Вы находитесь на странице: 1из 43

1

44-
, 21-30 , 2012
:
.


E-mail: icho2012@umd.edu
:
Seth N. Brown, University of Notre Dam
Michael P. Doyle, University of Maryland
Daniel E. Falvey, University of Maryland
George R. Helz, University of Maryland
Kaveh Jorabchi, Georgetown University
Douglas A. Julin, University of Maryland
J.L. Kiappes, University of Oxford
John Kotz, State University of New York
Evguenii Kozliak, University of North Dakota
Amy S. Mullin, University of Maryland
Garegin A. Papoian, University of Maryland
Elena Rybak-Akimova, Tufts University
Andrei N. Vedernikov, University of Maryland

:
, ,

, ,

4
4


1.
2.
3.

5
9
10

4.
5. .
6. :
7.
8. : ,
9.
10.
11.
12.
13.

11
12
13
14
15
16
17
18
19
20

14. :
15.
16. :
17.
18.
19.
20.
21.
22. -
23.

21
22
24
25
27
29
31
34
36
39

24. -
25. -
26.
27.

40
41
44
45



28. ()
29.

48
49
53

3
30.

55

31. :
32.
33. :

59
67
70

, ,






NA = 6.02211023 1
kB = 1.38071023 K1
R = 8.3145 K11 = 0.08205 K1 1
c = 2.9979108 1
h = 6.62611034
me = 9.109382151031
P = 1 = 105



1 () = 109
1 () = 1012

Patm = 1.01325105 = 760 . . = 760


273.15 K

. .
/.
. . 1H
X (, X = 11B). , . . -.
. . : . .
. , .
.
. . .


1.
() . 1912 (18761946), ,
. (19192011) 1976 .
) BH4.
) 1H BH4.

1:1:1:1 7 .
( 1H 1/2, 11B 3/2, 10B 3.) .
) , 11B BH4 1:4:6:4:1
JB-H = 85 .
) Al(BH4)3 , B Al , AlB 120.
BH4 AlHB,
H AlB3. Al(BH4)3 BH4
[Al(BH4)4]. 11B [Ph3MeP][Al(BH4)4]
1:4:6:4:1 J = 85 . 298 K 1H
7.5-8.0 .., 2.8 .. (J = 13 )
0.5 .. 203 K.
. ( 11B 3/2, 31P 1/2.)

2.

. , AlCl3
-, Al2(CH3)6 [(C2H5)2AlCl]2
-.
A.
) AlCl3 (.. = 192 C; 180
C) ,
Al2Cl6. , ( ).
) AlBr3 (.. = 98 C,
255 C), AlF3 (.. = 1291 C).
?
.
[(C2H5)2AlCl]2 NaF [(C2H5)2AlF]x. . [(C2H5)2AlF]x , , , ..?
) [(C2H5)2AlF]x . 1.097 65.26 ;
5.276 C. ( 5.500 C, 5.57 C /(/).)
x [(C2H5)2AlF]x?
) [(C2H5)2AlF]x.

3.
,
. ,
. O ( B(OH)3, BO33, B3O63)
, ( [BO4]5).

7
Na2B4O710H2O .
,
.
- BH4 .
,
.
) 0.5 M B(OH)3 pH. B(OH)4,
B4O5(OH)42 (, ) B3O3(OH)4.
i. , , , .
ii. .

) . ,
(HOCH2)3CNH2. :
B4O72(-) + 2 H3O+(-) + 3 H2O() 4 H3BO3(-)
(HOCH2)3CNH2(-) + H3O+(-) H2O() + (HOCH2)3CNH3+(-)
Na2CO3, ? , 0.1 ,
40.0 0.020 M HCl.

8
4.
, BN
CC. , B N.
, H3NBH3.
:
H3NBH3() 2.5 H2() + (, BNH)
( H3NBH3 BNH,
.) BN.
,
. ,
, ZnS. .
, BN.
a) .
?

