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Tiêu đề Inactivation of annexin II tetramer by S-nitrosoglutathione
Tác giả Lin Liu, Edward Enright, Peng Sun, Shwu Yar Tsai, Pragna Mehta, David L. Beckman, David M. Terrian
Trường học Oklahoma State University
Chuyên ngành Physiological Sciences
Thể loại journal article
Năm xuất bản 2002
Thành phố Stillwater
Định dạng
Số trang 10
Dung lượng 349,02 KB

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R E S U L T S Effect of NO donors on AIIt-mediated liposome aggregation To determine whether NO donors affect AIIt’s functions, we exposed AIIt to GSNO and measured AIIt-mediated liposom

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Inactivation of annexin II tetramer by S -nitrosoglutathione

Lin Liu1,2, Edward Enright2, Peng Sun1, Shwu Yar Tsai1, Pragna Mehta2, David L Beckman2

and David M Terrian3

1 Department of Physiological Sciences, Oklahoma State University, USA; Departments of 2 Physiology, and 3 Anatomy

and Cell Biology, East Carolina University, USA

We investigated the effect of nitric oxide (NO) donors on the

activities of annexin II tetramer (AIIt), a member of the

Ca2+-dependent phospholipid-binding protein family

Incubation of purified AIIt with S-nitrosoglutathione

(GSNO) led to the inhibition of AIIt-mediated liposome

aggregation This effect was dose-dependent with an IC50of

approximately 100 lM Sodium nitroprusside, another NO

donor also inhibited AIIt-mediated liposome aggregation,

whereas reduced glutathione, nitrate, or nitrite had no

effects GSNO also inhibited AIIt-mediated membrane

fusion, but not the binding of AIIt to the membrane GSNO

only has a modest effect on liposome aggregation mediated

by annexins I, III or IV The binding of AIIt to the mem-brane protected the reactive sites of GSNO on AIIt GSNO did not inhibit AIIt-mediated liposome aggregation in the presence of dithiothreitol Taken together, our results sug-gest that GSNO inactivates AIIt possibly via S-nitrosylation and/or the formation of disulfide bonds

Keywords: annexin; nitric oxide; S-nitrosoglutathione; lipo-some aggregation; membrane fusion

Annexins are a multigene family of Ca2+-dependent

phospholipid-binding proteins and plays roles in many

membrane-associated events including exocytosis,

endocy-tosis, ion transport, inflammation, anticoagulation,

inhi-bition of phospholipases, signal transduction, Ca2+

homeostasis, cell-matrix, cell-cell or cell–virus interaction,

etc [1–7] However, most studies were carried out in vitro

Physiological functions of annexins are still unclear

although progress has been made in the past several years

Annexin VI and VII knock-out mice [8,9], and annexin VI

over expression transgenic mice [10] have been generated

and annexin-related diseases (annexinopathies) have

recently been recognized [11]

Annexins share common structural features, i.e a

con-served core domain of four or eight repeats of

approxi-mately 70 amino acids and a short variable N-terminal

segment The C-terminal core domain contains Ca2+-and

phospholipid-binding sites N-termini of annexins are

regulatory and are subjected to various post-translational

modifications including proteolysis and phosphorylation

Annexin II, a member of this family, exists as a monomer

(p36) or a heterotetramer [(p36)2(p11)2] The latter consists

of two annexin II monomers; each associated with p11

protein, member of S100 family of Ca2+-binding proteins

Annexin II binds to acidic phospholipids or biological membranes and causes them to aggregate and fuse [12–14] The formation of annexin II tetramers (AIIt) markedly reduces the Ca2+requirement for its membrane aggregation activity compared to annexin II monomers [12,14] How-ever, the N-terminal phosphorylation of annexin II tetra-mer by protein kinase C (PKC) or protein tyrosine kinase pp60c–srcinhibits its membrane aggregation activity without affecting its membrane binding activity [15,16] In vitro incubation of annexin II tetramers with plasma membrane vesicles and chromaffin granules results in the formation of

a plasma membrane vesicle-annexin II tetramer-chromaffin granule complex [16] An annexin II bridge between the plasma membrane and secretory granules has been observed

in chromaffin cells and anterior pituitary secretory cells using electron microscopy [17,18] Reconstitution experi-ments have demonstrated that annexin II can enhance secretory activity from permeabilized chromaffin cells [19]

