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1 Kiroptikai spektroszkópia Összeállította: Pál Krisztina

Kiroptikai spektroszkópia

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Kiroptikai spektroszkópia. Összeállította: Pál Krisztina. Bevezető. A kiroptikai spektroszkópiák jelentősége abban áll, hogy segítségükkel különbséget tehetünk enantiomerek között, vagy diasztereomerek közt. Polarimetria (optikai forgatás adott hullámhosszon), - PowerPoint PPT Presentation

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  • *Kiroptikai spektroszkpiasszelltotta: Pl Krisztina

  • *BevezetA kiroptikai spektroszkpik jelentsge abban ll, hogy segtsgkkel klnbsget tehetnk enantiomerek kztt, vagy diasztereomerek kzt.Polarimetria (optikai forgats adott hullmhosszon), ORD /optikai rotcis diszperzi/ (optikai forgats a hullmhossz fggvnyben) CD /cikulris dikroizmus/ (jobbra s balra cirkulrisan polarizlt fny abszorpcija kzti klnbsget mri a hullmhossz fggvnyben)Mindegyik technika az (optikailag aktv) anyag s a polarizlt fny kzti klcsnhats mrsn alapszik.

  • *Optikailag aktv, kirlis anyagAz olyan anyagokat, amelyek a polros fny rezgsi skjt elforgatjk, optikailag aktv anyagoknak nevezzk. (A jelensget kezdetben csak a kristlyos anyagok szerkezetnek aszimmetrijval hoztk sszefggsbe).Arago, kvarckristly (1811)Biot, borksav vizes oldat (1838)Pasteur, aszimmetria optikai aktivits (1848-53)Kekul (1856-1863), Le Bel s van't Hoff (1874); aszimmetrikus, tetraderes C-atomKirlis: tkrkpvel nem fedsbe hozhat. Az egymssal fedsbe nem hozhat tkrkpi szerkezetek olyan viszonyban vannak egymssal, mint a jobb s bal kz (a kz grg nevbl - kheir - szrmazik az ilyen szerkezetek kirlis elnevezse). Optikai aktivits = forgatkpessg; kirlis molekulk nem racm halmaza optikailag aktv

  • *Enantiomerek (1)Egy enantiomer az egyike annak a kt sztereoizomernek, amelyek egymsnak fedsbe nem hozhat tkrkpei (mint a jobb s bal keznk; ugyanazok, de mgis ellenttei egymsnak).Szimmetrikus krnyezetben: azonos fizikai s kmiai tulajdonsgok Aszimmetrikus krnyezetben: klnbz tulajdonsgok. Kirlis molekulk egymshoz val viszonya

  • *Enantiomerek (2)Azonos olvads- s forrspont, trsmutat, oldhatsg, UV-lthat, IR- s NMR spektrum.A klnbz viselkeds kirlis genssel val klcsnhats esetn rvnyesl: Kirlis oldszerekben oldhatsguk klnbzikKirlis vegyletekkel klnflekpp reaglnak (pl. diasztereomer kpzs, rezolvls alapja)Kirlis fnnyel klnflekpp hatnak klcsn

    (Diasztereomerek: rszleges tkrkpei egymsnak; 1 vagy tbb aszimmetriacentrum abszolt konfigurcija eltr. Epimerek: csak egy aszimmetriacentrum abszolt konfigurcija ms)

  • *Kiralits fajti

    Centrlis kiralitsVonal kiralitsAnza kiralitsHeliklis kiralits

  • *A fny polarizcijaAz elektromgneses sugrzs (fny) egy halad hullm, amely oszcilll elektromos- s mgneses trbl ll, melyek klcsnsen merlegesek egymsra. ltalban az elektromos tr oszcillcija NEM egy fix (y,x) skon trtnik. Ilyenkor a sugrzs NEM polarizlt.xyzNem polarizlt fnySkban polarizlt fny

  • *Skban polarizlt fny ellltsaPolarizlatlan fnyA vertiklisan polarizlt komponens tjut.A horizontlisan polarizlt komponens abszorbeldik (nem jut t a szrn).A polarizcis szr a polarizlatlan fnyt skban (linerisan) polarizlt fnny alaktja. Erre j plda a Polaroid szr, mely hosszks molekulk prhuzamosan rendezett szlaibl ll. Csak a megfelel irnyban polarizlt fnykomponens jut t a szrn (az erre merleges komponens tkletesen abszorbeldik).