) ZnS- , ,
, . BN 3.45 /3.
BN.

5. .
298 K , . . - , , , . .
) , , ( 1 = 105 ).

fH, /

S ( 1 K1)

Sn(,)

2.016

44.14

Sn(,)

0.000

51.18

) . , a = b = 583.2 c = 318.1 , 4 Sn. ( 3).


) , , .

10

(Cu K, = 154.18 )
(111) 2= 23.74. ( 3).
) 1090 .

, , ? ,
(E), (S)
.

6. :
( ) .
-.
Si Si.
SinH2n+2 . SiSi,
.
a) SiSi Si2H6, :
HH = 436 /;
SiH = 304 /;
fH [Si()] = 450 /;
fH [Si2H6()] = 80.3 /.
) SiSi ( 347 /). , n 2.

11
7.
, 20
.. (18751946). ,
. 20 . .. (19122004), (1979) (, C4H8OBH3) .
N(SiH3)3, , . .
) NSi3 . , .
) rHo - [B(CH3)3]
:

rHo (), /

NH3

57.5

N(CH3)3

73.7

N(C2H5)3

42

C7H13N ()

83.4

i. N(CH3)3 , ,
.
ii. , .
) (CH3)3NB(CH3)3 100.0 C
0.050 . B(CH3)3 ? (
(CH3)3NB(CH3)3 Ho = 73.7 1, So = 191 11.)

12
8. : ,
. O2
N2 .
,
. .
A.
, , A O2,
120 , B. B (2.00 )
1.00 , - .
T, oC

p,

25

0.653

50

0.838

) A B.
) B ? H S .
.
B ( A) F2 C. C
D. D 1.000 0.5000 M
NaOH . 30.12
.
) C D D.
) D E. E.

9.
19 , .

13

A.
.
, . () ().
, .
) (II). .
i. (PPh3)2PtCl2 (Ph = );
ii. [Pt(NH3)()(NO2)(NH2OH)]+ ( 1926 .) NO2, NH2OH
(II) N;
iii. Pt(en)Cl2 (en = , H2NCH2CH2NH2).
)
(III) (III).
i. Co(py)3Cl3 (py = );
ii. [Cr(ox)2(H2O)2] (ox = -, [O2CCO2]2);
iii. [Co(en)(NH3)2Cl2]+.
.

.
(III), [Ru()()Cl4]. , (CH3)2SO
, , ,
O, S.

)
[Ru()()Cl4]?
C.
(OLED organic light-emitting diode) . -

14
. , , (III) 8-. , .

Al3+ 8- (C9H6NO)
.
) , Al3+ 6, , (C9H6NO)3Al? .

10.
pH
, , , pH . -
, . CO2 pH
: CO2 pH 0.0017 .
( 466.59 1)
. H2In0 pH
, . 298 K
( ): Ka2 = 108.090. () HIn In2 () :

436 (11)

596 (11)

HIn

13900

44.2

1930

33800

In

15
10.00 . :

436


596

0.052

0.023

0.651

0.882

pH .
.

11.
,
- . - . -
.
) , PbCrO4() pH = 6.000 . ,
Pb2+, CrO42, HCrO4 Cr2O72. 1.
.
Ksp = [Pb2+ ][CrO24 ] = 2.82 1013
Kw = [H2+ ][OH ] = 1.00 1014
Ka 2

[H + ][CrO42 ]
=
= 3.34 107

[HCrO4 ]

[Cr2O72 ]
KD =
= 3.13 1014
+ 2
2 2
[H ] [CrO4 ]

) ,
(CrT) HCrO4 Cr2O72 . , pH = 3.00, CrT.

12.
Th U , .

, . , , . .

16
, ,
1

222

Rn (-

222

t = 3.8 ) 4.2 (100 ) . Rn


226Ra (t = 1600 ), 6.7 1
(100 )1. .
226Ra 222Rn, 222Rn , -
.
) 222Rn : (100 )1 1.
) , , 1.
) , , , ?
) 222Rn -. ( ).