A role of annexin II in regulated exocytosis in pulmonary artery endothelial cells has been documented [20] We have previously shown that annexin II tetramer promotes in vitro fusion of lamellar bodies with liposomes This process is enhanced by arachidonic acid, a lung surfactant secreta-gogue and is inhibited by 4,4¢-diisothiocyanatostilbene-2, 2¢-disulfonic acid (DIDS) and phenothiazines, inhibitors of lung surfactant secretion [14,21] Annexin II also partially restores surfactant secretion from permeabilized type II cells [22] Furthermore, annexin II translocates from cytoplasm

to the plasma membrane of type II cells upon stimulation [23] These results suggest that annexin II is involved in membrane fusion during surfactant secretion

In addition to its well-studied membrane fusion activity

in exocytosis and endocytosis, biological activities of annexin II extend to both intracellular and extracellular compartments Annexin II may regulate the organization of cytoskeleton by binding to F-actin [24] Heterodimer formation between annexin II and DNA polymerase a

Correspondence to L Liu, Department of Physiological Sciences,

Oklahoma State University, 264 McElroy Hall, Stillwater, OK 74078,

USA Fax: + 1 405 744 8263, Tel.: + 1 405 744 4526,

E-mail: liulin@okstate.edu

Abbreviations: AIIt, annexin II tetramer; GSH, reduced glutathione;

GSNO, S-nitrosoglutathione; NBD-PtdEtn,

N-(7-nitro-2-1,3-ben-zoxadiazol-4-yl) diacyl PtdEtn; NO, nitric oxide; PtdEtn,

phospha-tidylethanolamine; PtdSer, phosphatidylserine; Rh-PtdEtn,

N-(lissamine rhodamine B sulfonyl) diacyl PtdEtn;

SNP, sodium nitroprusside.

(Received 13 May 2002, revised 11 July 2002, accepted 16 July 2002)

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indicates a role for annexin II in DNA replication [4].

Partitioning of annexin II between nuclei and cytoplasm is

controlled by a nuclear export signal and p11 [25]

Annexin II also exists in extracellular cell surface and acts

as a receptor for cytomegalovirus [26], tenascin C [27], and

tissue plasminogen activator [28] Annexin II tetramer has

been identified as a plasmin reductase [29] and may be

involved in cancer [30]

Nitric oxide (NO) is a membrane-permeable intracellular

and intercellular messenger and plays an important role in

vascular tone, neurotransmission and pulmonary functions

However, it can be toxic when generated in excess Alveolar

epithelium is constantly exposed to NO from two sources:

inhaled air and endogenous production from lung cells

inclu-ding macrophages, endothelial cells, vascular smooth muscle

cells, and epithelial cells NO is generated fromL-arginine by

NO synthase (NOS) Two types of NOS have been described

One is a Ca2+-dependent and constitutive form (cNOS),

which is stimulated by agents that increase intracellular

Ca2+ Another is a Ca2+-independent and inducible form

(iNOS), which is induced by cytokines and/or endotoxins

and is transcriptionally regulated Both types of NOS are

present in alveolar type II cells [31] NO has been shown to

alter lung surfactant metabolism [31] We have previously

shown that NO donors inhibit lung surfactant secretion from

cultured type II cells at high concentrations [32]

There are five cysteine residues in each annexin II

mononer (four in human) and two in the p11 subunit

However, the role of cysteine residues in AIIt’s functions has

not been appreciated We have previously shown that

treatment of AIIt by N-ethylmaleimide resulted in the loss

of its activity [33] NO and its derivatives have been reported

to react with the sulfhydryl groups of several cellular

proteins including calpain [34], protein kinase C [35], low

molecular weight phosphotyrosine protein phosphatase [36]

and glyceraldehyde-3-phosphate dehydrogenase [37], and

inactivate these proteins We reasoned that NO donors

might also inhibit AIIt’s activity, and this could be another

mechanism of NO-mediated inhibition of lung surfactant

secretion, in addition to the nitration of annexin II by

peroxynitrite [38] As nitrosothiols occur naturally in human

airways [39], we chosen S-nitrosoglutathione (GSNO) as a

NO donor In this report, we determined: (a) whether

GSNO influences annexin II’s activities including

mem-brane aggregation, memmem-brane fusion, and memmem-brane

bind-ing; (b) whether the GSNO effect is specific to annexin II;

(c) whether Ca2+and phospholipid alter the GSNO effect

on annexin II; and (d) whether the GSNO effect is due to

the modification of cysteine residues of annexin II

M A T E R I A L S A N D M E T H O D S

Materials

S-Nitrosoglutathione (GSNO) was purchased from Cayman

(Ann Arbor, MI, USA) Dithiothreitol, reduced glutathione

(GSH), sodium nitrate, sodium nitrite and sodium

nitro-prusside (SNP) were from Sigma (St Louis, MO, USA)