  • *A linerisan polarizlt fny kt cirkulris komponense

  • *Optikai forgatsA kirlis minta trsmutatja ms a skban polarizlt fny kt cirkulrisan polarizlt komponensre (jobbra s balra cirkulrisan polarizlt fny) nzve.nbalnjobbEbbl kvetkezen a kt cirkulris komponens sebessge ms s ms, amint kirlis mintn haladnak t.n=c/v Eredmny: a skban polarizlt fny polarizcis skja elfordul ( szggel).

  • *Optikai forgats (2)

  • *Polarimetria: Az optikai forgats adott hullmhosszon/589nm (Na D-vonal)/

  • *Optikai forgatsltalban specifikus forgatsknt van megadva [], melyet adott hmrskleten (T) s hullmhosszon (, lt. 589 nm) mrnek (a minta adott koncentrcij, adott oldszerrel kszlt oldatt alkalmazva).Megadsa: []D25 = +65 (c=1.0, EtOH) +, ramutat jrsval megegyez irny , ramutat jrsval ellenttesTisztasg meghatrozs: Mrt specifikus forgats*100 specifikus forgats(Pl.: (+6,76/+13,52)*100=50%)

  • *Optikai rotcis diszperzi (ORD)Az optikai forgatst mrjk a hullmhossz fggvnyben. (diszperzi = a hullmhossz fggvnyben)Polikromatikus fnyforrsDetektor: fotoelektron sokszoroz

  • *ORD spektrumEgyenletes lefuts grbe (n. plain curve) - ha a kirlis molekulban nincsen kromofr (nincs elnyels).Kromofrt tartalmaz kirlis minta esetn n. Cotton effektus (anomlia) rakdik a plain curve-re, ott ahol a minta elnyel. A cscs s a vly kzti metszspont hullmhossza jl egyezik az abszorpcis max al..

  • *Cirkulris dikroizmus

  • *Cirkulris dikroizmus (2)A skban polarizlt fny kt cirkulris komponense (jobbra s balra cirkulrisan polarizlt fny) klnbz mrtkben nyeldik el (abszorbeldik) kirlis mintn thaladva.Linerisan polarizlt fnyElliptikusan polarizlt fnysszegk:

  • *CD spektrumA CD spektrumban A-t, -t (egyezmnyesen bal-jobb) tntetik fel a hullmhossz fggvnyben. (nha az ellipticitst (), a molris ellipticitst [])AbalAjobb A /cl (A=Abal-Ajobb)= bal-jobb

    l=190-800nm, e- gerjesztsAAjobbAbal

  • *Enantiomerek CD spektrumajobb,(R)= bal,(S), bal,(R)= jobb,(S) bal, (R)- jobb,(R) = (R) = jobb, (S)- bal,(S) = (S)bal, (S)- jobb,(S)= (S)= jobb, (R)- bal,(R)= (R)

