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Dependence fluorestsentnyhsvojstv from parametres of medium. Tetraaril - tetratsiaioporfiraziiy as fluorescent molecular curls

It is supposed, that the developed photosensitizer will be delivered to target fabrics by means of preparation introduction in a blood channel. In this connection the important problem was definition of spectroscopic properties tetraariltetratsianoporfirazinov in blood whey.

We had been spotted quantities of quantum yields of fluorescence for tetraariltetratsianoporfirazinov as a part of various polymeric nanochastits in the distilled water, whey of blood and 10 % a solution albumina (drawing 15, table 5).

The fluorescence quantum yield tetraariltetratsianoporfirazinov as a part of various polymeric nanochastits, dissolved in water, has made 10"3-10" 4. Essential increase of this quantity has been registered in the presence of fibers of whey of blood. The greatest value of quantity of a quantum yield of fluorescence for all explored fluoroforov is registered in 10 % a solution albumina, for Pz (I) this value comes nearer to 0,85. Thus it is possible to speak about amplification of fluorescence to 400 times in relation to a water solution of the same linkings. Thus the fluorescence quantum yield in a solution albumina exceeded a quantum yield in blood whey in 3-5 time (table 5).

Interaction porfirazinov with fibers of whey of blood and, first of all, syvorotochnym albuminom, to components about 60 % can be one of mechanisms of observable effect

syvorotochnyh fibers. This guess proves to be true the well-known facts about ability syvorotochnogo albumina to relate the considerable number ligandov various chemical structure [81, 158].

However influence albumina on fluorescence explored porfirazinov is much more considerable, than it has been shown for others tetrapirrolnyh FS [134, 156, 269]. Besides, us it has been shown similar nonsingle amplification of fluorescence in bezbelkovyh mediums (etanolglitserinovye intermixtures), thus growth of viscosity of medium was accompanied by quantum yield magnification (drawing 16).

Table 5.

Quantities of a quantum yield of fluorescence and amplification constants _________ for Pz (I) and YbPz (I) as a part of various nanochastits

The sample Quantum yield *, f (amplification constant)
Water Whey

Blood

10 % a solution albumina
Pz (I) PEG 8,610-4 0,017 (20) 0,071 (83)
Pz (I) AlgNa 5,610-4 0,06 (109) 0,24 (441)
Pz (I) MTS 7,310-3 0,032 (4) 0,16 (22)
Pz (I) PSHCH 6,910-3 0,18 (26) 0,71 (103)
YbPz (I) PEG 9,710-4 0,016 (16) 0,074 (76)
YbPz (I) AlgNa 2,710-3 0,02 (8) 0,09 (31)
YbPz (I) MTS 4,910-3 0,036 (7) 0,17 (35)
YbPz (I) PSHCH 2,810-3 0,24 (86) 0,58 (207)
Pz (I) 2,210-3 0,32 (145) 0,84 (382)

*Относительно rodamina In water



Drawing 15. The Quantum yield of fluorescence for tetraariltetratsianoporfirazinov as a part of various polymeric nanochastits in the distilled water and in the presence of whey fibers

Blood


On the basis of the gained data about a strong dependence of a quantum yield of fluorescence of explored linkings from parametres of medium we had been made the guess about possible accessories tetraaril - tetratsianoporfirazinov to a class of fluorescent molecular curls.

Feature of these linkings is gyration (or intertwisting) one part of a molecule concerning another at transition in raised and, back, in the basic state (item 1.4 chapter 1). The intramolecular motion induced by light makes the strong impact on probability of a nonradiative and emissive relaxation of an excited state of a molecule. Such linkings show a strong dependence

Photophysical properties from viscosity of medium [115, 243].

By us it has been shown, that dependence of a quantum yield

To bloom explored tetraariltetratsianoporfirazinov f from viscosity ts submits to equation Fyorstera-Hoffmana erected for the molecular curls [108]:

lg (f) = g + alg (u),

Where g and and — constants.

Values of a tangent of a slope angle and the straight lines characterising a degree «vjazkostnoj sensitivity» a quantum yield of fluorescence,

Have made 0,5 and 0,37 for Pz (I) and Pz (II) accordingly (drawing 166). It is known, that for the molecular curls and it is spotted, on different radiants, in a gamut 0,5-0,75 [118, 137] or 0,33-0,67 [166, 261].

Similarly for fluorescent molecular curls dependence between viscosity and a lifetime of an excited state t [108] is represented:

lg (0 = lg (z / kr) + alg (u),

Where kr — a constant of velocity of the emissive transition, g — a constant.

Drawing 16. Dependence of a quantum yield of fluorescence Pz (I) and

Pz (II) from viscosity of medium.

a — spectrums of fluorescence Pz (I) in ethanol-glyceric intermixtures (1) — 0 %, (2) — 30 %, (3) — 70 %, (4)-97 glycerine %; — dependence of a quantum yield of fluorescence for Pz (I) and Pz (II) from viscosity of solvent, а1 — Pz (I); а2 — Pz (II)


We had been measured lifetimes of excited state Pz (I) in ethanol-glyceric intermixtures with various viscosity and is shown, that quantity of a tangent of a slope angle of a straight line and has made 0,49 (drawing 17).


And — curve signal attenuations of fluorescence Pz (I) in ethanol-glyceric intermixtures with

Known viscosity,

— dependence of a lifetime of excited state Pz (I) from viscosity

Solution

Thus, the erected dependences of the photophysical

Fluorescence parametres tetraariltetratsianoporfirazinov from viscosity of medium and good conformity of the calculated values and to data of other researchers confirm accessories explored tetraariltetratsianoporfirazinov to a class of fluorescent molecular curls. The mechanism of the photoinduced guessed by us

Intramolecular motion Pz (I) can be related to rotational displacement aromatic or CN-groups concerning a macrocycle plane (drawing 18).

Drawing 18. The prospective mechanism of a photoinduced intramolecular motion in Pz (I)


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A source: Shiljagina Natalia Jurevna. EXAMINATION TETRAARILTETRATSIANOPORFIRAZINOV As POTENTIAL PHOTOSENSITIZERS FOR PHOTODYNAMIC THERAPY And FLUORESCENT DIAGNOSTICS. 2014

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