Photolabile systems

B. The Different Types of Photolabile Systems. In the following, we will discuss the different systems which upon absorbing laser radiation at a specific frequency (the photolysis... 

Some of the processes that a photolabile system can undergo after the absorption of a light pulse are ... 

Multichannel detectors offer new possibilities for investigation of photolabile systems since less laser power is required to obtain a high S/N. 

Another interesting variation on the linkage holding together two benzocrowns was reported by Shinkai and coworkers In their case, the benzo groups on the crowns were also part of a photolabile azobenzene system. The azo-linked bis-crown was prepared as follows (see Eq. 3.34). 4 -Nitrobenzo-l 5-crown-5 was reductively dimerized... 

Despite the considerable amount of information that has been garnered from more traditional methods of study it is clearly desirable to be able to generate, spectroscopically characterize and follow the reaction kinetics of coordinatively unsaturated species in real time. Since desired timescales for reaction will typically be in the microsecond to sub-microsecond range, a system with a rapid time response will be required. Transient absorption systems employing a visible or UV probe which meet this criterion have been developed and have provided valuable information for metal carbonyl systems [14,15,27]. However, since metal carbonyls are extremely photolabile and their UV-visible absorption spectra are not very structure sensitive, the preferred choice for a spectroscopic probe is time resolved infrared spectroscopy. Unfortunately, infrared detectors are enormously less sensitive and significantly slower... 

This paper describes the successful synthesis and examination of polyfr-(amino /9-thiosulfate) ether] (PATE), a water soluble photolabile polymer. Evidence has been presented that the PATE polymer is zwitterionic and forms weak associations in aqueous solutions. Heat treatment of PATE films result in extensive crosslinking, presumably through a disulfide bond. This work presents strong evidence that PATE is activated by deep UV radiation, and that a disulfide crosslink is formed. Sensitization experiments demonstrate that the crosslinking reaction can be induced by a triplet sensitizer. Finally, preliminary results point out the potential for application of PATE films as active photoimaging systems. 

Various materials have been examined for use as deep UV resists poly(methyl methacrylate) (PMMA) (1), poly(methyl isopropenyl ketone) (PMIPK) fS.7L and the novolak-Meldrum s acid solution inhibition system (S). Each however has a problem related to sensitivity and/or resolution. While PMMA is insensitive to light of X > 230 nm because of its weak absorption, its high resolution properties make it an attractive starting point for the design of a resist that will perform well in the 230-280 region. The photochemical properties of PMMA could be modified by the incorporation of a small percentage of photolabile groups so as to have both the desired sensitivity and base polymer properties. 

Majjigapu, J.R.R., Kurchan, A.N., Kottani, R., Gustafson, T.P. and Kutateladze, A.G. (2005) Release and report a new photolabile caging system with a two-photon fluorescence reporting function. Journal of the American Chemical Society, 127, 12458-12459. 

C. The Basic Elements of the Experimental Setup. The basic elements of TRRR experiments are a photolysis source a laser probe source (whose scattered radiation by the photolabile sample contains the vibrational spectra of the photodecomposed sample and its transients) a dispersing instrument (e.g., a spectrometer) and an optical multichannel analyzer (OMA) system used as a detector. 

In addition to selecting the appropriate solvent system, pH, buffer species and then concentration, ionic strength, dielectric constant, type of container, and storage temperature, the following techniques may be used to enhance the photostability of photolabile drugs. 

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