J. Mass Spectrom. Soc. Jpn.

Vol. 58, No. 4, 2010

REVIEW
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Fundamentals of Mass Spectrometry
ῌFundamentals of Electrosprayῌ
Kenzo H>G6D@6  

Clean Energy Research Center, University of Yamanashi,

Kofu, YAMANASHI, JAPANElectrospray is an ultimate phenomenon that occurs when the liquid is exposed to the high electric ﬁeld. Inorder to fully exploit electrospray for the analytical science and technology, it is mandatory to understand themechanisms for the formation of charged droplets and the following formation of gas phase ions. This article
will explain the basic aspects of electrospray from various points of view. The contents are as follows: (i)electrospray ionization (ESI) is based on electrochemical reactions, (ii) what is the Taylor cone? (iii) disintegrationof charged liquid droplets, (iv) mechanism for the formation of gas-phase ions from the charged liquid droplets,(v) e#ect of surface tension of liquid on electrospray, (vi) positive- and negative-mode of ESI, (vii) suppression
e#ect by the presence of salts, (viii) down-sizing of electrospray, ESInanoESIProbe ESI, (ix) ﬁeld desorption,(x) ﬁeld ionization, (xi) formation of multiple-charge ions, (xii) application of electrospray.
(Received February 3, 2010; Accepted February 3, 2010)1. 

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Correspondence to: Kenzo H>G6D@6, Clean Energy ResearchCenter, University of Yamanashi, 4῍3῍11 Takeda, Kofu,
Yamanashi 400῍8511, JAPAN, e-mail: hiraoka@yamanashi.
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3M   d7l%X  b7!

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3.

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 +o+ Y_1 Ga, Bi KB!L«!

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" %Kp$q V!b7" l?2f*23#®¯z°% >%X9f

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KB!" m%rV  U!

 MN  stMNuOv wPx EF G±C  st uOv wPx

HQ (SIMS)  !"  %y z + #­°)µCVqY" @? ¶  RS nm {|!g}pT!~  U

%s·$q @? ¶%V+ !"  e!
 LWti2h+Y`6a!4sTaylor 4



nm !

!@

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° %8" QL !3M2 VqY"xa$ o[ +A2h+m¡0uO%T$q<)=>?@) MuO%¤¥02^¸ {|!3M2 b7!l2T¹  Pg sN\]7 s" x 2%^_ ]72

2 +¦ca|2RMx b7!l g n
k !v2qr   ]7aAN02> bY ]7a2 c2d d+ 

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=

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2qr 3)

! A3#Xm7Z " ]7!
 s` (1) ij 7Gp2 r 2+qr v ` (1)  K1x1)
"



%<)=>?@)(5):Y * E %X9]72 z§º!z{23pe$+N02>2fRVL sghv `* E !no r 2

7e R=g>[MN 

W1 _T$ s` (4)x !W12!



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2+*23;+]

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2: b7"

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A

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PE0.5e0E2(6)gi PE  Poisson !©`RV]7  8b3)

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2h+ b7!a%`6a24$q ;Yῌ 141 ῌA2K. Hiraoka

Fig. 2. IJKLMNOJ"µ@N0* ¶S 0.1 ·¸῎"@ (1 : 1) B * ¶S<R 1 mL/min U?VWX"
T¡ 100 mm U?VWX"RYZ  3.7 kV ¹QS 10 mm.

  PE

 P g 

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89

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:* Pg

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QRS d  g T!"* U?VWX"YZP1[\ PE]Pg ^_
 

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* 

Fig. 3.

Taylor !"#89FQ#de +F`ghi* +$ %fbF jk IJKLMNOJ"lm no&p* 3
q9rds'tuvw(x`  FG* N:  U R:
H¡ (mm) Dt: $3  FG:*
&Vº 2 `»¼1W½-* ῌ1993, American
Chemical Society)*R yzbF rdIJKLMNOJ" * IJKLMNOJ"A+`{0)lm|*3}+* Fig. 2 +~9,3IJKLMNOJ"-v1* (a) 89 (e)1 :* +A Rayleigh Q@A N  70
80 17 Taylor !"#89#df* I

JKLMNOJ"3 89BC uv`{./0NOJ"   IJKLMNO  3nDZ3 5nA RayleighJ"Au03 (electric sneeze) lbF* +QE3FG* Fig. 3   FG4

lmA1 ms : &2  kHz)*12)* N A R A H¡ ( mm) 1*Vertes 97 "@IJKLMNOJ"43<

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Q1;E Taylor !"# 89#df3 

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Rayleigh Q,n:* A<A=>0?9 : 20

