Non-invasive in situ monitoring of catalyzed chemical reactions can show and probe the stability of the catalyst and ensure a high yield of the desired chemical processes. Infrared in situ measurement techniques in attenuated total reflection (ATR) and transmission mode were used to assess the feasibility of these methods and ultimately compare their ability to monitor and detect active or degrading catalyst species. Four different process configurations were used, namely (i) a stirred tank reactor equipped with ATR-IR; (ii) a continuously operated miniplant with ATR-IR; (iii) a continuously operated miniplant with transmission-IR; (iv) a stirred tank reactor equipped with transmission-IR. The established hydroformylation of a long-chain olefin catalyzed by a rhodium-phosphite catalyst was taken as a representative reaction. The potential for process monitoring in molecular catalysis was evaluated. Advanced chemometric analyses by Band Target Entropy Minimization (BTEM) were performed following spectral monitoring to obtain pure component spectra estimates as well as relative time-dependent concentration profiles. In general, this study showed that infrared measurements in transmission mode are able to detect active catalytic species and can follow deactivation phenomena in batch reactions and continuously operated miniplants. Apart from the substrates and products, a number of catalytic intermediates appear to be in equilibrium exchange at reaction conditions and hence the deconvolution of multispecies spectra exhibits superimpositions of these species. Quantum chemical calculations support the structural identification of measured vibrational spectra. This comparative study of ATR versus transmission and batch experiment versus continuously operated miniplant shows that transmission IR is capable of getting in-depth spectroscopic data that can be deconvoluted by BTEM. A distinct dosing strategy is important to get meaningful data on the molecular catalyst under process conditions. This study gives a unique perspective on in situ spectroscopic infrared investigations in molecular catalysis and future process control.

In situ spectroscopic studies of metal-mediated syntheses of new and previously unstudied systems are being increasingly used to better understand speciation and mechanistic aspects. These types of experiments give rise to an interesting question: namely, can one deduce from in situ data alone, and with no a priori chemical knowledge (i.e. chemical assignments), which pure component spectral estimates correspond to intermediates? In the present contribution, a statistical 2D correlation analysis is introduced to solve this problem for unicyclic catalytic systems. Such a methodological development achieves two goals: (1) it allows the experimentalist to concentrate on the most meaningful information at the outset of a new exploratory study (focus on the species directly associated with the catalysis), and (2) it helps to free the experimentalist from chemical bias and prejudice, i.e. believing that a specific organometallic species has to be an intermediate due to one or more chemical arguments, when in fact it may be just a side product or spectator species in the metal-mediated synthesis. The 2D correlation analysis is first tested with a numerically simulated data set and then with a real in situ FTIR data set from an unmodified rhodium-catalyzed hydroformylation. The resulting statistical 2D correlation analysis provides a clear and correct answer.

Objectives: To assessement outcome of breast reconstruction with the ispilateral pedicled TRAM flap in breast cancer patient having the low abdominal scars. Methods : The pedicled TRAM flap breast reconstruction were performed in 48 patients after nipple sparing mastectomy as well as modified radical mastectomy from 2017 - 2019 at Hue Central Hospital. Results: There is 16/48 (33.3%) patient who have the low abdominal scars and 100% in which were operated by the ispilateral pedicled TRAM flap in breast reconstruction, part I, III of TRAM was using for 15/16 patients. Compare to the contralateral pedicled TRAM flap, the ispilateral pedicled TRAM flap have a shorter in surgical time (under 180 minutes) and time staying hospital (under 10 days). Most of them having the aesthetic results and satisfied with immediate or delay breast reconstruction. The rate of complication was 12.5%, no finding the severe complications of reconstruction in the total flap necrosis and hernia or bulge in this study. Conclusion: The ispilateral pedicled TRAM flap was a safe as well as contralateral pedicled TRAM flap and reliable procedure for breast cancer patient having the low abdominal scars. Key words: TRAM flap, breast cancer, breast reconstruction.