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1.
Angew Chem Int Ed Engl ; 56(36): 10952-10955, 2017 08 28.
Artigo em Inglês | MEDLINE | ID: mdl-28670830

RESUMO

Halogenated nucleobases are used as radiosensitizers in cancer radiation therapy, enhancing the reactivity of DNA to secondary low-energy electrons (LEEs). LEEs induce DNA strand breaks at specific energies (resonances) by dissociative electron attachment (DEA). Although halogenated nucleobases show intense DEA resonances at various electron energies in the gas phase, it is inherently difficult to investigate the influence of halogenated nucleobases on the actual DNA strand breakage over the broad range of electron energies at which DEA can take place (<12 eV). By using DNA origami nanostructures, we determined the energy dependence of the strand break cross-section for oligonucleotides modified with 8-bromoadenine (8Br A). These results were evaluated against DEA measurements with isolated 8Br A in the gas phase. Contrary to expectations, the major contribution to strand breaks is from resonances at around 7 eV while resonances at very low energy (<2 eV) have little influence on strand breaks.


Assuntos
DNA/química , Elétrons , Quebras de DNA de Cadeia Dupla
2.
J Chem Phys ; 137(4): 045101, 2012 Jul 28.
Artigo em Inglês | MEDLINE | ID: mdl-22852657

RESUMO

Low energy electrons (LEEs) are produced in copious amounts by the primary radiation used in radiation therapy. The damage caused to the DNA by these secondary electrons in the energy range 5-22 eV has been studied to understand their possible role in radiation induced damage. Electrons are irradiated on dried films of plasmid DNA (pQE30) and analysed using agarose gel electrophoresis. Single strand breaks (SSBs) induced by LEE to supercoiled plasmid DNA show resonance structures at 7, 12, and 15 eV for low doses and 6, 10, and ∼18 eV at saturation doses. The present measurements have an overall agreement with the literature that LEEs resonantly induce SSBs in DNA. Resonant peaks in the SSBs induced by LEEs at 7, 12, and 15 eV with the lowest employed dose in the current study are somewhat different from those reported earlier by two groups. The observed differences are perhaps related to the irradiation dose, conditions and the nature of DNA employed, which is further elaborated.


Assuntos
DNA Bacteriano/química , DNA Super-Helicoidal/química , Elétrons , Plasmídeos/química , Escherichia coli/química
3.
J Chem Phys ; 128(20): 204312, 2008 May 28.
Artigo em Inglês | MEDLINE | ID: mdl-18513024

RESUMO

High resolution laser induced fluorescence spectrum of jet-cooled SO(2) is recorded toward the blue side of the Clement's A-Band in the region of 314-319 nm. Time resolved fluorescence measurements have been carried out for all the prominent peaks in this region. Most of the peaks exhibited double exponential decay profiles. Some of the rovibronic bands exhibited quantum beats with strong quantum beats observed at 315.261 and 315.271 nm. This is the first observation of quantum beats in SO(2) in the absence of any external magnetic or electric fields. The decay profiles of the beating rovibronic bands were fitted using a four-level model by least-squares fitting method. The fitting shows that all the measured bands were double exponential with a similar first lifetime of approximately 3 mus and a varying second lifetime of the order of 1 micros-100 ns with a beating frequency of approximately 1 MHz. These quantum beats, in the absence of any external field, indicate rotational level mixing between the A (1)A(2) and the B (1)B(1) vibronic states which are near resonant due to the high density of states of these two states.

4.
Rev Sci Instrum ; 87(3): 034302, 2016 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-27036792

RESUMO

We have developed a multi target, Low Energy Electron (LEE), precise dose controlled irradiator for biomolecular films. Up to seven samples can be irradiated one after another at any preset electron energy and dose under UHV conditions without venting the chamber. In addition, one more sample goes through all the steps except irradiation, which can be used as control for comparison with the irradiated samples. All the samples are protected against stray electron irradiation by biasing them at -20 V during the entire period, except during irradiation. Ethernet based communication electronics hardware, LEE beam control electronics and computer interface were developed in house. The user Graphical User Interface to control the irradiation and dose measurement was developed using National Instruments Lab Windows CVI. The working and reliability of the dose controlled irradiator has been fully tested over the electron energy range of 0.5 to 500 eV by studying LEE induced single strand breaks to ΦX174 RF1 dsDNA.


Assuntos
DNA , Elétrons , Doses de Radiação , Equipamentos e Provisões para Radiação , DNA/genética , Quebras de DNA/efeitos da radiação , Desenho de Equipamento , Proteção Radiológica , Software , Interface Usuário-Computador
5.
Rev Sci Instrum ; 82(11): 113101, 2011 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-22128960

RESUMO

A new design of a linear time of flight mass spectrometer (ToFMS) is implemented that gives nearly field-free interaction region without compromising on the mass resolution. The design addresses problems that would arise in a conventional Wiley-McLaren type of ToFMS: (i) field leakages into the charged particle-molecule interaction region from various components of the mass spectrometer, including that through the high transparency mesh used to obtain evenly distributed electric fields; (ii) complete collection and transportation of the ions produced in the interaction region to the detector, which is essential for high sensitivity and cross section measurements. This ToFMS works over a wide range of masses from H(+) to a few hundred Daltons and would be the most suitable for low energy charged particle-molecule interaction studies. Performance of the ToFMS has been tested by measuring the partial ionization cross sections for electron impact on CF(4).

6.
J Chem Phys ; 120(13): 6005-9, 2004 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-15267482

RESUMO

Photoion yields from gaseous fullerenes, C(60) and C(70), for production of singly and doubly charged ions are measured by mass spectrometry combined with tunable synchrotron radiation at hnu=25-150 eV. Since the signal of triply or highly charged ions is very weak, the total photoionization yield curve can be estimated from the sum of the yields of the singly and doubly charged ions. A distinct feature appears in the resultant curve of C(60) which is absent in the calculated total photoabsorption cross section previously reported. This difference is attributed to C(60) (2+) ions chiefly produced by spectator Auger ionization of the shape resonance states followed by tunneling of the trapped electron or by cascade Auger ionization. Ratios between the yields of doubly and singly charged ions for C(60) and C(70) are larger than unity at hnu>50 eV. These ratios are quite different from those reported in the experiments using electron impact ionization.

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