Phosphatidylserine (PtdSer), phosphatidylethanolamine

(PtdEtn), N-(7-nitro-2-1,3-benzoxadiazol-4-yl) diacyl

PtdEtn (NBD-PtdEtn) and N-(lissamine rhodamine B

sulfonyl) diacyl PtdEtn (Rh-PtdEtn) were from Avanti Polar

Lipids (Alabaster, AL, USA) DEAE-Sepharose CL 6B,

Sephacryl S-300, Mono S and Mono Q columns were from Amersham Biosciences Corp (Piscataway, NJ, USA) 1,1¢-bis(4-anillino) naphthalene-5, 5¢-disulfonic acid (bis-ANS) was from Molecular Probes (Eugene, OR, USA) Biospin 6 column was from Bio-Rad (Melville, NY, USA) Anti-annexin I, II and IV antibodies were from Zymed (San Francisco, CA, USA) Anti-annexin III antibodies were kindly provided by Dr J D Ernst (University of California San Francisco, USA)

Purification of annexins I–IV Annexins were isolated from bovine lung tissue according

to Khanna et al [40] as previously described in detail [22] The bovine lung tissue (300 g) was powdered in a blender

at slightly above liquid nitrogen temperature One litre of buffer A (10 mMimidazole, pH 7.4, 150 mMNaCl, 1 mM

dithiothreitol, 100 lgÆmL)1soybean trypsin, 1 mMPMSF,

5 lgÆmL)1leupeptin and 2 mMEGTA) was added to the powder Once dissolved, the mixture was centrifuged at

650 g for 10 min Ca2+concentration in the supernatant was then adjusted to 2 mMby the addition of 0.1MCa2+ stock solution The membrane fraction was collected by centrifugation at 24 000 g for 40 min and washed three times in buffer B (10 mM imidazole, pH 7.4, 150 mM

NaCl, 1 mM dithiothreitol and 1 mM Ca2+) The final pellet was resuspended in buffer C (buffer B plus 5 mM

EGTA) and centrifuged at 100 000 g for 1 h The supernatant containing all annexins was dialyzed against buffer D (10 imidazole, pH 7.4, 0.5 mMdithiothreitol and

1 mM EGTA) for 2 days with three changes of buffer D The dialyzate was centrifuged at 100 000 g for 1 h The supernatant (the crude annexin preparation) was loaded

on a DEAE-sepharose column (2.5· 20 cm) and eluted using a linear salt gradient (0–0.3M NaCl in buffer D) Three peaks were resolved: peak A (10–35 mM NaCl) contained annexins I and II; peak B (45–60 mM NaCl) contained annexins III and IV and peak C (160–190 mM

NaCl) contained annexins V and VI Annexins were identified by Western blot using specific antibodies Fraction A was concentrated and applied to a Sephacryl S-300 column (1.5· 150 cm) equilibrated with buffer E (40 mM Tris/HCl, pH 7.4, 150 mM NaCl, 0.5 mM dithio-threitol and 1 mM EGTA) Two peaks containing annexin I plus annnexin II monomer, and annexin II tetramer were collected separately The low molecular weight peak was dialyzed against buffer F (25 mM Mes,

pH 6.0 and 0.5 mM dithiothreitol) and applied to an FPLC Mono S column at a flow rate of 1 mLÆmin)1 The column was developed with a gradient of 0–0.4MNaCl in buffer F Annexin I and annexin II monomer were eluted at 0.125M and 0.225M NaCl, respectively The higher molecular weight peak (annexin II tetramer) was also purified by Mono S column chromatography as decribed above Similarly, peak B, from the DEAE column, was concentrated and chromatographed on a Sephacryl S 300 column The major peak containing annexins III and IV was dialyzed against buffer G (40 mMTris, pH 8.5 and 0.5 mM

dithiothreitol) and applied to an FPLC Mono Q column Annexins III and IV were eluted at 0.114M and 0.077M

NaCl when a gradient of 0–0.15MNaCl in buffer G was applied All annexins were homogenous as revealed by SDS/ PAGE and staining with coommassie Brilliant Blue

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Preparation of liposomes

Liposomes were prepared by the extrusion method [41]

Phospholipids dissolved in chloroform were dried in a test

tube under a stream of nitrogen gas The lipid film was

hydrated with liposome buffer (40 mM Hepes, pH 7.0,

100 mM KCl) by vigorously vortexing The resulting

suspension was passed through a 0.1-lm-filter membrane

three times using an Extruder (Lipex Biomembrane,

Vancouver, Canada)

Preparation of lamellar bodies

Lamellar bodies were isolated from male Sprague–Dawley

rat lung tissue by upward flotation [42] on a discontinuous

sucrose gradient (1.0, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, and 0.2M)