897 15  ²de9F  ¬R³´A 2
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b  * " c6?@ /   s (C/m2) &ACU & 67 D& -. /0 12 (4) 3451) 67 8&D A  B

*9  *:;' ,,C5 0G 0 ?@0&  r1, r2, ' s1, s2, <' E1, E2 0

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r1/r2>s2/s1>E2/E1

 
= 
   ?@D EFG1)

JK N /L'MN O0N )& (^0  

!0  T "#V  & %' (^
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ab/0d -.+

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= J¡ B<g 1¢!$W0RU X&Y67 N $W0
T ' N  2 \ ,& JdDD   BC5 §?@7 

(9)Q 0RST H' Z0[(^ GGr£¤¥¦nT¡k5 9KN>(ge0R3)0.5P8p

2UC K N

=J  )

Rayleigh #$ ; R  H I

2 (9)  R3

108 V/m Q"C& # D

(8)

  A=B

 s 6C

<

M°'±G07   j  UCJdH.5 DD

,h-

BC5

  \=²= C0 

c6'?@0 =DB J

5 Nleigh #$

  i^0  Ns

Ray-

2 (10) B   =0G (Fig. 3) 7 5 c6'?@06C

Fig. 1

Ns>N/4pR2>2(e0g)1/2/R1/2

O

³Ilmnopqrms

1tuvwxs); ´100 mm5 0?0µ¶(10)2UC Rayleigh #$  +@ j ;JK mm    (^B; _kB Ns '"*RU lmnopqrms
'G0 

tuvwxs; R'GB Ns '$yB  

Rayleigh #$UC   5P104  " lmnopqrms¨© &:  10῍5 M 0 ; 1.5 mm  )

tuvwxs;(^0:¡K J 105  K 'G0 tuvwxs./<$yK _`%& ·KG  :z 12 (1) ,)2 (6) 345}0& 

5.  !"#$%&'()*+,-./01"

lmnopqrms0?0" JH'0?]{





" "

 lmnopqrms

10῍5 M  :'¨©0 LG& U 67?¸¹ '"*? k



Ray-

leigh #$%&|1  C UC23c}0!~)'0 (Fig. 3) nsp

NaCl  150 mM (0.9º) IJ <g
1.5 mm   ¸¹

ῌ

;

῍

J 10  Na  Cl IJ
9

10῍5 M »M5:IJ&<g :¡KNaῌ  Cl῍ JN

4 234-5.-<g" NO"EGIJ Naῌ  Cl῍ U

 C»M5'BC5 c6 =©0 H_UC5c6?@0

ῌ7  1charged residue

 CRM5 ,) ῍0  1ion evaporation

 IEM5 &$=c6¯F0 L& O0½(0¹ 6789:;-<= J ¹

*8& 7 

Fig. 3  9K   5 :

kP¼ G »D G G * lmnopqrms0? G

ῌ 143 ῌ

K. Hiraoka   8     !"#$%&'()*+ ,-. 

/

 

0 9

6. 



 

Fig. 4.

1 234 526
78 9  !"#$%& 12#T 33tL (a) 3( H(]3¨©T (b) S ;p3
2fZD(]3¨©T F: ¥¦d:;17<=> 1
? 8 4@A!"#$%& 1
 B >C 7D E< 12
7<F0G !"#$%& 7F8  g?H I gJ72K10ῌ3

0 3 3( E<YP0< 2)v.8 )v. 

3 73 2)v.8 H> }QR

N/m 1L2!"#$%&8 7

  0< i   H  !"#$%&MN OP

QNi 3 ?E; 9)v&

89C 9  L RS-&T (gJ

!"#$%&  SiX& 9p3

22K10ῌ3N/m) FUV#W#XT (gJ28K10ῌ3 N/m) 2

 C iT 3 7D

YZ !"#$%& 7F8 0

7<3 3 SiX& rH? 0 i !["#Y\]1 ; CU5VW0 9  ;)v&C 0  RS-&TFUV#W#XT  $  iX& ;p3 CA 3 

6<A%&D^ 1 _'7F8 

iX&JK; X ;E<LY YP0 Z[C b!