    TKRKPI VISZONY

    Diagram3

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    -3.8368453.836845

    -3.7939153.793915

    -3.7574453.757445

    -3.6966853.696685

    -3.6645853.664585

    -3.6505153.650515

    -3.6267053.626705

    -3.588963.58896

    -3.5555453.555545

    -3.5358353.535835

    -3.5156653.515665

    -3.4758753.475875

    -3.4472153.447215

    -3.422753.42275

    -3.386253.38625

    -3.3365053.336505

    -3.3079253.307925

    -3.2619253.261925

    -3.216863.21686

    -3.167763.16776

    -3.1117253.111725

    -3.066793.06679

    -3.032673.03267

    -3.0363653.036365

    -3.0125253.012525

    -2.956862.95686

    -2.9157152.915715

    -2.868462.86846

    -2.819742.81974

    -2.7735652.773565

    -2.7471252.747125

    -2.7325152.732515

    -2.7149652.714965

    -2.7158452.715845

    -2.7224452.722445

    -2.7195652.719565

    -2.708072.70807

    -2.705872.70587

    -2.6957852.695785

    -2.6561252.656125

    -2.6010152.601015

    -2.5680252.568025

    -2.5262452.526245

    -2.467162.46716

    -2.417622.41762

    -2.3939252.393925

    -2.3701152.370115

    -2.367362.36736

    -2.3774552.377455

    -2.3588252.358825

    -2.3459652.345965

    -2.3355152.335515

    -2.3151852.315185

    -2.3074652.307465

    -2.286852.28685

    -2.2242652.224265

    -2.125842.12584

    -2.031072.03107

    -1.976551.97655

    -1.92721.9272

    -1.898771.89877

    -1.857251.85725

    -1.8243351.824335

    -1.780131.78013

    -1.745231.74523

    -1.694171.69417

    -1.6533751.653375

    -1.5851951.585195

    -1.533161.53316

    -1.468761.46876

    -1.40211.4021

    -1.3244251.324425

    -1.273231.27323

    -1.219831.21983

    -1.179721.17972

    -1.1365351.136535

    -1.1090551.109055

    -1.0764851.076485

    -1.019091.01909

    -0.9577250.957725

    -0.8865750.886575

    -0.820840.82084

    -0.7732050.773205

    -0.7242050.724205

    -0.660450.66045

    -0.6108150.610815

    -0.5695150.569515

    -0.544890.54489

    -0.5396850.539685

    -0.5690950.569095

    -0.570280.57028

    -0.5446550.544655

    -0.5417250.541725

    -0.52980.5298

    -0.5285950.528595

    -0.54990.5499

    -0.5389350.538935

    -0.48937650.4893765

    -0.4546320.454632

    -0.43729150.4372915

    -0.4012590.401259

    -0.33323850.3332385

    -0.2907060.290706

    -0.2680150.268015

    -0.2751420.275142

    -0.2765510.276551

    -0.2694790.269479

    -0.27256450.2725645

    -0.26183750.2618375

    -0.2431050.243105

    -0.2272360.227236

    -0.2254340.225434

    -0.2513670.251367

    -0.23312950.2331295

    -0.24120550.2412055

    -0.2356870.235687

    -0.18569950.1856995

    -0.1440730.144073

    -0.1509680.150968

    -0.1509950.150995

    -0.12270250.1227025

    -0.12802850.1280285

    -0.11354250.1135425

    -0.13093650.1309365

    -0.14608050.1460805

    -0.15692150.1569215

    -0.13151150.1315115

    -0.0907830.090783

    -0.01114750.0111475

    0.04295135-0.04295135

    0.050228-0.050228

    0.0361614-0.0361614

    0.0623415-0.0623415

    0.1081595-0.1081595

    0.1247105-0.1247105

    0.1036435-0.1036435

    0.0834055-0.0834055

    0.079478-0.079478

    0.134468-0.134468

    0.1899385-0.1899385

    0.245852-0.245852

    0.3106815-0.3106815

    0.3478695-0.3478695

    0.3679885-0.3679885

    0.4245775-0.4245775

    0.4737555-0.4737555

    0.51966-0.51966

    0.577105-0.577105

    0.58705-0.58705

    0.59207-0.59207

    0.5639-0.5639

    0.600725-0.600725

    0.68978-0.68978

    0.68258-0.68258

    0.737105-0.737105

    0.849905-0.849905

    0.984395-0.984395

    1.09996-1.09996

    1.223105-1.223105

    1.391345-1.391345

    1.489135-1.489135

    1.537065-1.537065

    1.53243-1.53243

    1.52942-1.52942

    1.653755-1.653755

    1.737935-1.737935

    1.786305-1.786305

    1.819225-1.819225

    1.85758-1.85758

    1.895255-1.895255

    2.01009-2.01009

    2.071005-2.071005

    2.113915-2.113915

    2.115045-2.115045

    2.140495-2.140495

    2.19661-2.19661

    2.298335-2.298335

    2.378475-2.378475

    2.52472-2.52472

    2.65763-2.65763

    2.71857-2.71857

    2.9076-2.9076

    3.020115-3.020115

    3.183295-3.183295

    3.320805-3.320805

    3.365465-3.365465

    3.49058-3.49058

    3.653405-3.653405

    3.72551-3.72551

    3.7537-3.7537

    3.794855-3.794855

    3.84882-3.84882

    3.85659-3.85659

    3.90189-3.90189

    3.955655-3.955655

    4.212065-4.212065

    4.42175-4.42175

    4.55857-4.55857

    4.556695-4.556695

    4.57663-4.57663

    4.59124-4.59124

    4.648125-4.648125

    4.727535-4.727535

    4.7039-4.7039

    4.67133-4.67133

    4.627005-4.627005

    4.57993-4.57993

    4.558925-4.558925

    4.575285-4.575285

    4.61553-4.61553

    4.55152-4.55152

    4.39617-4.39617

    4.301315-4.301315

    4.321505-4.321505

    4.180015-4.180015

    4.028015-4.028015

    3.983765-3.983765

    3.99636-3.99636

    3.949945-3.949945

    3.80916-3.80916

    3.665205-3.665205

    3.60567-3.60567

    3.556125-3.556125

    3.54541-3.54541

    3.651765-3.651765

    3.595795-3.595795

    3.75516-3.75516

    3.87267-3.87267

    3.845015-3.845015

    3.933385-3.933385

    4.13698-4.13698

    4.30855-4.30855

    4.44407-4.44407

    4.62129-4.62129

    4.89613-4.89613

    4.897325-4.897325

    5.16895-5.16895

    5.21555-5.21555

    5.1897-5.1897

    5.21295-5.21295

    5.26485-5.26485

    5.17305-5.17305

    4.994975-4.994975

    5.17645-5.17645

    5.25765-5.25765

    5.14525-5.14525

    hullmhossz [nm]

    De [dm3 mol-1 cm-1]

