in all lines independently

It seems, however, much more likely that the gene was duplicated in an ancestor mammal In this respect, it is interesting that analyses in the frog as an amphibian gave no indications of two CYP11B genes [11] Thus, the differential mineralocorticoid and glucocorticoid synthesis is presum-ably an exclusive property of mammals

A C K N O W L E D G E M E N T S

We thank K Denner, B Bo¨ttner and members of the Bernhardt lab for helpful discussions and advice We also thank W Oelkers and

V Ba¨hr for guinea pig adrenal tissues This work was supported by the Deutsche Forschungsgemeinschaft Grant DFG Be 13436-1.

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