2)v.7< i2=F8H @["/c \]" *8!["+ D \SiX&JK7#TdT"+A3,e ? f-2g7h? +3 7F8 3 i] i%.f-288A



`(]

$6<a)8;jh/H 0;370H

Fig. 4k (5) ;   (g) gl Pg

 g$18

Hmn2H3l!"#$%&2

=

? C"o2;7D(

8¢_`2£8 S63 ` £8  Fermi ¤23¥¦d (F)(]2(] C 8q29r: sq2;
1

 r:7<2wx !"#$%&7F8 B  tu&23DY0D;p3(a@b!0<H 32c ^¡=D^] 1o45 167o45A3p
r:H tu&)v C 0 \SJK

E< S63 #T E< ^¡

fZ0G

ce8!T§&23

H  S

pH;3¨©T 2Y8 SX3 *ª

;E<w  3  og H?«¬$)hi l 234Ho2!"#$%& 8 $y7

lJh/mvJh/p(11)

H 0  ;r: 8Pzo 167 <{7F

h: Planck Gd m: 3og v: 3P5 p: 3

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­jg «¬$)hi lkl® Dx¯

A~@0 ; C 9r:7F8HL ) 3 ¥¦dkl F 2mZe  #T

v@[ @D;r:7F8H)v >3A[

X 7`8 ? 0 3*+,->
C ;)v&!"#$%& 0F8H
7. 

!"





iX&JK; #T 3!#$%

 °P0F8HL3 7F8 OH

&'()ῌ

iX&JK §±§±nED7 dXC

!"#$%&BC2 8 9)v $ 5; L37F8o² ,pC

6< ;)vDBC $y)H EF|z`  \Sq3ªJK; 3#TL

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t ·O0<H 3tL¸u¹ª#$%&2 G H=Z I  

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iX&JK 8$,L3iC p3(;)v ; »¼G½0 3xy&2£8Y0<H MNn ;O3 iX&JK i 8iῌ 144 ῌ

KLMNO9PL½o



=|$  )\2 012J    !"#$K/?-,S  &'( )K% %&'( )*+,-,. / 012"

,

&

%

3



012456,"6LM KLMNO9PL%7 SF6 89*:;3 . <!

%+&'( )B &"# K

CCl4 ,=*

f: C0 %%+, D{ (15)H . N

6%>

6%?

,kCe " '@A*BC KK. Q.O tP Taylor 2

 4,A* %> D& EF)WQ

AG )H 6 ef: 10ῌ2 M *SbT.
ῌ(12῍1)

ῌJ SF5 IF(12῍2)

CCl4Ie J ClῌICCl3(13)

SF6Ie J SF6

8. 

 KLMNO9PLRB%/

KLMNO9PLUV,S - 


%W,N

!:;Bkl KLMNO
9PL 3--,%> Y-"=qe  Q }q !2

 N" !4 79 %ef

KLMNO9PL%+&'( )Q!01:6 N"!$ :2 TDC (Fig. 1) " !&"# K R$3 K

 DX QS E UfF,¡¢

%&S % 6'   NL£MO2  D¤n

qY¥H . KLMNO9PL 3-

(14)

TDCTK

n (" UV)WQS X,. 0.2  0.4 (*6-,6rb C, 150 mM  <Z][:6*  K %%KLMNO9PL%

EF Debye E\ lD " { (15) kl 1 nm

" %+&'( )+,6¦§ :ef!,6 01

%> Y-"'(.EF&'(2L£ CWA/?@A7¨] )%Q-' Y-%> .,=&'( )E" ,Z-/?,*[.

 &

C,6k

P%" Qq,^0

12$ ©ª%«¬k'( )"01\23,  D]3^_`a]:!*KLMNO9PLQq63 ­,=H b cdef" g4 %+^¥*G®6 KLMNO9PL

'hij )"\23, Bkl m%

_k.%& `¯)+,5n67  KLMNO9PLY-+ 150 mM ]:*B !,=*0

B7-\o % ,pQq,Y-+

1KLMNO9PL a3 "Qq,<b*rb E- ef!8g6sgtuv*

Q 33 °±2b @ 8g6sg79%/?,uv w D8
g6sg79E

s01268012: x

Qq #$



%" !,= <Z]:[!c²KLM
NO9PL D9 dH

w uv* yz Poisson ;{<e

Fig. 1 ³ Qq KLMNO9PL%" H t=|%"u>'",}6, ~/&*´3" !&"# K D ,kCef: C0H %" 42µ2¶6, e·uv2b

Dg6?@S 

%?, g4 79 w/?,uv6 6Dg#4 N ¸Q

S =|" ef!012 Debyef+ D2µ2¶¹H

!" lD @A6,
C 0 "!012

(16)

QCºV

lD(nm)0.305/C01/2

Q "2µ2¶ R C "2µ2¶c(15)

:%> ef!