13.
,
, , , .
, . .
.
- [Co(en)2Cl2]+ (en = ) Cl : a) , ) .
Associative Mechanism

Cl
NH2

Cl

+ Cl

Co
NH2

Cl

NH2

k1
[Co(en)2Cl3]
k-1

H2N

k2

NH2
Co
NH2

Assoc. Intermed.

Cl

NH2

+ Cl

NH2

-
trans isomer

-
cis isomer

Dissociative Mechanism

Cl
NH2

Cl

k1

Co
NH2

NH2
H2 N

k-1

[Co(en)2Cl]2+ + Cl

Dissoc.
Intermed.

cis isomer
-
H2N

Cl

NH 2CH2CH2NH2
NH 2 = ethylenediamine,

k2

NH2
Co
NH2
Cl

NH2
NH2

-
trans isomer

17
) , .
) , ,
: (i) , (ii) .
) , k.
) , ?

14. :
1920 ,
, 1,2- () . . , . (Pc) . .
) ,
(III) .

) - SO2 . -
SO2.
) , ,
NaHSO2. , -.
) .
i. (III) PcFeIII (II) PcFeII:

18
S2O42 + PcFeIII PcFeII + ()
:
r1 = k [PcFeIII][S2O42]
ii. , (II)
(I)
S2O42 + PcFeII PcFeI + ( )
:
r2 = k [PcFeII][S2O42]0.5.
iii. (II) (I):
S2O42 + PcCoII PcCoI + ()
:
r3 = k3 [S2O42]
, .

15.
, , , . , ,
.
(1H)
(2H, D) (3H, T).
, , 1
E0 = h,
2
1 k
=
2
k , = m1m 2 . m1 m 2
, .
, , : ,
, . (kH/kD),
58 . ,
, : kH/kD < 1.4.

19

,
. 2--6,8- 4- :
O3S

H/D

N2
OH
3

+
O3S
1

Cl
2

) 4- 2 .
) 3 ( H 1)
.
) 1H ( 1 H
) 2 (pH = 6.6)
. ,
1H, 2. , .
?
) 1H 2 , 1D 2
(k1H/k1D = 6.55). , 4 5
(k4H/k4D = 0.97). .
OH

N2
H/D

CH3O
6

SO3
4

) 1H 1D 2 , . [py]. ( , , pH 6.6).
[py], 1

k1H, 11

k1D, 11

kH/kD

0.0232

6.01

1.00

6.01

0.0467

11.0

0.0931

22.4

0.140

29.5

20
0.232

46.8

0.463

80.1

0.576

86.1

0.687

102.

0.800

106.

0.905

110.

30.4

3.62

) , 4H 5
.
) 1 ( ):
:

N2

N2

N2

Cl
Cl

k1H/k1D:

6.55

NO2

5.48

4.78

16. :
80% . ,
. , , , . , .
Hg
. , , , .
, ,
11 000 K. Ar . , -
Ar
, ,

21
.
, ,
Ar, ,
Te = 11 000 K, T = 313 K.
: 120
, 3.6 , Ar 3 (1 = 1 .. = 1/760 ).
) , , Ar 4.9103 3
ne = 5.01017 3, = 7.91010 ?
) Ar, Je-Ar ( 1)
?
, , fe->Ar = 2.5105, Ar , Ar 3/2 kBT, kB
, T . ,
.
, ,
Ar :

I Ar = Ar (TAr T )

St
,
R

Ar = 1.772104 11K1 , R = 3.6 , St 120 .


)
Ar, TAr.
) Ar , 40 (1 = 1).
) TAr 1 10 , .
, , ~ P1. A
.

22
17.
, . , , . , ,
.

P [P], , , P:

( ). :

Kd =

[P ] []
[P ]

[] , [P]
, , Kd .

v = 640 /. , , . ( 1).
:
l = 5 n = 16 .
.