The lamellar bodies enriched at the interface between 0.4

and 0.5Msucrose were collected and resuspended in 0.2M

sucrose, 10 mMHepes/Tris buffer (pH 7.4)

Treatment of annexin with NO donors

The following standard procedure was used unless stated

otherwise Annexin II tetramer (5 lg) was mixed in 50 lL

of 40 mMHepes, pH 7.4 with GSNO or other agents After

a 30 min incubation at room temperature, the treated

annexin was then tested for its ability to aggregate and fuse

membrane In some experiments, the unreacted GSNO was

removed by gel filtration using a Biospin 6 chromatography

column according to the manufacture’s instructions In this

case, in order to improve the recovery of annexin protein,

1 mgÆmL)1 of BSA was added to the reaction mixture

before loading on the column

Liposome aggregation and binding assays

Liposome aggregation activity was determined by

monit-oring the changes in turbidity as previously described [14]

Liposomes (PtdSer, 100 lg of lipid) were mixed in 1 mL of

Ca2+-EGTA buffer (40 mMHepes, pH.7.0, 100 mMKCl,

2 mMMgCl2, 1 mMEGTA and various concentrations of

Ca2+) After recording the zero time value (A540nm) of

absorbance at 540 nm, annexin was added to initiate

liposome aggregation and incubation continued for

30 min At the end of incubation, the absorbance at

540 nm (A30540nm) was read again The aggregation activity

was expressed as (A30540nm ) A540nm) For the

time-depend-ence of AIIt-mediated liposome aggregation, the

absorb-ance at 540 nm was read every 2 min At the end of the

liposome aggregation assay, the sample was centrifuged at

100 000 g for 1 h The pellet was analyzed on 10% SDS/

PAGE to determine the amount of AIIt bound to

liposomes The bands were quantitated by densitometry

(GS-710 Calibrated Imaging Densitometer, Bio-Rad,

Hercules, CA) Ca2+-EGTA buffer was prepared according

to the method of Bers [43] and the free Ca2+concentration

was verified using a Ca2+-selective electrophode (Orion

Research, Inc, Boston, MA)

Membrane fusion assay

Membrane fusion between lamellar bodies and liposomes

mediated by AIIt was measured, as described previously

[14], according to the method of Struck et al [44] Fusion was monitored by following the decrease in the efficiency of resonance energy transfer between two fluorescent-labeled phospholipid probes: NBD-PtdEtn (donor) and Rh-PtdEtn (acceptor), due to the dilution of the probes upon membrane fusion Liposomes were composed of PtdSer/ PtdEtn/NBD-PtdEtn/Rh-PtdEtn (24.5 : 74 : 0.75 : 0.75) Labeled liposomes (4 lMin lipid) were mixed with lamellar bodies (20 lgÆmL)1) in 0.5 mL of the assay buffer (40 mM

Hepes, pH 7.0, 100 mMKCl, 2 mM MgCl2, 1 mM EGTA and 2 mM CaCl2) After a 1 min incubation, AIIt was added to initiate the reaction NBD-PtdEtn fluorescence (lambda Ex¼ 450 nm and lambda Em ¼ 530 nm) was monitored as a function of time Fusion was expressed as a percentage of the maximal NBD-PtdEtn fluorescence, which was determined after disrupting the membrane with 0.1% Triton X-100 Because Trition X-100 causes the fluorescence quenching, the maximal fluorescence was corrected by a factor of 1.3 [13]

Other methods Protein concentration was determined by the method of Bradford [45], using bovine plasma gamma globulin as a standard SDS/PAGE was carried out according to Laemmli [46], using a Bio-Rad mini-protean II apparatus

R E S U L T S

Effect of NO donors on AIIt-mediated liposome aggregation

To determine whether NO donors affect AIIt’s functions,

we exposed AIIt to GSNO and measured AIIt-mediated liposome aggregation activity as assessed by monitoring the changes in absorbance at 540 nm Figure 1A shows the time course of AIIt-mediated liposome aggregation in the presence of various concentrations of GSNO Figure 1B depicts a dose-dependence of GSNO inhibition of AIIt-mediated liposome aggregation The concentration effecting 50% inhibition (IC50) was approximately 100 lM Ca2+ (1 mM) and/or GSNO (2 mM) did not cause liposome aggregation in the absence of AIIt under our assay conditions Sodium nitropresside (SNP), another NO donor structurally different from GSNO, also inhibited AIIt-mediated liposome aggregation (Fig 1B) although the IC50 (approximately 2 mM) was higher than that of GSNO To exclude the effect of the unreactive GSNO on liposome aggregation, we removed these small molecules from annexin II protein by gel filtration using a Biospin 6 chromatography column at the end of preincubation and measured its liposome aggregation We observed a similar inhibition to these without column purification (data not shown) Furthermore, GSH, nitrite and nitrate had no effects (Fig 2) GSNO inhibited AIIt-mediated liposome aggregation at all the AIIt concentrations and all the Ca2+ concentrations tested (Figs 3 and 4) At a higher concen-tration of AIIt (10 lg) less inhibition was observed Effect of GSNO on AIIt-mediated membrane fusion Although the mechanisms by which AIIt mediates mem-brane fusion are still unclear, at least three steps are

