Study of Interfacial Charge Transfer from an Electron Rich Organic Molecule to CdTe Quantum Dot by using Stern-Volmer and Stochastic Kinetic Models.

Photoinduced electron transfer (PET) from N-methylaniline (NMA) to a photoexcited CdTe quantum dot (QD*) is studied in toluene. The PET mechanism at low to moderate quencher (NMA) concentrations (<0.08 M) remains mostly collisional with some contributions from QD-NMA complex formation. However, at high quencher concentrations (>0.10 M), QDs form larger numbers of static complexes with NMA molecules leading to a steep positive deviation in the steady-state Stern-Volmer curves. An isothermal titration calorimetry (ITC) study confirms the formation of QD-NMA complexes (K∼150 M-1 ) at high quencher concentrations. Fitting our experimental data using a stochastic kinetic model indicates that the number of NMA molecules attached per QD at highest NMA concentration (∼0.16 M) used in this study decreases from ∼0.76 to ∼0.47 with reducing the QD size from ∼5.2 nm to ∼3.2 nm. However, the PET rate increases with decreasing QD size, which is commensurate with the observation that the chemical driving force (ΔG) increases with decreasing the QD particle size. We have analyzed the PET kinetics mainly by using Stern-Volmer fittings. However, in some cases Tachiya's stochastic kinetic model is used for stoichiometric analysis, which seems to be useful only at high quencher concentrations. The measured PET rate coefficients in all the cases are found to be at least an order of magnitude lower when compared to the diffusion-controlled rate of the reaction medium.

Role of Emissive and Non-Emissive Complex Formations in Photoinduced Electron Transfer Reaction of CdTe Quantum Dots.

Bimolecular photoinduced electron transfer (PET) from excited state CdTe quantum dot (QD*) to an electron deficient molecule 2,4-dinitrotoluene (DNT) is studied in toluene. We observed two types of QD-DNT complex formations; (i) non-emissive complex, in which DNT is embedded deep inside the surface polymer layer of QD and (ii) emissive complex, in which DNT molecules are attached to QDs but approach to the QD core is shielded by polymer layer. Because of its non-emissive nature, the lifetime of QD is not affected by dark complex formation, though the steady-state emission is greatly quenched. However, emissive complex formation causes both, lifetime and steady-state emission quenching. In our fitting model, consideration of Poisson distribution of the attached quencher (DNT) molecules at QD surface enables a comprehensive fitting to our time resolved data. QD-DNT complex formation was confirmed by an isothermal titration calorimetry (ITC) study. Fitting to the time resolved data using a stochastic kinetic model shows moderate increase (0.05 ns-1 to 0.072 ns-1 ) of intrinsic quenching rate with increasing the QD particle size (from ≈3.2 nm to ≈5.2 nm). Our fitting also reveals that the number of DNT molecules attached to a single QD increases from ≈0.1-0.2 to ≈1.2-1.7, as the DNT concentration is increased from ≈1 mm to 17.5 mm. Complex formation at higher quencher concentration assures that the observed PET kinetics is a thermodynamically controlled process where solvent diffusion has no role on it.

Reactive intramammary lymph node mimicking recurrence on MRI study in a patient with prior breast conservation therapy.

Breast conservative therapy (BCT) is a well accepted form of treatment for patients with early stage breast cancer. The incidence of ipsilateral breast tumor recurrence is higher in patients undergoing BCT than in those patients undergoing Modified Radical Mastectomy (MRM) without any adverse effect on survival. Patients treated with BCT are put on active surveillance using clinical breast examination and mammography. The radiologist reading the follow-up mammograms is on high alert and any neo-density is viewed with suspicion. MRI may be used as a problem solving tool. At such a time, an innocuous intra-mammary node can mimic malignancy on MRI. We want to showcase one such typical example with histological proof and highlight that type III curve may be seen in an intramammary node. Our case also reinforces the utility of second look ultrasound which is a faster, cheaper and easier method for localization and biopsy of abnormalities seen on MRI.