23
, , .
: Kd = 0.5106, [P] = 100 , [] = 10 .

18.
-
.

.
.
- , .
, - . - -1,3,5-.

-1,3,5-
= nL/2, n
, n = 1, L ,
289 867 -1,3,5-. - (1):

n2h2
En =
8me L2

(1)

n ( 1 ), h , me
, L .
.
a) , :
i. - ;
ii. - 1,3,5-.
) -
. n
.

24
) , - .
) -.
-. L = 1850
.

--
, , ,
-.

- :

En =

n2h2
82 me R 2

(2)

n 0 R . ,
n
, , n = 0.
139 368 , .
) (2), - . .
. .
)
.

25
)
.
) , . ( ) .

19.
HFSbF5 B, 1H (60 ) . 97 oC. ..: 9.38 (d, 2H), 8.40 (d, 2H), 5.05 (m, 2H), 3.30 (t,
3H). 510
..
CH3
HF-SbF5

) B, 97 C.
) 97 C ()
B.
) / , .
) ,
.
) 3.30 .. 97 C .
(J = 4.4 )?

26

27

20.
20 .
(LDH) - -, NADH. - H NADH H+:
NH2

NH2

O
CO2-

H3C

+ H+ +

CO2-

H3C

OH

pyruvate

NAD+

lactate

NADH

- SO32- NAD+:
NH2

NH2

O
SO32-

O
N

O3S

NADH, LDH, 1. ;
.
1
Gln-102

Thr-246

Arg-109
NH
H2N

H
O

H
O

OH

CH3
O

His-195

H3C

NH
H

NH2

HN

Asp-168

NH
NH

Arg-171

(NADH)
Dihydronicotinamide

(NADH)
NH2
H3C

C2H5
Ile-250

( NADH) ( NAD+) , LDH, pH. .


pKa = 7, His-195 LDH.

28

B
log (kcat/Km)

log (kcat/Km)

7
pH

10

10

pH

) , ?
1, Arg-109 His-195
.
) Arg-109
His-195 ? .
Ile-250
NADH ( 1).
) Ile-250 NADH?
Arg-109 LDH . Arg-109 . :
NADH 1400
, .
, 15 .
NAD+ .
) , , Arg-109 , LDH?
Asp-168 His-195 (
1). Asp-168 LDH:
1) Asp-168 His-195 His-195 .
2) Asp-168 His-195 His-195,
.
Asp-168 Ala ( 2) Asn ( 1),
. .

29

(Asp-168)

1
(Asn-168 )

:
/
1

2
(Ala-168 )

:
/
2

:
Km (),

0.06

10

0.006

3.3

0.018

kcat, 1

250

20

12.5

5.5

45

kcat/Km,
M11

4.2106

2103

2080

1.7103

2500

:
Km (),

40

120

0.33

80

0.5

kcat, 1

0.12

75

0.09

100

kcat/Km,
M11

2.2102

225

1.13

200

) Asp-168 (1) (2)


?

20 ( ).

30

21.
20.
C , Bacillus amyloliquefasciens :
O

R
+ H2O

N
H

R
O-

H3N


RCO-L - Nuc, :
O

O
R

+ Nuc

Nuc

+ L

31
-
( ). Ser221
His64.