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involved: (a) the binding of AIIt to membrane; (b)

membrane aggregation and (c) membrane fusion We have

previously shown that AIIt promotes the fusion of

liposomes with lamellar bodies, the secretory granules of lung alveolar type II cells [14,22] We therefore examined whether GSNO also blocks this process Membrane fusion was monitored by a lipid mixing assay [44] The addition of AIIt caused a rapid fusion of lamellar bodies with liposomes Pre-treatment of AIIt with 0.1 and 1 mMGSNO resulted in 70 ± 4% and 83 ± 10% inhibition of AIIt-mediated membrane fusion, respectively (Fig 5) It was noted that AIIt-mediated membrane fusion was more sensitive to GSNO compared to the membrane aggregation This is probably because GSNO not only affects the membrane aggregation step, but also the membrane fusion step

Fig 1 NO donors inhibit annexin II tetramer (AIIt)–mediated liposome aggregation in a dose-dependent fashion Purified AIIt (5 lg) was incubated in

50 lL of 40 m M Hepes (pH 7.4) buffer containing varying concentrations of S-nitrosoglutathione (GSNO) or sodium nitroprusside (SNP) at room temperature for 30 min Liposome aggregation activity was measured by monitoring the turbidity change (A 540nm ) The aggregation assay was carried out in 1 mL of Ca2+-EGTA buffer (40 m M Hepes, pH 7.0, 100 m M KCl, 1 m M EGTA, and 2 m M Ca2+) containing 100 lg phosphatidylserine liposomes AIIt was used to initiate liposome aggregation (A) A representative time course curve of AIIt-mediated liposme aggregation in the presence of various concentrations of GSNO (d) 0 m M (j) 0.001 m M (m ) 0.1 m M ( ) 1 m M (r) 10 m M (B) Dose-dependence of NO donor-mediated inhibition of AIIt-donor-mediated liposome aggregation The activity was expressed as the increase in absorbance at 540 nm after a 30 min incubation over the initial value The results were expressed as percentage control The control was treated the same way as other samples except that

no other reagents were added The data shown are mean ± SE from three experiments (GSNO, d) or mean from two experiments (SNP, j).

Fig 2 Sodium nitroprusside and S-nitrosoglutathione inhibit

AIIt-mediated liposome aggregation, whereas reduced glutathione, nitrate or

nitrite has little effect AIIt (5 lg) was incubated with sodium

nitro-prusside (SNP, 2 m M ), S-nitrosoglutathione (GSNO, 2 m M ), reduced

glutathione (GSH, 2 m M ), nitrate (2 m M ) or nitrite (2 m M ) in 50 lL of

40 m M Hepes buffer (pH 7.4) for 30 min The treated AIIt was tested

for its ability to mediate liposome aggregation The results were

expressed as a percentage of the control The control was treated the

same way as other samples except that no other reagents were added.

The data shown are mean ± SE from three experiments wP < 0.05

vs control.

Fig 3 A dose-dependence of AIIt-mediated liposome aggregation in the presence or absence of GSNO Various concentrations of AIIt (0–10 lg) were incubated with or without 2 m M GSNO in 50 lL of

40 m M Hepes buffer (pH 7.4) for 30 min Liposome aggregation was determined and expressed as the increase in absorbance at 540 nm after a 30 min incubation over the initial value.

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Effect of GSNO on the binding of AIIt to membrane

As the binding of AIIt to membrane would be the

first step of AIIt-mediated membrane fusion, we also

investigated whether GSNO inhibits the binding of AIIt

to liposomes We treated AIIt with GSNO for 30 min and mixed the samples with liposomes and 1 mM Ca2+ After a 30 min incubation, we pelleted liposomes by centrifugation and analyzed AIIt associated with lipo-somes on 10% SDS/PAGE As shown in Fig 6A, GSNO had no effect on the amount of AIIt associated with liposomes In the absence of Ca2+, little AIIt was bound to liposomes The results indicate that the modification of annexin II by GSNO does not affect the binding of AIIt to membrane When different amounts of AIIt were treated with GSNO, no inhibition were observed for the binding of AIIt to liposmes at all the AIIt concentrations tested (Fig 6B)