R V "2µ2¶b ¥%> 

80126s012 D& 012" hB0126 kef! 6%

H "E MO2% C &'( )+. #g4 gS

,kC801279"s012. s012.
"8012S  E *3 

!h.S
" Rayleigh g»j3- i3 !
 i!k63

Dg

QS  012 w DMO2H  DS l¼ " /&6 qf*´3 2µ2

012%E UfF lD G=|"&F¶&M DmH 3

H6,

6%? ef: (C0) -,

6 lD -, D{ (15)HDNnY-H,kC 8g6sg

4 79 w/?,uv=|I-,S- . =|/?-,  
ῌ 145 ῌ

Qq,B%>

K. Hiraoka

9. 

  ESI, nanoESI,




!"#$%&'()*+,-. /&01&*+2
5)   !"#$%& 
'$()*+, -."/0
12 1 3 
4. 56678%  



3

4 9:;<=>?1 @AB

C.?DE1"FG$HI

@ABCJ

>?1KC> !

LMNO

EPQ85G$C> 1

.R%Fig. 6. +,

¤0

 van Berkel S T.E 
6) > !U .9:;<.VW2X > !YZ["G !#=\5]()!Y$"G !.%SX^& _`ab'E Fig. 5 . c( 
d)e* mmh jkl+, d*E 1X kG#\]^& _"&RF !GH.R]  <  .>  2X!G IA2

d9:;<= )ef g100 mmh i

/a.j% !UJ

X > F !G JK]G F !G

-eg700 nmh ".
0.jm34 1n@1| LM}9&s 1XS }.k8%
U tNE

o23"pE +,".&  4qSr5$

9:;<= 6StE!U "bS$%

(probe electrospray: PESI) >

5 !Y$"G !U| ^& _VW+,

E 1X c( .I%i7)g9)
@ABC s /56$%9:;<=tu7v>

 .kUt}9n.s5]1

w?1x c(

d9:;<= )ef g100 mmh

k.* mL/min"OPE 2S. +,"./a> !U

"yGz8{> !| ^& _VW }9:! ! $5]S~"] 1 x  ;. $.55 <.@<  ])> JKRSE

+,"Q5SEm]¡&#\5]G ¢x%}9k 56T£U

Fig. 6 . +,

¤0 ¥V"p>!" E=.2X% !U"E 1 =B> 9:;<= Ex 9:;<= > ?

+,"-¦ § >N/¨2+% /©.j%

9:;<=
=

".% 

.9:;<0.s"E )? 9:;<=> @ A?1G.55] dPaschen

+,

9:;<=

0>

.XY$U" 2+x <  ".E1> kGs.*E1>\ 1

0U"RS2+1>U"XY$ N©

.j%- s "*$%

BCh 1

"9:;<=

W7G.+,".

Fig. 7 . +,

@ABCkGDE2X%

<ª«U d10ῌ5 M.XY2X* pL

S jkl 10

ῌ2

M Z¬­

¦®¯°

[

!h  2X\± d²¥Vh "pE9) +,| *  ³2.5 kV >
] 1 ms µ^$Z>E>. +,2]!_ dTaylor ·*´. fL ^ ¶h 3X ¸

6S

56¹ 10 ms 6S 15 ms >¡#.]  56>. 1 ms ^ dº)h`a'

 +,leigh ¢».v^&/h0>@ABC> Ray-_VW2X. ms ^ dºZ[661"¼bE RG 

 3 @ABCcd]
+, > J+,
5S$!U.}9k5^&
Fig. 5. 

½¯  « 

"Q_VW2X> c( #i >ῌ 146 ῌ¥¦+,§)¨¦f3¼½

Fig. 7.

2.5 kV 3¡¢ £P¤3IJ3¥¦+,§)¨¦f©6 IJGª 700 nm, IJ !ª « pL, !ª 10῍5 M ¬b­ h S ®W¯ 10῍2 M °p±h²³´µ3 5
/¶· 9 W¸}.$¹º ῌ2008, American Chemical SocietyA

  

 !"#$ !%&'())*+,. /01 21345 6478 9:; <=5>!?@A7), 8)  BCC3DEF
GHIJ'KKLM' N3 Kῌ OP4<=Q R SETUV53WX<YZ[\364!3
GHQ]' !^3())*+,- . _`3a+b'c())*+,-. 'd.())*+,- Z3+b)efaghNaῌ (NaCl)n,i=<Xj^kl'  64!m3Z37n'Zo1agh3
po 2Cl῍qCl2

 !m3ragh[\ stu R6nu5vwax agh"R<y\R'z{o$ <=|u}~  d#<  
! IJ3>W  Fig. 6 3I
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Fig. 11.

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XYZ[G1 Fig. 12(b)  5l1e&e 

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12.

(18)

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Keywords: Electrospray, Probe electrospray, Laser spray,
Field desorption, Field ionization

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