    Munka1

    AZMAmademadee

    400-0.4505430.2913564000.145678-0.145678

    399.9-0.4578260.286351399.90.1431755-0.1431755

    399.8-0.4609240.291248399.80.145624-0.145624

    399.7-0.4568340.301722399.70.150861-0.150861

    399.6-0.4553990.296641399.60.1483205-0.1483205

    399.5-0.4581240.296138399.50.148069-0.148069

    399.4-0.4723630.30416399.40.15208-0.15208

    399.3-0.4888530.295196399.30.147598-0.147598

    399.2-0.4907560.299084399.20.149542-0.149542

    399.1-0.4890410.303925399.10.1519625-0.1519625

    399-0.4939180.3194083990.159704-0.159704

    398.9-0.4904660.325356398.90.162678-0.162678

    398.8-0.4881260.311136398.80.155568-0.155568

    398.7-0.4992150.286041398.70.1430205-0.1430205

    398.6-0.5072710.283707398.60.1418535-0.1418535

    398.5-0.4928320.288541398.50.1442705-0.1442705

    398.4-0.4714130.298598398.40.149299-0.149299

    398.3-0.4547890.323126398.30.161563-0.161563

    398.2-0.432020.361208398.20.180604-0.180604

    398.1-0.4285930.381544398.10.190772-0.190772

    398-0.4207310.3939053980.1969525-0.1969525

    397.9-0.4213260.386374397.90.193187-0.193187

    397.8-0.4314260.356919397.80.1784595-0.1784595

    397.7-0.4315580.327059397.70.1635295-0.1635295

    397.6-0.4249170.332059397.60.1660295-0.1660295

    397.5-0.4248910.333874397.50.166937-0.166937

    397.4-0.4447350.310594397.40.155297-0.155297

    397.3-0.4643280.289087397.30.1445435-0.1445435

    397.2-0.4706750.278751397.20.1393755-0.1393755

    397.1-0.4587020.285753397.10.1428765-0.1428765

    397-0.4395480.3123823970.156191-0.156191

    396.9-0.3962640.352324396.90.176162-0.176162

    396.8-0.3807070.378056396.80.189028-0.189028

    396.7-0.400380.3775396.70.18875-0.18875

    396.6-0.4104990.386683396.60.1933415-0.1933415

    396.5-0.4110730.383722396.50.191861-0.191861

    396.4-0.4088420.388767396.40.1943835-0.1943835

    396.3-0.4013440.388396.30.194-0.194

    396.2-0.3839410.388816396.20.194408-0.194408

    396.1-0.3741390.378386396.10.189193-0.189193

    396-0.3749760.3658943960.182947-0.182947

    395.9-0.3672630.359684395.90.179842-0.179842

    395.8-0.3662410.348803395.80.1744015-0.1744015

    395.7-0.3584750.339189395.70.1695945-0.1695945

    395.6-0.3465840.336165395.60.1680825-0.1680825

    395.5-0.3295240.341506395.50.170753-0.170753

    395.4-0.3016010.358164395.40.179082-0.179082

    395.3-0.2894290.352315395.30.1761575-0.1761575

    395.2-0.2865320.353182395.20.176591-0.176591

    395.1-0.299530.351679395.10.1758395-0.1758395

    395-0.3051990.3439973950.1719985-0.1719985

    394.9-0.3239950.320618394.90.160309-0.160309

    394.8-0.3374980.310313394.80.1551565-0.1551565

    394.7-0.3424920.316132394.70.158066-0.158066

    394.6-0.3323910.329715394.60.1648575-0.1648575

    394.5-0.3200710.33026394.50.16513-0.16513

    394.4-0.3033120.345101394.40.1725505-0.1725505

    394.3-0.2977810.341326394.30.170663-0.170663

    394.2-0.2952240.333258394.20.166629-0.166629

    394.1-0.2944370.344788394.10.172394-0.172394