Effect of GSNO on liposome aggregation mediated

by annexins I, III and IV Annexins are a large gene family In mammals, so far, 12 members have been identified and in other organisms more than 60 and over 200 isoforms [47] Annexins share common structural features and some biochemical pro-perties All annexins bind to phospholipids in the presence of Ca2+ Some annexins (I, II, III, IV and VII) are able to mediate liposome aggregation although their Ca2+sensitivities differ [22] We therefore examined whether GSNO inhibits liposome aggregation mediated

by various annexins As shown in Fig 7, GSNO only has a modest effect on liposome aggregation mediated by other annexins

Effect of Ca2+and phospholipid on GSNO inhibition

Ca2+causes protein conformational changes in annexin II [48] and may alter the environment of reactive sites of annexin II by GSNO We tested whether such changes influence the GSNO inhibition of the activity of annexin II AIIt (5 lg) was preincubated in 50 lL of buffer containing 1 mM Ca2+ for 30 min to induce protein conformational changes The mixture was then added to 1 mL of the assay buffer containing 100 lg liposome for measuring liposome aggregation As shown

in Fig 8 (two bars with minus liposome during the preincubation), a similar inhibition was observed when AIIt was pretreated with EGTA or Ca2+, suggesting that the conformational changes caused by Ca2+had no effect

on the GSNO inhibition

After binding to the membrane, some residues in AIIt may be hidden due to the polymerization of AIIt on the membrane or a protein conformational change, and are

no longer accessible to GSNO To test this possibility, AIIt (5 lg) was preincubated with 50 lg liposomes in

50 lL of buffer containing 1 mM Ca2+ to allow AIIt binding to liposomes and then treated with 1 mMGSNO

At the end of preincubation, the mixture was added to

1 mL of assay buffer containing 50 lg liposomes for measuring liposome aggregation As expected, GSNO still inhibited AIIt-mediated liposome aggregation when no

Ca2+existed and thus AIIt did not bind to the membrane during the preincubation However, in the presence of

Ca2+and liposomes during the preincubation, AIIt was bound to the membrane before the addition of GSNO In this case, no significant inhibition was observed (Fig 8)

Fig 4 Ca 2+ -dependence of AIIt-mediated liposome aggregation in the

presence or absence of GSNO AIIt (5 lg) was incubated with or

without 2 m M GSNO in 50 lL of 40 m M Hepes buffer (pH 7.4) for

30 min Liposome aggregation was measured in various

concentra-tions of Ca2+-EGTA buffer and expressed as the increase in

absorb-ance at 540 nm after a 30 min incubation over the initial value.

Fig 5 GSNO inhibits AIIt-mediated fusion of lamellar bodies with

liposomes AIIt (5 lg) was incubated with 0.1 m M or 1 m M GSNO in

50 lL of 40 m M Hepes (pH 7.4) for 30 min and AIIt- mediated

membrane fusion was measured Lipid (4 l M ) in labeled liposomes

(PtdSer/PtdEtn/NBD-PtdEtn/Rh-PtdEtn, 24.5 : 74 : 0.75 : 0.75)

were mixed with 20 lgÆmL)1lamellar bodies in 0.5 mL Ca2+-EGTA

buffer (1 m M free Ca2+) After a stable baseline was established,

AIIt was added to initiate the reaction Fusion was monitored by

following the increase in NBD-PtdEtn fluorescence (Ex ¼ 450 nm,

Em ¼ 530 nm) The data shown are a representative from three

experiments.

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In an additional experiment, GSNO (1 mM) was directly

added to liposome aggregation assay medium before the

addition of AIIt Under these conditions, a 48% inhibition

was observed However, if GSNO was added 5 min or

10 min after the addition of AIIt, less inhibition (26% or

17%) was seen (data not shown) Presumably, this is due

to the binding of AIIt to liposomes These results indicate

that the reactive sites on AIIt were protected by the

binding of AIIt to the membrane

Fig 6 GSNO does not affect the binding of AIIt to liposomes (A) AIIt was incubated with GSNO (1 m M ) for 30 min At the end of incubation, AIIt was mixed with liposomes in the presence of 1 m M EGTA or Ca2+ After a 30 min incubation, liposomes were sedimented by centrifugation and AIIt associated with liposomes was analyzed by 10% SDS/PAGE The data shown are a representative from three experiments (B) A dose dependence of AIIt binding to liposomes in the presence or absence of GSNO The conditions were the same as in the figure legend of Fig 3 At the end of the aggregation assay, liposomes were sedimented by centrifugation AIIt associated with liposomes were analyzed by SDS/PAGE and quantitated by densitometry The results were expressed as the percentage of the maximal binding (i.e 10 lg AIIt without GSNO).