,
N- . , S1S4. C (. ): Gly166 S1, Asn62 S2 Tyr104 S4.
,
.
- Ala-Ala-Pro-Phe ,
4
( Ala-Ala-Pro-Phe S4S1 ).
.
Gly166 Ile ( Gly166Ile)
:
I
Ala-Ala-Pro-Phe--
II
Ala-Ala-Pro-Ala--
III
Ala-Ala-Pro-Glu--
IV
Ala-Ala-Pro-Tyr--

32

) ( ,
kcat / Km)?
S1, S2 S4
, . :
1:
Gly166 Asp
2:
Gly166 Asp Asn62 Asp
3:
Gly166 Asp, Asn62 Asp Tyr104 Asp
:
I
V
VI

Ala-Ala-Pro-Phe--
Ala-Ala-Lys-Phe--
Arg-Ala-Lys-Arg--

VII
VIII
IX
X
XI
XII
XIII

Arg-Gly-Lys-Glu--
Ala-Ala-Pro-Arg--
Ala-Gly-Glu-Arg--
Phe-Gly-Lys-Arg--
Leu-Gly-Phe-Arg--
Ala-Ala-Lys-Arg--
Arg-Gly-Ala-Arg--

XIV Arg-Gly-Lys-Phe--
) ?

22. -
( 2002 )
() -
.
, ,
.
- - . , . .
.
,
. - 160 -

33
, . 1 3 CH3OH,
1 3 CD3OH.
) () (), () .
CH3OH 1, CD3OH
2. 2 .
10 0.1% , . - (), .
:

) 1 2. ?
,
+1, +2, +3 .. , M
( ) -
[M+H]+, [M+2H]2+ [M+3H]3+. ( ),
-,
(m/z) .
- ( 1
2) m/z: 703.9 (100), 704.4 (81), 704.9 (36), 705.4 (61), 705.9 (44) 706.4

34
(19). ( ).
) ?
) , , .
) m/z , ?
) () .
,
, .
) , ,
.
) , CD3OH 13CH3OH? ,
12CH3OH 13CH3OH.
) 13CH3OH
CD3OH?

23.
,
. , , .
1950- , B1 .
1990- (. ). .

) , CH2, ( ), ( ).
) IIV, .
) ?
) CH2 . , IIV
, . ?

35
) AD D:
CH3

I2/PPh3

BrC2H4OH
H 3C

NH2

H
N

CH3

PhNH3Cl
HC(OEt)3

KOC(CH3)3

HCOOH

) , . I.

24. -
1928 :

-
. ,
.
) .., 1990
- . , (*).

. - -.
(N, O, S .), . -
.
) :

36

i. D E.
ii. , , .
) -.
:

.
) ,
, ,
-.
:

25. -
() , ,
, . -. ,
, ..
..

37
, , 1981
( ., ). ,
(),
, , (),
.
, , - () . -
:
-,

4n

4n+2

,
:
i.

38
ii.

) . , , ,
(-).
i. Y, Z F G
.

ii. (i)(v):

i
ii
iii
iv
v
.
:

39
, , 1,5-, 13C ( ) , .
) SNF4435 C ( , ) .
i. :

LDA, Me3SiCl
()

ii. V, ? , - .

40
26.

.
.. ( )
Pfizer 1962 . .
AI.
: (1) E F ; (2) A, B, C, D E 7.8 ..; G, H I .
psi = ; 1 psi 6894.76 .
O
OCH3

base
A + CH3OH

+ CH3COOCH3
OCH3

base
A

BrCH2COOCH3
B

- (base)H+ +
- H

base
C

+ CH2=CHCOOCH3

CH3OH
+
H+ H
(
(selective

esterification)

H3O+

reflux
. .

H2, 200 psi

+ CO2 + 3CH3OH

Cl2

-HCl

(-)
Pd (catalyst)
Cl

HF
H

-H2O

COOCH3

CH3OOCCOOCH3
base

OH
OCH3 O

OH

Cl
H3C

COOCH3

OH

N(CH3)2
OH
NH2

OH
OCH3 O

OH

several
steps

OH

41
27.
, , . , , . . DNJ,
.
) AD :

DBU = 1,8-[5.4.0]-7

42
) i. JP :

ii. (Tf)
. : (1) (5).

iii. Q DNJ 3 .
Q' Q":

43

) DNJ, ,
, , . X Y, , Z.
: (S, S)
.

( 70%)

( 98%)

( 99%)

( 88%)