    394-0.2795670.3514253940.1757125-0.1757125

    393.9-0.2665440.344337393.90.1721685-0.1721685

    393.8-0.2679530.329738393.80.164869-0.164869

    393.7-0.257150.317874393.70.158937-0.158937

    393.6-0.2709880.290435393.60.1452175-0.1452175

    393.5-0.2748470.283391393.50.1416955-0.1416955

    393.4-0.2630620.284168393.40.142084-0.142084

    393.3-0.260710.284574393.30.142287-0.142287

    393.2-0.2707480.275178393.20.137589-0.137589

    393.1-0.2842510.264349393.10.1321745-0.1321745

    393-0.2892080.2594893930.1297445-0.1297445

    392.9-0.30640.250402392.90.125201-0.125201

    392.8-0.3220440.255777392.80.1278885-0.1278885

    392.7-0.3197470.266464392.70.133232-0.133232

    392.6-0.3234820.276985392.60.1384925-0.1384925

    392.5-0.3462830.270995392.50.1354975-0.1354975

    392.4-0.3632680.256861392.40.1284305-0.1284305

    392.3-0.3584270.244343392.30.1221715-0.1221715

    392.2-0.3496460.244015392.20.1220075-0.1220075

    392.1-0.3506190.251997392.10.1259985-0.1259985

    392-0.3434760.2639273920.1319635-0.1319635

    391.9-0.3473510.257451391.90.1287255-0.1287255

    391.8-0.3353540.251178391.80.125589-0.125589

    391.7-0.3396010.252454391.70.126227-0.126227

    391.6-0.323210.269041391.60.1345205-0.1345205

    391.5-0.3076040.264174391.50.132087-0.132087

    391.4-0.310590.236413391.40.1182065-0.1182065

    391.3-0.3163210.221135391.30.1105675-0.1105675

    391.2-0.3319390.218517391.20.1092585-0.1092585

    391.1-0.3504530.218024391.10.109012-0.109012

    391-0.3761280.2112963910.105648-0.105648

    390.9-0.3891070.217726390.90.108863-0.108863

    390.8-0.3825340.216822390.80.108411-0.108411

    390.7-0.3954440.202247390.70.1011235-0.1011235

    390.6-0.4128550.200179390.60.1000895-0.1000895

    390.5-0.4192250.204189390.50.1020945-0.1020945

    390.4-0.4450910.191092390.40.095546-0.095546

    390.3-0.4634470.198668390.30.099334-0.099334

    390.2-0.4747690.195622390.20.097811-0.097811

    390.1-0.4786950.192344390.10.096172-0.096172

    390-0.4726430.1927683900.096384-0.096384

    389.9-0.4695150.185536389.90.092768-0.092768

    389.8-0.4416360.197723389.80.0988615-0.0988615

    389.7-0.4190070.209463389.70.1047315-0.1047315

    389.6-0.4056140.23762389.60.11881-0.11881

    389.5-0.3957180.247522389.50.123761-0.123761

    389.4-0.3891630.242112389.40.121056-0.121056

    389.3-0.3809310.239526389.30.119763-0.119763

    389.2-0.3750640.232701389.20.1163505-0.1163505

    389.1-0.3745080.234795389.10.1173975-0.1173975

    389-0.3837720.2470273890.1235135-0.1235135

    388.9-0.4151340.245711388.90.1228555-0.1228555

    388.8-0.4391830.240617388.80.1203085-0.1203085

    388.7-0.4435620.232761388.70.1163805-0.1163805

    388.6-0.4228540.243227388.60.1216135-0.1216135

    388.5-0.4375950.232855388.50.1164275-0.1164275

    388.4-0.4421840.216361388.40.1081805-0.1081805

    388.3-0.4436980.197549388.30.0987745-0.0987745

    388.2-0.4585790.180978388.20.090489-0.090489

    388.1-0.4600080.203615388.10.1018075-0.1018075