Fig 7 A dose-dependence of liposome aggregation mediated by

ann-exin I, III and IV in the presence or absence of GSNO Various amounts

of annexins I, III and IV (0–10 lg) were incubated with or without

2 m M GSNO for 30 min Liposome aggregation was determined and

expressed as the increase in absorbance at 540 nm after a 30 min

incubation over the initial value For the comparison, the results were

expressed as percentages of the maximal activity (i.e 10 lg of annexins

without GSNO treatment) The latter values were 0.28, 0.32, and 0.23

for annexins I, III, and IV, respectively (d) AI (s) AI + GSNO (.)

AIII (,) AIII + GSNO (j) AIV (h) AIV + GSNO.

Fig 8 Ca2+-induced protein conformational change in AIIt has no effect on GSNO inhibition of AIIt-mediated liposome aggregation However, GSNO does not inhibit AIIt-mediated liposome aggregation once AIIt binds to membrane For the first two bars, AIIt (5 lg) was incubated with or without 1 m M GSNO in 50 lL of 40 m M Hepes (pH 7.4) containing 1 m M EGTA or 1 m M Ca2+for 30 min The samples were added to 1 mL of the assay buffer containing 100 lg liposome for aggregation activity determination For the last two bars, AIIt (5 lg) was preincubated with 50 lg liposome in the presence or absence of 1 m M GSNO in 50 lL of 40 m M Hepes (pH 7.4) containing

1 m M EGTA or Ca 2+ for 30 min The samples were then added to

1 mL of assay buffer containing 50 lg liposome for aggregation activity determination The zero time absorbance was recorded sepa-rately using 1 mL of the assay buffer containing 100 lg liposomes The results were expressed as percentage control (i.e activity of GSNO-treated AIIt/activity of unGSNO-treated AIIt · 100%) The data shown are mean ± SE from three experiments.

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Effect of dithiothreitol on GSNO inhibition

of AIIt-mediated liposome aggregation

To evaluate whether the GSNO inhibition of AIIt-mediated

liposome aggregation is involved in the formation of

disulfide bonds, we incubated purified AIIt (5 lg) with

GSNO (1 mM) in the presence of the reducing agent,

dithiothreitol As shown in Fig 9, when dithiothreitol

(0.5 mM) was included in the incubation medium, the

inhibition of AIIt-mediated liposome aggregation by

GSNO was no longer observed, suggesting that the

inactivation of AIIt may be due to the formation of

disulfide bridges However, no intermolecular disulfide

bonds between annexin molecules were formed, because

when GSNO-treated AIIt was resolved on nonreduced

SDS/PAGE, no extra-bands were seen (data not shown)

However, we cannot rule out the possibility of disulfide

bond formation between AIIt and glutathione because of

the resolution of SDS/PAGE

Conformational changes

To detect possible conformational changes of AIIt treated

with GSNO, we used the hydrophobic fluorescent probe,

bis-ANS This dye binds to hydrophobic sites of proteins

and causes an increase of intensity in fluorescence with a

concomitant shift to the lower wavelength [49] As expected,

the addition of AIIt to the bis-ANS aqueous solution, the

fluorescence increased and maximal emission wavelength

was shifted from 510 nm to 490 nm (data not shown)

Those changes are less, compared to annexin I [50]

GSNO-treated AIIt had a similar increase of fluorescence and wavelength shifts GSNO itself had no effect on either fluorescence or maximum wavelength The results suggest that GSNO does not cause a major conformational change

of AIIt as detected by the fluorescent dye, bis-ANS However, it is possible that the method used here may not

be able to detect small conformational changes

D I S C U S S I O N

Annexins are subjected to various post-translational modi-fications Although the phosphorylation of tyrosine or serine/threonine residues in annexin has been extensively studied, the relationship between other residues and annex-in’s activity attracted less attention When AIIt was treated with N-ethylmaleimide, a sulfhydryl agent, AIIt’s activity was reduced [33] However, modification of annexin by reactive nitrogen species has not been reported Our recent study has shown that AIIt can be nitrated by peroxynitrite

to form nitrotyrosine and such modification inhibited AIIt-mediated liposome aggregation [38] In the present study,

we, for the first time, showed that NO donors, GSNO and SNP, also inhibit annexin II’s activities including membrane aggregation and fusion This modification was abolished in the presence of dithiothreitol Although physiological significance of this in vitro observation remains to be determined, it might imply a new post-translational modi-fication and possibly a regulatory mechanism for annexin II

in cells Recently, Fas-induced caspase-3 de-nitrosylation was observed in lymphocyte cells, but the factors responsible for the de-nitrosylation was not identified [51] Because NO inhibits surfactant secretion from alveoar type II cells [32] and AIIt is a criticial component for the secretion of lung surfactant in type II cells [14,22], NO inhibition of AIIt’s activity may provide an alternative mechanism

of NO-mediated reduction of lung surfactant secretion Annexins including annexin II have also shown to be associated with oxidative stress [52–56], NO modification may also have implications in this process as well as other biological activities of annexin II