    388-0.4675750.2152343880.107617-0.107617

    387.9-0.4548330.22987387.90.114935-0.114935

    387.8-0.4436420.247372387.80.123686-0.123686

    387.7-0.4332230.259921387.70.1299605-0.1299605

    387.6-0.420920.256456387.60.128228-0.128228

    387.5-0.4272870.243247387.50.1216235-0.1216235

    387.4-0.4300760.253276387.40.126638-0.126638

    387.3-0.429190.269923387.30.1349615-0.1349615

    387.2-0.4339010.269037387.20.1345185-0.1345185

    387.1-0.4243530.266121387.10.1330605-0.1330605

    387-0.4199840.2559743870.127987-0.127987

    386.9-0.4043930.24542386.90.12271-0.12271

    386.8-0.394520.24025386.80.120125-0.120125

    386.7-0.4000530.220372386.70.110186-0.110186

    386.6-0.3850840.230173386.60.1150865-0.1150865

    386.5-0.3695840.2415386.50.12075-0.12075

    386.4-0.3749820.24983386.40.124915-0.124915

    386.3-0.3758050.246346386.30.123173-0.123173

    386.2-0.3725550.246538386.20.123269-0.123269

    386.1-0.3663570.248268386.10.124134-0.124134

    386-0.3593340.2445443860.122272-0.122272

    385.9-0.350230.240879385.90.1204395-0.1204395

    385.8-0.3447050.233044385.80.116522-0.116522

    385.7-0.3384980.225168385.70.112584-0.112584

    385.6-0.3339450.217693385.60.1088465-0.1088465

    385.5-0.3277890.208513385.50.1042565-0.1042565

    385.4-0.3356180.198472385.40.099236-0.099236

    385.3-0.3561810.195116385.30.097558-0.097558

    385.2-0.3585530.217864385.20.108932-0.108932

    385.1-0.3318940.252043385.10.1260215-0.1260215

    385-0.3233570.2718243850.135912-0.135912

    384.9-0.3152030.279389384.90.1396945-0.1396945

    384.8-0.3034740.283732384.80.141866-0.141866

    384.7-0.3032620.270332384.70.135166-0.135166

    384.6-0.2950520.262922384.60.131461-0.131461

    384.5-0.2996680.245669384.50.1228345-0.1228345

    384.4-0.3010310.242965384.40.1214825-0.1214825

    384.3-0.2863410.24845384.30.124225-0.124225

    384.2-0.2593630.26282384.20.13141-0.13141

    384.1-0.2296370.270782384.10.135391-0.135391

    384-0.2170390.2559173840.1279585-0.1279585

    383.9-0.186740.257816383.90.128908-0.128908

    383.8-0.1632060.272202383.80.136101-0.136101

    383.7-0.1423870.294147383.70.1470735-0.1470735

    383.6-0.1345470.313215383.60.1566075-0.1566075

    383.5-0.137580.323187383.50.1615935-0.1615935

    383.4-0.1461160.34112383.40.17056-0.17056

    383.3-0.1542850.35526383.30.17763-0.17763

    383.2-0.1778020.350524383.20.175262-0.175262

    383.1-0.1902070.33901383.10.169505-0.169505

    383-0.19460.3250993830.1625495-0.1625495

    382.9-0.1892030.319205382.90.1596025-0.1596025

    382.8-0.1995930.301009382.80.1505045-0.1505045

    382.7-0.2198530.296639382.70.1483195-0.1483195

    382.6-0.2292320.314808382.60.157404-0.157404

    382.5-0.2280650.345457382.50.1727285-0.1727285

    382.4-0.2247920.365836382.40.182918-0.182918

    382.3-0.2204690.371001382.30.1855005-0.1855005

    382.2-0.2305390.370317382.20.1851585-0.1851585

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    3