NO and its derivatives can attack protein targets involved

in many physiological processes and thus modifies their functions Interaction of NO with the heme or nonheme iron of proteins leads to activation of soluble guanylyl cyclase [57] and inactivation of cyclooxygenase [58] or mitochondrial complexes I and II [59] NO also regulates protein functions by covalent attachment of the NO group

to cysteine residues in proteins via S-nitrosylation, which may involve other nitrogen species such as NO+ Increasing amounts of evidence demonstrate that this post-transla-tional modification may represent an important cellular regulatory mechanism [34–37] Depending on different proteins, S-nitrosylation may be followed by secondary modification For example, for glyceraldehyde-3-phosphate dehydrogenase, S-nitrosylation of four active site cysteines

in the tetramer ultimately results in S-ADP-ribosylation and inactivation [37] If vicinal thiols in the protein are S-nitrosylated, a more stable disulfide may be formed One of the examples is the N-methyl-D-asparate receptor [60] Our present study has shown that the GSNO inhibition

of annexin II-mediated liposome aggregation is no longer observed in the presence of dithiothreitol, suggesting that, most likely, the modification of annexin II’s activity by

Fig 9 Effect of ditiothreitol on the inhibition of AIIt-mediated liposome

aggregation caused by GSNO AIIt (5 lg) was incubated with 1 m M

GSNO in the presence of the reducing agent, dithiothreitol (0, 0.1, 0.5,

1.0 m M ) After a 30 min incubation, liposome aggregation activity was

determined The results were expressed as a percentage of the control.

The control was treated as the same way as other samples except that

no GSNO and dithiothreitol was added The data shown are

mean ± SE from three experiments.

Trang 8

GSNO is through S-transnitrosylation and the formation of

disulfide bond(s) As no dimers or polymers in

GSNO-treated AIIt were observed on nonreduced SDS/PAGE, the

disulfide bonds could be formed either within the AIIt

molecules or between annexin II thiol and GSNO [61]

UV and fluorescence studies of annexin II revealed a

Ca2+-induced conformational change in which the

aroma-tic amino acids, tyrosine and tryptophan, expose more to

the aqueous phase [48] For annexin V, Ca2+ causes

conformational changes in domain III that leads to the

formation of an additional Ca2+-binding site and exposure

of Trp187 to the solvent [62,63] These conformational

changes appear not to affect the GSNO reaction with

annexin II, as a similar inhibition of AIIt-mediated

lipo-some aggregation by GSNO was observed whether AIIt

was pretreated with Ca2+ or not prior to the liposome

aggregation assay Probably, because Ca2+only induced a

modest conformational change circular dichroism studies

failed to detect major changes in secondary structure of

Ca2+-bound annexin II [48]

The present study indicated that GSNO no longer inhibits

AIIt-mediated liposome aggregation once the protein binds

to the membrane This is consistent with the finding that

some annexins are accessible to quenchers in the solution

more than in the membrane-bound state [64] There are

several possibilities: (a) after the binding of annexin II, the

reactive sites were hidden by membrane; (b) the binding of

AIIt to membrane causes a conformational change [65], such

changes may bury the reactive sites of GSNO more deeply in

the protein matrix therefore rendering them inaccessible to

GSNO; (c) annexins V and XII has been shown to form

trimers or hexamers on membrane [66,67] We have

previ-ously shown that AIIt can self-associate in the presence of

Ca2+[23] Therefore, it is possible that AIIt forms polymers

on membrane, thus hiding the reactive sites

Nitrosothiols occur naturally in human plasma mainly as

the nitrosothiol of human serum albumin [68]

S-nitroso-glutathione has been identified on normal airways [39] and

in neutrophils [69] S-nitrothiol concentrations in inflamed

and transplanted lungs were much higher than normal

subjects The half-life of GSNO in the lavage fluid is

approximately 3 h, much longer than NO [39] Therefore,

GSNO may contribute to physiological and pathological

processes in the lung and GSNO regulation of annexin II

activity may be physiologically relevant

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

This work was supported by US Public Health Service Grant NHLBI

HL-52146, OCAST HR01-093 and OAES (to L L.) We thank Ms.

Dierra Davis and Ms Krista J Schone for secretarial assistance.

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